CN108101077A - Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer - Google Patents
Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer Download PDFInfo
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- CN108101077A CN108101077A CN201711462129.4A CN201711462129A CN108101077A CN 108101077 A CN108101077 A CN 108101077A CN 201711462129 A CN201711462129 A CN 201711462129A CN 108101077 A CN108101077 A CN 108101077A
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- China
- Prior art keywords
- lithium
- spodumene
- mineral fertilizer
- carried
- phase analysis
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 150
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 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 title claims abstract description 111
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 88
- 239000003337 fertilizer Substances 0.000 title claims abstract description 86
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 73
- 239000011707 mineral Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000008569 process Effects 0.000 title claims abstract description 47
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000002386 leaching Methods 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000007654 immersion Methods 0.000 claims abstract description 29
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 24
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000013329 compounding Methods 0.000 claims abstract description 10
- 235000010755 mineral Nutrition 0.000 claims description 69
- 238000004458 analytical method Methods 0.000 claims description 60
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 26
- 235000012255 calcium oxide Nutrition 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 16
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 16
- 235000013619 trace mineral Nutrition 0.000 claims description 16
- 239000011573 trace mineral Substances 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 15
- 230000009466 transformation Effects 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- -1 silicon-calcium-potassium-lithium Chemical compound 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 30
- 239000011575 calcium Substances 0.000 description 27
- 229910052791 calcium Inorganic materials 0.000 description 26
- 239000000047 product Substances 0.000 description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- YCHYHTRNWQTVOU-UHFFFAOYSA-N [Mg].[Li].[K] Chemical compound [Mg].[Li].[K] YCHYHTRNWQTVOU-UHFFFAOYSA-N 0.000 description 14
- 229910052644 β-spodumene Inorganic materials 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 229910001760 lithium mineral Inorganic materials 0.000 description 10
- 229910052643 α-spodumene Inorganic materials 0.000 description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 235000019738 Limestone Nutrition 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052611 pyroxene Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000031018 biological processes and functions Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 235000012055 fruits and vegetables Nutrition 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- WLTAGFPJBPFMAA-UHFFFAOYSA-N [Li].[K].[Mg].[Ca] Chemical compound [Li].[K].[Mg].[Ca] WLTAGFPJBPFMAA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 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
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/02—Superphosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses an integrated process for extracting lithium and synthesizing mineral fertilizer by utilizing spodumene, which comprises the following steps of preparing lithium ore pulp by roasting, grinding and slurrying the spodumene; leaching the lithium ore pulp and sulfuric acid at high temperature and high pressure to obtain a leaching solution and leaching residues; neutralizing and removing impurities from the immersion liquid to obtain lithium sulfate; the mineral fertilizer is prepared by compatibility, modification and compounding of the leaching residue. By adopting the process steps of the invention, on one hand, the separation, enrichment and recovery of spodumene for extracting lithium are realized, on the other hand, the silicon-calcium-potassium-lithium multi-element mineral fertilizer can be co-produced, and a new way is opened up for the comprehensive utilization and recovery of spodumene for extracting lithium.
Description
Technical field
The present invention is a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, and in particular to utilizes spodumene
Ore phase reconstruction integrates the integral manufacturing technique for carrying lithium and synthetic mineral fertilizer, belongs to minerals extractive technique and waste disposal neck
Domain.
Background technology
Lithium possesses light-weight, and quality is soft, and specific heat is big, a series of good characteristics of negative potential height etc., battery, ceramics,
The industries extensive use such as glass, lubricant, refrigerating fluid, nuclear industry and photoelectricity is referred to as " energy metal " and " before promoting the world
Into important element " be considered as important strategic resource by many countries.2015-2017 years, from lithium, this small metal was by " industry
Monosodium glutamate " grows into " energy metal ", " global videoization new cycle " is marched toward by " Industrial Metal cycle " since, the exploitation of lithium resource
Into the period of developing by leaps and bounds.At present, spodumene ore resources exploitation gets most of the attention, and has accounted within 2016 global lithium resource supply proportion
40%.Spodumene（LiAlSi2O6)）Ore is also to prepare other lithium salts and lithium metal as a kind of important industrial chemicals
Primary raw material, generally containing Li2O 1~2%, by can reach 5~7% after beneficiation enrichment.
China is the country of spodumene concentrate reserves maximum in the world, and Xinjiang and Sichuan are the most important production bases of lithium salts
Ground, domestic at present mainly to carry lithium using sulfuric acid process, α-spodumene is carried out transformation of crystal roasting first, is transformed into it by this method
Higher β-the spodumene of activity, then lithium sulfate is generated with strong sulfuric acid response, reaction mixture goes out, by water logging after sodium carbonate conversion
Prepare lithium carbonate.It is existing lithium carbonate is prepared using sulfuric acid process to have many advantages, such as that the recovery rate of lithium in ore is high, but it is also deposited
Complex process, baking flue gas desulfurization load is big the shortcomings of.On this basis, existing patent document CN107089674A（It is a kind of
Spodumene sodium sulphate pressure leaching carries lithium technique, 2017.08.25）It discloses and a kind of is obtained using α-spodumene conversion crystal form
β-spodumene, after finely ground and sodium sulphate, additive, circulating mother liquor are made into slurry, then pressurized leaching obtains lithium carbonate product
Process, leaching mother liquor returns again in reactor dispensing and reacts, and has that technological process is short, energy consumption is low, equipment investment is small, right
The features such as environmental nonpollution.
In using the concentrated sulfuric acid-technical process of the calcium carbonate method to refine lithium carbonate, due to existing for byproduct lithium slag with
Lower situation：（1）Lithium slag is unevenly distributed China；（2）Though lithium slag has Pozzolanic feature, its activity is relatively low；（3）To lithium slag
The inadequate diversification of mode that utility value understanding deficiency and lithium slag utilize；（4）Lithium slag moisture content is big, and when utilization needs to dry, and gives
It is using making troubles, so that the utilization of lithium slag is restricted.
Oil is controlled in " comprehensive utilization of lithium slag " clearly（《Xinjiang mining and metallurgy》, 1985.07.02,28-35）In mention, lithium slag can be wide
General is applied to building material field, such as mixed as cement admixture, accelerator, the raw material for producing glaze for glazed tile, preparation
Solidifying soil etc., in addition, lithium slag also have the application prospect in agriculture field, it has been investigated that, lithium has actively and good
Biological action, the storability energy of the products such as fruit and vegetable can be improved, it is expected to improve the disease-resistant performance of some crops.Lab scale
It proves, has good effect to the storability of tomato, grape fruit using lithium slag.
Based on the above situation, in lithium sulfate extraction process, to improve lithium slag in the scale application of agriculture field, this hair
It is bright to come into being.
The content of the invention
It is an object of the invention to provide a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the one
Chemical industry skill extracts the process of lithium by improving existing spodumene, on the basis of efficiently lithium is carried, to propose by-product coproduction obtained by lithium
Mineral fertilizer is prepared, efficiently carry lithium for spodumene opens a new road with green cleaning comprehensive utilization.
The present invention is achieved through the following technical solutions：A kind of integral chemical industry that lithium and synthetic mineral fertilizer are carried using spodumene
Skill, it is characterised in that：Comprise the following steps
（1）Lithium ore pulp is made in spodumene after calcining, ore grinding, pulp；
（2）High temperature and pressure extraction is carried out to lithium ore pulp and sulfuric acid, obtains immersion liquid and phase analysis；
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities；
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
The step（1）In, spodumene carries out transformation of crystal roasting at a temperature of 1000~1200 DEG C, in spodumene
α-spodumene is converted into β-spodumene.
The step（1）In, the granularity of material after ore grinding<74 μm, account for 100%.
The step（1）In, the solid-to-liquid ratio of lithium ore pulp is controlled 2.5：1~12：1.
The step（2）In, lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, is leached
Condition meets：Sour ore deposit leaches sulfuric acid concentration 2~10% than 200~800 kg/t dry mines, 120~200 DEG C of extraction temperature, during leaching
Between 20~240min, leach pressure 0.2~1.6MPa.
The step（2）In, lithium content in immersion liquid is 1~40 g/L, the Li in phase analysis2O content is 0.1~0.5%.
The step（4）In, select quick lime and caustic potash and the phase analysis to carry out compatibility, pressure phase analysis, quick lime, caustic potash
Mass ratio is 70~80：20~30：5~15.
The step（4）In, the phase analysis after compatibility carries out modification by calcination, roasting time at a temperature of 700~1200 DEG C
For 20~240min, modified phase analysis is compounded after water quenching, ball milling again.
The step（4）In, the compounding is that trace element is added into modified phase analysis to prepare mineral fertilizer
Process.
The step（4）In, after the binding agent of 5~10wt% and the water of 10~15wt% are added into the mineral fertilizer,
Mineral fertilizer product is made after being granulated, drying again.Clay, kaolin, sepiolite powder, attapulgite, swelling can be selected in binding agent
One kind in soil, medical stone etc..
Reaction mechanism of the present invention is analyzed as follows, and more difficult be changed into sulfuric acid (salt) reaction of natural α-spodumene can
The lithium sulfate of dissolubility, it is necessary to α-spodumene be transformed into soluble β-spodumene, while the crystalline substance of spodumene by high-temperature roasting
Lattice structure also changes, and is converted into open structure by compact texture, volume expansion about 30% is conducive to subsequent sulfuric acid leaching
Go out.Sulfuric acid pressure leaching, which is reacted, is：
2LiAl(SiO3)2 +H2SO4→Li2SO4 +Al2O3·4SiO2 + H2O
The ionic radius data of element（pm）：H---1.2;Li---76;Na---102;K---138.Lithium is in the aluminium silicon of spodumene
Occupy in hydrochlorate core special position-abut side position, under temperature-pressure environment, under sulfuric acid medium system, hydrogen ion with
Displacement reaction occurs for lithium ion, with efficiently separating for sour solvable ingredient and aluminosilicate, amorphous silica, that is, amorphous state
Silica excites to form the characteristics such as high activity, high adsorption, high fineness therewith.
Compared with prior art, the present invention haing the following advantages and advantageous effect：
（1）Now some researches show that, lithium has good biological action, the storability that can improve the products such as fruit and vegetable can be with
And the disease-resistant performance of respective crop, the agriculture field that is dropped in of lithium slag also have relevant report, but it is limited to lithium mineral class and extraction work
The difference of skill, gained lithium slag certainly exist difference, since application of the existing lithium slag in agricultural production process only rests on lab scale
Stage lacks extensive widely applied basis, and based on this, the present invention proposes a kind of combination spodumene and efficiently carries lithium and by-product
The integral process that lithium slag prepares mineral fertilizer and carries out, the lithium dissolution on the one hand realized in spodumene carry lithium, on the other hand
Can also coproduction can scale application mineral fertilizer, for spodumene efficiently carry lithium and green cleaning comprehensive utilization open one it is new
Road.
（2）Present invention process, can be by major part using spodumene calcining and sulfuric acid pressure leaching mode during lithium is carried
Lithium dissolves out, and simplifies conventional sulfuric acid curing roasting roasting-water logging technique, and linking traditional handicraft is good, and through sulfuric acid pressure leaching side
The phase analysis that formula obtains is conducive to successive modified obtained mineral fertilizer, while reduces flue gas desulfurization and solidification disposal of waste load, so as to significantly
Save the cost that spodumene entirely puies forward lithium technique.
（3）The present invention using lithium calcining sulfuric acid system pressure leaching mode, in particular to spodumene in sulfuric acid medium system,
Under high temperature and high pressure environment, hardly possible leaching spodumene is easy to released ion, after sulfuric acid and ore pulp are added in autoclave together, pressurization,
It is sulfuric acid system pressure leaching mode that control sulfuric acid, which reaches certain pressure,, can when it is 0.2~1.6MPa to meet sulfuric acid pressure
The advantages of taking into account the most of lithium of recycling and excitation phase analysis indefiniteness silica, it is one to simplify sulfuric acid curing roasting-water logging technique
Segment process reduces the load of sulfuric acid flue gas desulfurization.
（4）To utilizing lithium calcining and sodium sulphate, additive disclosed in existing patent document CN107089674A（CaO、Ca
(OH)2、NaOH、KOH、NaHCO3Or KHCO3）, for the pressurized leaching of the slurry that is made into of circulating mother liquor obtains lithium carbonate product,
The leaching process temperature is high, and the reaction time is long, and lithium dissolution efficiency is not high, and there are alkaline mediums to press leaching spodumene general character problem ---
Pressure leaching temperature is high, and industrial equipment is immature, the nodes such as filtration difficulty, silicate mineral such as amorphous silica and crystallization dioxy
Certain solubility in citric acid activation occurs in high pressure alkaline medium for SiClx, and launching efficiency is relatively low.The leaching process is difficult to reach the present invention
" continuous industry pressure leaching can take into account the advantages of most of lithium of recycling and excitation phase analysis indefiniteness silica ".Its principle is
Spodumene is leached as under alkaline medium, high temperature and pressure strengthens alkali metal ion substitution displacement lithium ion under environment, because alkali metal from
Sub- radius is much larger than hydrogen ion radius, and lithium ion displacement reaction rate is compared to relatively low, addition sodium sulphate and additive in the patent
Effect be to form high sodium ion concentration and alkaline media system respectively.With the sulfuric acid reaction system pH-Electric Potential condition in the present invention
It is inconsistent, under acid condition, when adding in sodium potassium alkali metal ions pressure leaching, due to alkali metal common-ion effect, lithium can be inhibited
Dissolution efficiency.
（5）Present invention process can not only realize efficient molten lithium using spodumene calcining and sulfuric acid pressure leaching mode, obtain
To the immersion liquid that lithium content is 1~40 g/L, moreover it is possible to obtain Li2O content is 0.1~0.5% phase analysis, and now there are some researches prove lithium tools
There is positive and good biological action, the storability energy of the products such as fruit and vegetable can be improved, it is expected to improve some crops
Disease-resistant performance.
（6）The present invention is using the phase analysis that spodumene calcining and sulfuric acid pressure leaching mode are prepared and quick lime, causticity
Compatibility is homogenized potassium in proportion, modified through high-temperature roasting so that the SiO in the mineral such as si-al-li stone, potassium feldspar of phase analysis2、Li、
The Hubeiwans such as K are partly activated, and are obtained required mineral fertilizer beneficial to follow-up compounding, are conducive to improve the comprehensive of lithium ore
Close utilization ratio.
（7）In present invention process, to spodumene into being grouped into or the place of production is without selective requirement, spodumene or lithium brightness
Stone leaching lithium slag Li2It is good to enter to soak spodumene requirement transformation of crystal for O content 0.2~9.2%.
（8）The present invention prepares mineral fertilizer using lithium slag（Siliceous fertilizer）During, especially using quick lime and causticity
During potassium carries out compatibility, according to the recipe requirements of siliceous fertilizer, can be used a kind of carry out compatibility in quick lime and caustic potash or
Person can also use other equivalent substances to replace, such as：Quick lime or caustic potash, lime stone, plant ash, calcium superphosphate, sodium carbonate,
One kind or its mixture of the alkali and alkaline earth metal ions alkaloid compound such as potassium carbonate, magnesia.
Description of the drawings
Fig. 1 is the flow diagram of integral process of the present invention.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Lithium ore pulp is made in spodumene after calcining, ore grinding, pulp；
（2）High temperature and pressure extraction is carried out to lithium ore pulp and sulfuric acid, obtains immersion liquid and phase analysis；
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities；
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
Embodiment 2：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1000 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 70 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 2.5：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 0.2Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 2% than 200kg/t dry mine, 120 DEG C of extraction temperature,
Extraction time 240min obtains the immersion liquid and Li that lithium content is 1g/L2O content is 0.1% phase analysis.
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities.
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
Embodiment 3：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1200 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 72 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 12：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 1.6Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 10%, extraction temperature 200 than 800 kg/t dry mines
DEG C, extraction time 20min obtains lithium content as 3g/L immersion liquid and Li2O content is 0.3% phase analysis.Lithium leaching rate 95.2%.
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities.
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
Embodiment 4：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1150 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 65 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 4：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 1.4Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 8%, extraction temperature 150 than 500 kg/t dry mines
DEG C, extraction time 180min obtains the immersion liquid that lithium content is 17 g/L and the phase analysis that Li2O contents are 0.2%.Lithium leaching rate
96.5%。
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities.
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
Embodiment 5：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1200 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 73 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 8：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 1.5Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 6%, extraction temperature 200 than 450 kg/t dry mines
DEG C, extraction time 220min obtains the immersion liquid and Li that lithium content is 8g/L2O content be 0.5% phase analysis, lithium leaching rate 96.1%.
（3）Immersion liquid is neutralized through lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove the impurity such as Fe, Ca, Mg, Al, is obtained
The lithium sulfate solution of purification, lithium sulfate solution prepare the lithium salts such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation.
（4）Quick lime and caustic potash is selected to carry out compatibility with phase analysis, pressure phase analysis, quick lime, the mass ratio of caustic potash are 70：
20：5, the phase analysis after compatibility carries out modification by calcination at a temperature of 1200 DEG C, and roasting time 240min, modified phase analysis is again
After water quenching obtains cooling slag, ball milling in ball mill is sent into, the trace element needed for addition into the powder after ball milling（Ratio can root
It is made choice according to the requirement of silico-calcium potassium magnesium lithium multi-element mineral fertilizer compound mineral fertilizer gauge lattice）It is compounded to obtain mineral fertilizer,
After the binding agent of 5wt% and the water of 10wt% are added into the mineral fertilizer, then mineral fertilizer product is made after being granulated, drying.
Embodiment 6：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1050 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 68 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 5：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 1.2Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 7%, extraction temperature 135 than 600 kg/t dry mines
DEG C, extraction time 165min obtains the immersion liquid and Li that lithium content is 40 g/L2O content be 0.36% phase analysis, lithium leaching rate
96.7%。
（3）Immersion liquid is neutralized through lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove the impurity such as Fe, Ca, Mg, Al, is obtained
The lithium sulfate solution of purification, lithium sulfate solution prepare the lithium salts such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation.
（4）Quick lime and caustic potash is selected to carry out compatibility with phase analysis, pressure phase analysis, quick lime, the mass ratio of caustic potash are 80：
30：15, the phase analysis after compatibility carries out modification by calcination at a temperature of 900 DEG C, and roasting time 20min, modified phase analysis is again
After water quenching obtains cooling slag, ball milling in ball mill is sent into, the trace element needed for addition into the powder after ball milling（Ratio can root
It is made choice according to the requirement of silico-calcium potassium magnesium lithium multi-element mineral fertilizer compound mineral fertilizer gauge lattice）It is compounded to obtain mineral fertilizer,
After the binding agent of 10wt% and the water of 15wt% are added into the mineral fertilizer, then mineral fertilizer product is made after being granulated, drying.
Embodiment 7：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）Using spodumene as raw material, spodumene is subjected to transformation of crystal roasting at a temperature of 1200 DEG C, α-lithium in spodumene
Pyroxene is converted into β-spodumene, and ore grinding is carried out to the material after calcining, after its granularity is made to be 70 μm, adds water thereto and mixes equal
It is even, solid-to-liquid ratio is obtained as 10：1 lithium ore pulp.
（2）Lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, sulphur in control pressure container
The pressure of acid is 1.4Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 4%, extraction temperature 150 than 700 kg/t dry mines
DEG C, extraction time 200min obtains the immersion liquid and Li that lithium content is 6g/L2O content be 0.4% phase analysis, lithium leaching rate 95.8%.
（3）Immersion liquid is neutralized through lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove the impurity such as Fe, Ca, Mg, Al, is obtained
The lithium sulfate solution of purification, lithium sulfate solution prepare the lithium salts such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation.
（4）Quick lime and caustic potash is selected to carry out compatibility with phase analysis, pressure phase analysis, quick lime, the mass ratio of caustic potash are 80：
25：10, the phase analysis after compatibility carries out modification by calcination, roasting time 200min, modified phase analysis at a temperature of 1000 DEG C
Again after water quenching obtains cooling slag, ball milling in ball mill is sent into, the trace element needed for addition into the powder after ball milling（Ratio can
It is made choice according to the requirement of silico-calcium potassium magnesium lithium multi-element mineral fertilizer compound mineral fertilizer gauge lattice）It is compounded to obtain mineral fertilizer
After the binding agent of 6wt% and the water of 12wt% are added into the mineral fertilizer, then mineral fertilizer product is made in material after being granulated, drying.
Embodiment 8：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）With 1000g spodumenes（Li2O 6.2%, SiO2 69%, Fe2O3 0.5%）For raw material, by temperature of the spodumene at 1200 DEG C
It spends and carries out transformation of crystal roasting down, α-spodumene in spodumene is converted into β-spodumene, adds 500ml water to the material after calcining
It is roughly ground into ore mill, ore grinding 10min, after its granularity is made to be 65 μm, adds water thereto and be uniformly mixed, obtain solid-to-liquid ratio as 6：
1 lithium ore pulp:, pulp density 14%.
（2）Lithium ore pulp is added in the autoclave of 2L, extracted by sulfuric acid pressure leaching mode, in control pressure container
The pressure of sulfuric acid is 1.5Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 8%, extraction temperature 180 than 600 kg/t dry mines
DEG C, after leaching, separation of solid and liquid is carried out using vacuum filtration machine by extraction time 100min, speed of agitator 1000r/min,
Obtain the immersion liquid and Li that lithium content is 12g/L2O content be 0.28% phase analysis, lithium leaching rate 96.8%.
（3）It is miscellaneous that above-mentioned immersion liquid is neutralized by lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove Fe, Ca, Mg, Al etc.
Matter, the lithium sulfate solution being purified, lithium sulfate solution prepare the lithiums such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation
Salt.
（4）Compatibility is carried out with 239g quick limes and 44g caustic potash and above-mentioned phase analysis, temperature of the phase analysis after compatibility at 800 DEG C
The lower progress modification by calcination of degree, roasting time 180min, modified phase analysis after water quenching obtains cooling slag, are sent into ball mill again
Middle ball milling, the trace element needed for addition into the powder after ball milling, such as according to silico-calcium potassium magnesium lithium multi-element mineral fertilizer complex mineral
The related trace element of requirement addition of fertilizer specification is compounded to obtain silico-calcium potassium magnesium lithium minerals fertilizer, is added into the mineral fertilizer
It after the binding agent of 5wt% and the water of 10wt%, is granulated in fertilizer granulator, 1260g silico-calcium potassium magnesium lithium minerals fertilizer is obtained after dry
Product.Analyze the trace element such as effective potassium 4.7%, effective silicon 22%, effective calcium 26%, effective magnesium 1.2%, S, Zn, Fe, Ti 2.6%.
Comparative example 1：
This comparative example is disclosed a kind of lithium slag obtained after lithium that carried using conventional sulfuric acid curing roasting-water logging technique and is used to prepare silicon
The process of calcium potassium magnesium lithium minerals fertilizer, different, the specific steps that differ only in the molten lithium process used of the comparative example and embodiment 8
It is summarized as follows：
（1）With 1000g spodumenes（Li2O 6.2%, SiO2 69%, Fe2O3 0.5%）For raw material, by temperature of the spodumene at 1200 DEG C
It spends and carries out transformation of crystal roasting down, α-spodumene in spodumene is converted into β-spodumene, adds 500ml water to the material after calcining
It is roughly ground into ore mill, ore grinding 10min, after its granularity is made to be 65 μm, adds water thereto and be uniformly mixed, obtain solid-to-liquid ratio as 6：
1 lithium ore pulp:, pulp density 14%.
（2）Lithium ore pulp, the concentrated sulfuric acid are added in the reaction kettle of 2L, reaction condition meets：Sour ore deposit is than 600 kg/t dry mines, sulphur
Acid concentration 5%, 160 DEG C, reaction time 70min of temperature after reaction, go out using water logging, are prepared after sodium carbonate conversion
Lithium content is the Lithium carbonate solution and Li of 10g/L2O content be 0.2% lithium slag, lithium leaching rate 93.8%.
（3）Lithium slag step as described in embodiment 8（4）It is prepared, obtains silico-calcium potassium magnesium lithium minerals fertilizer product.Analysis is effective
The trace element such as potassium 4.8%, effective silicon 21.86%, effective calcium 26%, effective magnesium 1.1%, S, Zn, Fe, Ti 2.5%.
Embodiment 9：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, the integral process step
It is as follows：
（1）With 1500g spodumenes（Li2O 6.2%, SiO2 69%, Fe2O3 0.5%）For raw material, by temperature of the spodumene at 1100 DEG C
It spends and carries out transformation of crystal roasting down, α-spodumene in spodumene is converted into β-spodumene, adds 800ml water to the material after calcining
It is roughly ground into ore mill, ore grinding 15min, after its granularity is made to be 70 μm, adds water thereto and be uniformly mixed, obtaining solid-to-liquid ratio is
10：1 lithium ore pulp, pulp density 21%.
（2）Lithium ore pulp is added in the autoclave of 3L, extracted by sulfuric acid pressure leaching mode, in control pressure container
The pressure of sulfuric acid is 1.3Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 6%, extraction temperature 180 than 400 kg/t dry mines
DEG C, after leaching, separation of solid and liquid is carried out using vacuum filtration machine by extraction time 200min, speed of agitator 1000r/min,
Obtain the immersion liquid and Li that lithium content is 8 g/L2O content be 0.3% phase analysis, lithium leaching rate 95.7%.
（3）It is miscellaneous that above-mentioned immersion liquid is neutralized by lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove Fe, Ca, Mg, Al etc.
Matter, the lithium sulfate solution being purified, lithium sulfate solution prepare the lithiums such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation
Salt.
（4）Compatibility is carried out with 188g caustic potash and above-mentioned phase analysis, and the phase analysis after compatibility is roasted at a temperature of 1000 DEG C
It burns and is modified, roasting time 150min, modified phase analysis after water quenching obtains cooling slag, is sent into ball milling in ball mill again, to
Trace element needed for 375g quick limes and addition are compounded in powder after ball milling, is such as answered according to silico-calcium potassium magnesium lithium multi-element mineral fertilizer
The related trace element of requirement addition for closing mineral fertilizer specification is compounded to obtain silico-calcium potassium magnesium lithium minerals fertilizer, to the mineral fertilizer
After the binding agent of middle addition 8wt% and the water of 14wt%, it is granulated in fertilizer granulator, 1890g silico-calcium potassium magnesium lithiums is obtained after dry
Mineral fertilizer product analyzes the trace elements such as effective potassium 5%, effective silicon 20%, effective calcium 28%, effective magnesium 1.5%, S, Zn, Fe, Ti
2.2%。
Comparative example 2：
This comparative example is disclosed a kind of lithium slag obtained after lithium that carried using sodium sulphate pressure leaching and is used to prepare silico-calcium potassium magnesium lithium ore deposit
The process of object fertilizer, what the differing only in of the comparative example and embodiment 9 used carry, and lithium process is different, and specific steps are summarized as follows：
（1）With 1500g spodumenes（Li2O 6.2%, SiO2 69%, Fe2O3 0.5%）For raw material, by temperature of the spodumene at 1100 DEG C
It spends and carries out transformation of crystal roasting down, α-spodumene in spodumene is converted into β-spodumene, adds 800ml water to the material after calcining
It is roughly ground into ore mill, ore grinding 15min, after its granularity is made to be 70 μm, adds water thereto and be uniformly mixed, obtaining solid-to-liquid ratio is
10：1 lithium ore pulp, pulp density 21%.
（2）Lithium ore pulp, sodium sulphate, additive are added in the autoclave of 3L and extracted, extracting condition meets：180 DEG C,
Pressure control when the reaction time is 5 small, obtains immersion liquid and lithium slag in 2.5MPa.
（3）Lithium slag step as described in embodiment 9（4）It is prepared, obtains silico-calcium potassium magnesium lithium minerals fertilizer product.Analysis is effective
2.9 % of the trace element such as potassium 6.2%, effective silicon 24%, effective calcium 27.3%, effective 1.05 % of magnesium, S, Zn, Fe, Ti.
Embodiment 10：
The present embodiment proposes a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, as shown in Figure 1, the one
It is as follows to change processing step：
（1）With 1800g spodumenes（Li2O 6.2%, SiO2 69%, Fe2O3 0.5%）For raw material, by temperature of the spodumene at 1000 DEG C
It spends and carries out transformation of crystal roasting down, α-spodumene in spodumene is converted into β-spodumene, adds 1000ml to the material after calcining
Water enters ore mill corase grinding, and ore grinding 20min after its granularity is made to be 68 μm, adds water and be uniformly mixed, obtaining solid-to-liquid ratio is thereto
7：1 lithium ore pulp, pulp density 16%.
（2）Lithium ore pulp is added in the autoclave of 4L, extracted by sulfuric acid pressure leaching mode, in control pressure container
The pressure of sulfuric acid is 1.0Mpa, and leaching condition meets：Sour ore deposit leaches sulfuric acid concentration 6%, extraction temperature 160 than 650 kg/t dry mines
DEG C, after leaching, separation of solid and liquid is carried out using vacuum filtration machine by extraction time 180min, speed of agitator 1000r/min,
Obtain the immersion liquid and Li that lithium content is 9g/L2O content be 0.45% phase analysis, lithium leaching rate 93.17%.
（3）It is miscellaneous that above-mentioned immersion liquid is neutralized by lime stone, the substeps intermediate processings such as removal of impurities that alkalize remove Fe, Ca, Mg, Al etc.
Matter, the lithium sulfate solution being purified, lithium sulfate solution prepare the lithiums such as lithium carbonate, lithium hydroxide, lithium chloride according to product orientation
Salt.
（4）Compatibility is carried out with 600g quick limes and 240g caustic potash and above-mentioned phase analysis, temperature of the phase analysis after compatibility at 900 DEG C
The lower progress modification by calcination of degree, roasting time 200min, modified phase analysis after water quenching obtains cooling slag, are sent into ball mill again
Middle ball milling, the trace element needed for addition into the powder after ball milling, such as according to silico-calcium potassium magnesium lithium multi-element mineral fertilizer complex mineral
The related trace element of requirement addition of fertilizer specification is compounded to obtain silico-calcium potassium magnesium lithium minerals fertilizer, is added into the mineral fertilizer
It after the binding agent of 8wt% and the water of 12wt%, is granulated in fertilizer granulator, 2215g silico-calcium potassium magnesium lithium minerals fertilizer is obtained after dry
Product analyzes the trace element such as effective potassium 4%, effective silicon 23%, effective calcium 26.5%, effective magnesium 1.4%, S, Zn, Fe, Ti 2.5%.
The analysis and accounting of economic benefit are carried out to the integral manufacturing technique that above-described embodiment 10 is related to, such as the following table 1 institute
Show.
1 integral manufacturing technique cost outline of table is estimated
The above is only presently preferred embodiments of the present invention, and limitation in any form is not done to the present invention, every according to this
Any simple modification that the technical spirit of invention makees above example, equivalent variations, each fall within protection scope of the present invention
Within.
Claims (10)
1. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene, it is characterised in that：Comprise the following steps
（1）Lithium ore pulp is made in spodumene after calcining, ore grinding, pulp；
（2）High temperature and pressure extraction is carried out to lithium ore pulp and sulfuric acid, obtains immersion liquid and phase analysis；
（3）Immersion liquid is neutralized, obtains lithium sulfate after removal of impurities；
（4）Mineral fertilizer is made in phase analysis after compatibility, modification, compounding.
2. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（1）In, spodumene carries out transformation of crystal roasting at a temperature of 1000~1200 DEG C.
3. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（1）In, the granularity of material after ore grinding<74μm.
4. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（1）In, the solid-to-liquid ratio of lithium ore pulp is controlled 2.5：1~12：1.
5. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（2）In, lithium ore pulp is added in pressure vessel, is extracted by sulfuric acid pressure leaching mode, leaching condition is full
Foot：Sour ore deposit leaches sulfuric acid concentration 2~10% than 200~800 kg/t dry mines, 120~200 DEG C of extraction temperature, and extraction time 20~
240min leaches 0.2~1.6MPa of pressure.
6. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（2）In, lithium content in immersion liquid is 1~40 g/L, the Li in phase analysis2O content is 0.1~0.5%.
7. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（4）In, quick lime and caustic potash is selected to carry out compatibility, pressure phase analysis, quick lime, the quality of caustic potash with phase analysis
Than for 70~80：20~30：5~15.
8. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（4）In, the phase analysis after compatibility carries out modification by calcination, roasting time 20 at a temperature of 700~1200 DEG C
~240min, modified phase analysis are compounded after water quenching, ball milling again.
9. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（4）In, the compounding is that trace element is added into modified phase analysis to prepare the process of mineral fertilizer.
10. a kind of integral process that lithium and synthetic mineral fertilizer are carried using spodumene according to claim 1, feature are existed
In：The step（4）In, after the binding agent of 5~10wt% and the water of 10~15wt% are added into the mineral fertilizer, then through making
Mineral fertilizer product is made after grain, drying.
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| CN109133775A (en) * | 2018-08-16 | 2019-01-04 | 湖北上和化学有限公司 | Lithium slag mixture gravel type cement concrete and preparation method thereof |
| CN109411742A (en) * | 2018-10-24 | 2019-03-01 | 浙江晨阳新材料有限公司 | The method for preparing lithium battery material |
| CN109534369A (en) * | 2018-12-07 | 2019-03-29 | 杭州水处理技术研究开发中心有限公司 | A kind of film is integrated to prepare lithium chloride device and method thereof |
| CN112456507A (en) * | 2020-12-22 | 2021-03-09 | 成都大川锂电科技有限公司 | Method for fluidized extraction of spodumene by using sulfide |
| CN114477241A (en) * | 2022-01-14 | 2022-05-13 | 广东省科学院资源利用与稀土开发研究所 | Method for extracting lithium from spodumene |
| CN115466854A (en) * | 2022-10-13 | 2022-12-13 | 江西闪凝科技有限公司 | Comprehensive extraction method for lithium ore |
| CN116287778A (en) * | 2023-03-24 | 2023-06-23 | 华东理工大学 | Method for strengthening phase reconstruction of diaspore ore and reaction device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109133775A (en) * | 2018-08-16 | 2019-01-04 | 湖北上和化学有限公司 | Lithium slag mixture gravel type cement concrete and preparation method thereof |
| CN109133775B (en) * | 2018-08-16 | 2021-09-14 | 湖北金泉新材料有限公司 | Lithium slag mixed gravel type cement concrete and preparation method thereof |
| CN109411742A (en) * | 2018-10-24 | 2019-03-01 | 浙江晨阳新材料有限公司 | The method for preparing lithium battery material |
| CN109534369A (en) * | 2018-12-07 | 2019-03-29 | 杭州水处理技术研究开发中心有限公司 | A kind of film is integrated to prepare lithium chloride device and method thereof |
| CN112456507A (en) * | 2020-12-22 | 2021-03-09 | 成都大川锂电科技有限公司 | Method for fluidized extraction of spodumene by using sulfide |
| CN114477241A (en) * | 2022-01-14 | 2022-05-13 | 广东省科学院资源利用与稀土开发研究所 | Method for extracting lithium from spodumene |
| CN115466854A (en) * | 2022-10-13 | 2022-12-13 | 江西闪凝科技有限公司 | Comprehensive extraction method for lithium ore |
| CN115466854B (en) * | 2022-10-13 | 2024-01-16 | 江西闪凝科技有限公司 | Comprehensive extraction method of lithium ore |
| CN116287778A (en) * | 2023-03-24 | 2023-06-23 | 华东理工大学 | Method for strengthening phase reconstruction of diaspore ore and reaction device thereof |
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