CN117551867A - Treatment method of titanium-containing blast furnace slag - Google Patents
Treatment method of titanium-containing blast furnace slag Download PDFInfo
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- CN117551867A CN117551867A CN202410033129.6A CN202410033129A CN117551867A CN 117551867 A CN117551867 A CN 117551867A CN 202410033129 A CN202410033129 A CN 202410033129A CN 117551867 A CN117551867 A CN 117551867A
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- China
- Prior art keywords
- titanium
- leaching
- blast furnace
- furnace slag
- containing blast
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000010936 titanium Substances 0.000 title claims abstract description 161
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 161
- 239000002893 slag Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000002386 leaching Methods 0.000 claims abstract description 169
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011777 magnesium Substances 0.000 claims abstract description 25
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 14
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 229910052611 pyroxene Inorganic materials 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- 239000000460 chlorine Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 235000010215 titanium dioxide Nutrition 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000000227 grinding Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- -1 calcium magnesium aluminum Chemical compound 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 3
- 229910052637 diopside Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/1245—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application provides a treatment method of titanium-containing blast furnace slag, and relates to the technical field of chemical smelting. The method for treating the titanium-containing blast furnace slag comprises the following steps: mixing and roasting titanium-containing blast furnace slag and an auxiliary agent to obtain calcine; leaching the calcine to obtain leaching liquid and titanium-containing leaching slag; and (3) introducing the gas generated by roasting into the leaching solution, regulating the pH value, and carrying out solid-liquid separation to obtain filtrate and filter residues containing aluminum and magnesium. According to the method, through roasting-leaching processes with the auxiliary agent, perovskite, pyroxene and other mineral phases in the titanium-containing blast furnace slag are decomposed, so that the acid solubility of impurity elements such as calcium, magnesium and aluminum is improved, further, selective leaching is realized in the leaching process, titanium is enriched in leached slag, a feasible comprehensive recycling process flow of the titanium-containing blast furnace slag is provided, and the environmental problem caused by mass storage of the titanium-containing blast furnace slag is relieved.
Description
Technical Field
The application relates to the technical field of chemical metallurgy, in particular to a treatment method of titanium-containing blast furnace slag.
Background
Panzhihua-Xichang region contains a large amount of vanadium titanomagnetite, and has been found to have a reserve of 96.6 hundred million tons and contains more than 10 important resources such as titanium, iron, vanadium, chromium, cobalt, nickel, gallium, scandium, etc., and TiO 2 The reserves have been found to be 8.7 hundred million tons. According to the existing vanadium titano-magnetite smelting technology, about 50% of titanium resources after ore dressing enter a blast furnace smelting process along with iron concentrate to extract iron and vanadium, and titanium forms TiO-containing substances with complex minerals such as perovskite, panti diopside and the like 2 20% -26% of blast furnace slag. Most of minerals in the titanium-containing blast furnace slag are high-temperature minerals, perovskite and pan titanium diopside are poor in acid solubility, calcium magnesium aluminum is high in content, properties are stable at normal temperature, and valuable elements such as titanium in slag are difficult to extract or enrich through conventional means such as acid leaching, so that a large amount of titanium-containing blast furnace slag generated in the pan western region is piled up, environmental pollution and damage are caused, and abundant titanium resources and other valuable components are not effectively utilized, so that resources are seriously wasted. It has been counted that about 8000 ten thousand tons of titanium-containing blast furnace slag have been produced in the region cumulatively and at a rate of 300 ten thousand tons per year. Despite the great amount of research work performed by the scientific community at home and abroad on comprehensive utilization of blast furnace slag in recent decades, a plurality of problems still exist although some achievements are achieved.
At present, the titanium extraction and utilization process of the high titanium type blast furnace slag mainly comprises the following steps: (1) selective enrichment-sorting; (2) high temperature carbonization-low temperature chlorination; (3) acidolysis to extract titanium; and (4) roasting ammonium sulfate. The method (1) has the problems of low quality of beneficiation products, difficult utilization and the like, and causes resource waste; although the method (2) has high titanium recovery rate, the process condition is harsh, the treatment capacity is limited, and the problems of serious equipment corrosion, high production cost, large industrial application difficulty and the like exist; in the method (3), during the direct acidolysis process, a large amount of aluminum and magnesium impurities enter the titanium liquid, so that the viscosity of the titanium liquid is high, the hydrolysis is difficult, and qualified titanium white products are difficult to prepare; the method (4) needs to perform fused salt roasting in the presence of a large amount of ammonium sulfate, and has high medicament cost and great regeneration and circulation difficulty. Based on the problems existing in the treatment process, a method for efficiently treating the titanium-containing blast furnace slag with low consumption is needed to be developed at present, so that the recycling of the titanium-containing blast furnace slag is realized, and the influence of the titanium-containing hazardous waste on the environment is reduced.
Disclosure of Invention
The invention aims to provide a treatment method of titanium-containing blast furnace slag, which decomposes ore phases such as perovskite, pan titanium diopside and the like in the titanium-containing blast furnace slag through procedures such as roasting and leaching, improves the dissolubility of impurity elements such as calcium, magnesium, aluminum and the like, and the obtained titanium-containing leaching slag can obtain titanium liquid in a sulfuric acid process titanium white production flow through acidolysis and water leaching, meanwhile, can recover the impurity elements in leaching liquid, fully utilizes titanium-containing blast furnace slag resources, and improves the mass stockpiling current situation of titanium-containing blast furnace slag in pan western regions.
In order to achieve the above object, the technical scheme of the present application is as follows:
the application provides a treatment method of titanium-containing blast furnace slag, which comprises the following steps:
mixing and roasting titanium-containing blast furnace slag and an auxiliary agent to obtain calcine;
leaching the calcine to obtain leaching liquid and titanium-containing leaching slag;
and (3) introducing the gas generated by roasting into the leaching solution, regulating the pH value, and carrying out solid-liquid separation to obtain filtrate and filter residues containing aluminum and magnesium.
Preferably, the treatment method of the titanium-containing blast furnace slag satisfies at least one of the following conditions:
a. the auxiliary agent comprises NH 4 Cl、CH 3 COONH 4 、(NH 4 ) 3 PO 4 、(NH 4 ) 2 HPO 4 、NH 4 H 2 PO 4 At least one of (a) and (b);
b. the mass ratio of the titanium-containing blast furnace slag to the auxiliary agent is 1 (0.1-1);
c. the roasting temperature is 200-900 ℃, the heating rate is 2-15 ℃/min, and the roasting time is 0.5-5 h.
Preferably, the method for treating titanium-containing blast furnace slag further satisfies at least one of the following conditions:
d. the leaching treatment is normal pressure leaching;
e. the leaching treatment comprises: mixing water or acid liquor with the calcine according to a liquid-solid ratio of (2-20) mL: mixing 1g, leaching for 0.5-6 h at 20-100 ℃ and carrying out solid-liquid separation;
f. in the leaching treatment process, the acid concentration of a leaching system is not more than 150g/L;
g. TiO in the titanium-containing leaching slag 2 The content is more than 30wt%.
Further preferably, the acid in the acid solution comprises HCl, CH 3 COOH、H 3 PO 4 、H 2 SO 4 At least one of them.
Preferably, the method for treating titanium-containing blast furnace slag further comprises:
mixing the titanium-containing leaching residues with sulfuric acid, and reacting to obtain acidolysis residues;
and leaching the acidolysis slag with water, and carrying out solid-liquid separation to obtain titanium liquid and silicon-rich slag.
Further preferably, the treatment method of the titanium-containing blast furnace slag satisfies at least one of the following conditions:
h. the mass ratio of the titanium-containing leaching slag to the sulfuric acid is 1 (0.8-1.8);
i. the concentration of the sulfuric acid is not less than 80wt%;
j. the reaction time is 0.5h-10h;
k. when the acid hydrolysis slag is immersed in water, the liquid-solid ratio of water to acid hydrolysis slag is (2-4) mL, 1g, and the leaching time is 0.5-2h.
Preferably, the adjusting pH comprises:
introducing the gas into the leaching solution, regulating the pH value of the system to 3-7, and carrying out solid-liquid separation to obtain a separation liquid and aluminum-containing filter residues;
and regulating the pH value of the separation liquid to 10-12, and carrying out solid-liquid separation to obtain filtrate and magnesium-containing filter residues.
Preferably, after the filtrate is obtained, the method further comprises:
adding ammonium sulfate into the filtrate, and carrying out precipitation separation to obtain calcium-containing precipitate and a precipitate-containing liquid;
evaporating and concentrating the precipitated liquid to obtain the auxiliary agent.
Further preferably, at least one of the following conditions is satisfied:
the adding amount of the ammonium sulfate is 0.1 to 1.0 times of the mass of the titanium-containing blast furnace slag;
and m, mixing the auxiliary agent obtained after evaporation and concentration with the titanium-containing blast furnace slag, and roasting to obtain the calcine.
Preferably, the titanium-containing blast furnace slag comprises titanium, aluminum, calcium, magnesium and silicon elements.
The beneficial effects of this application:
according to the treatment method of the titanium-containing blast furnace slag, roasting is carried out by using the auxiliary agent, and then leaching is carried out, so that ore phases such as perovskite, pyroxene and the like in the titanium-containing blast furnace slag are decomposed, and then the acid solubility of impurity elements such as calcium, magnesium, aluminum and the like is improved, after the leaching process, the impurity elements can be selectively leached in the leaching liquid, so that titanium-rich leaching slag is obtained, and the titanium-rich leaching slag can be used as a raw material for preparing titanium white by a sulfuric acid method, so that the titanium-containing blast furnace slag is recycled, and the environmental pressure is relieved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a flow chart of a process for treating titanium-containing blast furnace slag according to an embodiment of the present application.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus. The conjunction "consisting of … …" excludes any unspecified element, step or component.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
At present, in the titanium extraction and utilization process of high titanium type blast furnace slag, the following four processes are mainly used: (1) Selective enrichment-sorting. The titanium-rich material is obtained by mainly carrying out high-temperature oxidation modification to enrich most of titanium in titanium-containing blast furnace slag in perovskite, ti (C, N) and other phases and selecting the perovskite and the like in a mineral separation mode; researchers propose to mix titanium-containing blast furnace slag with coke, carry out modification treatment at 1400-1600 ℃ to promote the enrichment and growth of TiC crystals, and obtain titanium-rich materials by separating TiC by magnetic separation. The process has the problems of low quality of beneficiation products, difficult utilization and the like, and causes resource waste.
(2) High temperature carbonization-low temperature chlorination: carbonizing titanium-containing blast furnace slag at a temperature of more than 1500 ℃, and selectively chlorinating carbonized products at 400-600 ℃ to obtain TiCl 4 Refining and removing impurities from the gas to obtain an intermediate product capable of manufacturing titanium sponge and titanium white; researchers have carbonized and chlorinated titanium-containing blast furnace slag, then removed vanadium by adopting fatty acid, and finally obtained TiO by rectification and oxidation 2 And recycle chlorine, its technical principle is:
TiO 2 + 3C→TiC + 2CO；
TiC + 2Cl 2 →TiCl 4 + C。
the titanium recovery rate in the process is high, but the process condition is harsh, the treatment capacity is limited, and the problems of high production cost, large industrial application difficulty and the like exist.
(3) Acidolysis titanium extraction: reacting high-concentration sulfuric acid with titanium-containing blast furnace slag to obtain acidolysis slag, and finally recovering titanium in the form of titanium white powder through water leaching, hydrolysis, calcination and other processes; mixing titanium-containing blast furnace slag with a surfactant and a complexing agent, adding 80% -95% sulfuric acid solution, reacting for 0.5-3 hours at 80-180 ℃ to obtain acidolysis products, and finally obtaining titanium dioxide through the processes of water leaching, hydrolysis, calcination and the like, wherein the technical principle is as follows:
CaTiO 3 + 2H 2 SO 4 = TiOSO 4 + CaSO 4 + 2H 2 O；
TiOSO 4 + 3H 2 O = H 4 TiO 4 ↓ + H 2 SO 4 ；
H 4 TiO 4 = TiO 2 + 2H 2 O。
CaO and Al in acidolysis slag of the process 2 O 3 Acidolysis reaction can occur on MgO and the like, so that a large amount of aluminum magnesium enters the titanium liquid, the viscosity of the titanium liquid is increased, the concentration of TiO2 is difficult to reach the subsequent hydrolysis requirement through concentration, qualified titanium white products are difficult to prepare, waste acid is difficult to utilize, and industrial production is difficult.
Based on the defects of the existing technical schemes, the application provides a treatment method of titanium-containing blast furnace slag, which comprises the following steps:
s1, mixing titanium-containing blast furnace slag with an auxiliary agent, and roasting to obtain calcine;
s2, leaching the calcine to obtain leaching liquid and titanium-containing leaching residues;
and S3, introducing the gas generated by roasting into the leaching solution, regulating the pH value, and carrying out solid-liquid separation to obtain filtrate and filter residues containing aluminum and magnesium elements.
In some preferred embodiments of the present application, the titanium-containing blast furnace slag in S1 includes titanium, aluminum, calcium, magnesium, and silicon and elements.
It is understood that the titanium-containing blast furnace slag contains a large amount of oxides such as titanium dioxide, aluminum oxide, magnesium oxide, and silicon dioxide, which constitute stable ore phases such as perovskite, pyroxene, and spinel that are difficult to treat by simple physicochemical processes.
In some preferred embodiments of the present application, the adjuvant in S1 comprises NH 4 Cl、CH 3 COONH 4 、(NH 4 ) 3 PO 4 、(NH 4 ) 2 HPO 4 、NH 4 H 2 PO 4 At least one of them.
In some preferred embodiments of the present application, the mass ratio of the titanium-containing blast furnace slag to the auxiliary agent in S1 is 1: (0.1-1), for example, may be 1:0.1, 1:0.3, 1:0.5, 1:0.7, 1:0.9, 1:1 or 1: (0.1-1).
In some preferred embodiments of the present application, the temperature of the firing in S1 is 200 ℃ to 900 ℃, e.g. can be 200 ℃, 300 ℃, 500 ℃, 700 ℃, 900 ℃ or any value between 200 ℃ to 900 ℃; the heating rate is 2 ℃/min-15 ℃/min, for example, can be 2 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min or any value between 2 ℃/min-15 ℃/min; the calcination time is 0.5h to 5h, and may be, for example, 0.5h, 1h, 2h, 3h, 4h, 5h, or any value between 0.5h and 5h.
Taking ammonium chloride as an example, at a firing temperature of 500 ℃, the reactions that may occur during the firing process are:
NH 4 Cl=NH 3 (g)+HCl(g)；
NH 4 Cl+0.5MgO=0.5MgCl 2 (g)+NH 3 (g)+0.5H 2 O(g)；
NH 4 Cl+0.17Fe 2 O 3 =0.33FeCl 3 (g)+NH 3 (g)+0.5H 2 O(g)；
NH 4 Cl+0.17Al 2 O 3 =0.33AlCl 3 (g)+NH 3 (g)+0.5H 2 O(g)；
NH 4 Cl+0.5FeO=0.5FeCl 2 (g)+NH 3 (g)+0.5H 2 O(g)；
NH 4 Cl+0.5CaO=0.5CaCl 2 (g)+NH 3 (g)+0.5H 2 O(g)。
according to the reactions, after roasting by using an ammonium chloride auxiliary agent, calcium oxide in perovskite or pyroxene of the titanium-containing blast furnace slag reacts with ammonium chloride to generate calcium chloride and water, magnesium oxide in spinel reacts with ammonium chloride to generate magnesium chloride and water, the original ore phase structure is destroyed, soluble chloride is generated, and elements such as calcium, magnesium and aluminum can be separated from titanium in subsequent leaching treatment.
In some preferred embodiments of the present application, the leaching treatment of S2 is atmospheric leaching.
In some preferred embodiments of the present application, the leaching treatment of S2 comprises: mixing water or acid liquor with the calcine according to a liquid-solid ratio of (2-20) mL:1g, for example, may be 2mL:1g, 5mL:1g, 8mL:1g, 10mL:1g, 12mL:1g, 15mL:1g, 18mL:1g, 20mL:1g or (2-20) mL, 1 g; leaching for 0.5h-6h at a temperature of 20-100 ℃, for example, leaching for 6h at a temperature of 20 ℃, leaching for 4h at a temperature of 50 ℃, leaching for 3h at a temperature of 60 ℃, leaching for 1.5h at a temperature of 80 ℃ or leaching for 0.5h at a temperature of 100 ℃; after the leaching process is finished, solid-liquid separation is carried out.
The solid-liquid separation method in the present application is not particularly limited, and may be performed by any method such as filtration, suction filtration, and press filtration.
In some preferred embodiments of the present application, the acid concentration of the leaching system does not exceed 150g/L during the leaching treatment of S2.
It will be appreciated that during leaching of the calcine with water, magnesium salts, calcium salts, aluminium salts and the like produced by the reaction can be leached in the leaching solution, while titanium dioxide exists in the form of titanium-containing leaching residues, however, during the roasting process, partial magnesium-containing oxides, calcium-containing oxides and the like may not react with the auxiliary agent to produce soluble salt substances, so that the acidity in the leaching system is adjusted to ensure that the impurity elements can be reacted and dissolved in the solution, but the acidity is not more than 150g/L, otherwise oxides such as titanium dioxide react with acid and are dissolved in the leaching solution, and the impurity elements are difficult to separate from titanium.
In some preferred embodiments of the present application, when acid is used for the leaching treatment of S2, the acid in the acid comprises HCl, CH 3 COOH、H 3 PO 4 、H 2 SO 4 At least one of them.
It will be appreciated that in order to prevent calcium ions from reacting with sulphate ions to precipitate and affecting the purity of the titaniferous leach residue, the present application uses an acid which is not readily associated with metal ions to precipitate during the leaching process.
In some preferred embodiments of the present application, the TiO in the titanium-containing leaching residue of S2 2 The content is more than 30wt%.
In some preferred embodiments of the present application, after the leaching treatment in S2 to obtain the titanium-containing leaching residue, the method further comprises: mixing the titanium-containing leaching slag with sulfuric acid, reacting to obtain acidolysis slag, leaching the acidolysis slag with water, and carrying out solid-liquid separation to obtain titanium liquid and silicon-rich slag.
The titanium-containing leaching slag is a titanium-rich material capable of performing a sulfuric acid process titanium white production process, wherein the technological conditions of acidolysis, water leaching and the like are consistent with the technological conditions of a common sulfuric acid process titanium white production process. In the titanium liquid obtained by acidolysis and water leaching, besides a small amount of magnesium sulfate and aluminum sulfate impurities, the titanium oxide is mainly contained, and titanium oxide can be used as a raw material to prepare titanium dioxide. In actual processes, titanium in titanyl sulfate is often converted to TiO 2 The content of the titanium liquid is further described.
In some preferred embodiments of the present application, the mass ratio of titanium-containing leaching residue to sulfuric acid is 1 (0.8-1.8), and may be, for example, any value between 1:0.8, 1:1.0, 1:1.2, 1:1.4, 1:1.6, 1:1.8, or 1 (0.8-1.8).
In some preferred embodiments of the present application, the concentration of sulfuric acid is not less than 85wt%. If the sulfuric acid concentration is too low, it is difficult to react to produce titanyl sulfate.
In some preferred embodiments of the present application, when the acidolysis residue is leached with water, the liquid-solid ratio of water to acidolysis residue is (2-4) mL:1g, which may be, for example, 2mL:1g, 3mL:1g, 4mL:1g, or any value between (2-4) mL:1 g; the time of the leaching reaction is 0.5h-10h, and may be, for example, 0.5h, 1h, 3h, 5h, 8h, 10h, or any value between 0.5h-10 h.
In some preferred embodiments of the present application, adjusting the pH in S3 comprises: introducing gas generated by roasting into the leaching solution, regulating the pH value of the system to 3-7, and carrying out solid-liquid separation to obtain a separation liquid and aluminum-containing filter residues; and continuously regulating the pH value of the separating liquid to 10-12, and carrying out solid-liquid separation to obtain filtrate and magnesium-containing filter residues.
It is understood that the gas generated by roasting contains ammonia gas and possibly chloride gas of iron, aluminum, magnesium and the like, so that the gas is introduced into the leaching solution, on one hand, the ammonia gas can be dissolved in water to be alkaline to adjust the pH value of the leaching solution system, and on the other hand, the aluminum magnesium substances can be recycled as much as possible, so that the air is prevented from being polluted due to the fact that the aluminum magnesium substances are discharged along with the gas.
In some preferred embodiments of the present application, after obtaining the filtrate in S3, further comprises: adding ammonium sulfate into the filtrate, and separating the precipitate to obtain calcium-containing precipitate and a precipitate-containing solution; evaporating and concentrating the precipitated liquid to obtain the auxiliary agent.
After the pH value of the leaching solution is adjusted, iron, aluminum and magnesium in the leaching solution are removed, but calcium ions are also contained in the filtrate, so that the precipitation reaction of sulfate ions and calcium ions can be utilized by adding ammonium sulfate, and then the calcium ions are removed, so that calcium-containing precipitate is obtained, and meanwhile, the introduced ammonium ions can not cause secondary pollution to the filtrate.
In some preferred embodiments of the present application, the ammonium sulfate is added in an amount of 0.1 to 1.0 times the mass of the titanium-containing blast furnace slag, and may be, for example, 0.1 times, 0.5 times, 1 times, 3 times, 5 times, 8 times, or any value between 0.1 to 1.0 times.
In some preferred embodiments of the present application, the material obtained after evaporating and concentrating the post-precipitation liquid is the same as the auxiliary agent in the treatment method S1 of titanium-containing blast furnace slag. Therefore, the substance obtained after evaporation and concentration can be used as an auxiliary agent and returned to the step S1 to be mixed with the titanium-containing blast furnace slag and roasted to obtain calcine.
According to the method, after iron, aluminum, magnesium and calcium are removed from the leaching solution, the elements are recovered, and meanwhile, the obtained precipitated solution is evaporated and concentrated, so that the auxiliary agent is regenerated, the auxiliary agent can be recycled, the reagent cost is greatly reduced, and the cost of the whole treatment process is reduced.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The contents of the main components of the titanium-containing blast furnace slag used in the following examples and comparative examples are shown in Table 1.
TABLE 1 content ratio of main component of titanium-containing blast furnace slag
Example 1
The embodiment provides a treatment method of titanium-containing blast furnace slag, a process flow chart of which is shown in fig. 1, and the specific preparation method comprises the following steps:
roasting: grinding titanium-containing blast furnace slag, and then grinding with an auxiliary agent NH 4 Cl mixing, wherein the auxiliary NH 4 The adding amount of Cl is 0.4 times of the mass of the titanium-containing blast furnace slag, and the roasting sand is obtained under the conditions that the roasting temperature is 450 ℃, the heating rate is 6 ℃/min and the roasting time is 2 hours after the adding amount of Cl and the titanium-containing blast furnace slag are uniformly mixed.
Leaching: leaching the calcine under the following conditions: the temperature is 80 ℃, the hydrochloric acid concentration is 30g/L, the time is 1h, the liquid-solid ratio is 8mL:1g, and the titaniferous leaching residue and the leaching liquid are obtained. At this time, the leaching rate of calcium was 55%, the leaching rate of aluminum was 83%, and the leaching rate of magnesium was 84%.
Acidolysis-water leaching of titanium-containing leaching residues: the acidolysis conditions are as follows: adding concentrated sulfuric acid with the concentration of 80-95 wt% into the titanium-containing leaching slag, wherein the mass ratio of the concentrated sulfuric acid to the titanium-containing leaching slag is 1.2, and acidolysis time is 6 hours, so as to obtain acidolysis slag; the water immersion conditions are as follows: the liquid-solid ratio of water to acidolysis slag is 3mL:1g, the leaching temperature is 60 ℃, the leaching time is 2h, and TiO in the titanium liquid obtained after water leaching 2 The content is 70.4g/L.
Element recovery and auxiliary agent regeneration of leaching liquid: introducing gas generated by roasting into the leaching solution, regulating the pH value of the leaching solution to 5, precipitating iron and aluminum, filtering, continuously introducing gas to regulate the pH value of the filtrate to 10, filtering magnesium precipitate, adding ammonium sulfate into the filtrate, wherein the adding amount of the ammonium sulfate is 0.6 time of the mass of the titanium-containing blast furnace slag, filtering calcium ion precipitate, obtaining a de-iron aluminum magnesium calcium rear liquid, evaporating and concentrating to obtain NH 4 Cl。
Example 2
The embodiment provides a treatment method of titanium-containing blast furnace slag, a process flow chart of which is shown in fig. 1, and the specific preparation method comprises the following steps:
roasting: grinding titanium-containing blast furnace slag, and then grinding with an auxiliary agent NH 4 Cl mixing, wherein the auxiliary NH 4 The adding amount of Cl is 0.8 times of the mass of the titanium-containing blast furnace slag, and the roasting sand is obtained under the conditions that the roasting temperature is 600 ℃, the heating rate is 8 ℃/min and the roasting time is 2 hours after the adding amount of Cl and the titanium-containing blast furnace slag are uniformly mixed.
Leaching: leaching the calcine under the following conditions: the temperature is 80 ℃, the hydrochloric acid concentration is 20g/L, the time is 1h, the liquid-solid ratio is 10mL:1g, and the titanium-containing leaching residue and the leaching liquid are obtained. At this time, the leaching rate of calcium was 63%, the leaching rate of aluminum was 87%, and the leaching rate of magnesium was 84%.
Acidolysis-water leaching of titanium-containing leaching residues: the acidolysis conditions are as follows: adding concentrated sulfuric acid with the concentration of 80-95 wt% into the titanium-containing leaching slag, wherein the mass ratio of the concentrated sulfuric acid to the titanium-containing leaching slag is 1.1, and the acidolysis time is 6 hours; the water immersion conditions are as follows: the liquid-solid ratio of water to acidolysis slag is 3mL:1g, the leaching temperature is 60 ℃, the leaching time is 2h, and at the moment, the TiO in the obtained titanium liquid is 2 The content was 73.4g/L.
The leaching solution element recovery and additive regeneration process was the same as in example 1.
Example 3
The embodiment provides a treatment method of titanium-containing blast furnace slag, a process flow chart of which is shown in fig. 1, and the specific preparation method comprises the following steps:
roasting: grinding titanium-containing blast furnace slag, and then grinding with an auxiliary agent NH 4 Cl、CH 3 COONH 4 Mixing, wherein the auxiliary agent NH 4 Cl、CH 3 COONH 4 The adding amount of the catalyst is 0.1 times and 0.1 times of the mass of the titanium-containing blast furnace slag respectively, and the calcine is obtained under the conditions that the roasting temperature is 450 ℃, the heating rate is 4 ℃/min and the roasting time is 1h after the mixture is uniformly mixed.
Leaching: leaching the calcine under the following conditions: the temperature is 90 ℃, the nitric acid concentration is 10g/L, the time is 1h, the liquid-solid ratio is 8mL:1g, and the titanium-containing leaching residue and the leaching liquid are obtained. At this time, the leaching rate of calcium was 65%, the leaching rate of aluminum was 93%, and the leaching rate of magnesium was 92%.
Acidolysis-water leaching of titanium-containing leaching residues: the acidolysis conditions are as follows: in the presence ofAdding concentrated sulfuric acid with the concentration of 80-95 wt% into the titanium leaching slag, wherein the mass ratio of the concentrated sulfuric acid to the titanium leaching slag is 1.2, and the acidolysis time is 4 hours; the water immersion conditions are as follows: the liquid-solid ratio of water to acidolysis slag is 3mL:1g, the leaching temperature is 50 ℃, the leaching time is 2h, and at the moment, the TiO in the obtained titanium liquid is 2 The content is 68.4g/L.
The element recovery and the auxiliary agent regeneration process of the leaching solution are the same as in example 1, and NH is finally obtained by evaporation and concentration 4 Cl and CH 3 COONH 4 。
Example 4
The embodiment provides a treatment method of titanium-containing blast furnace slag, a process flow chart of which is shown in fig. 1, and the specific preparation method comprises the following steps:
roasting: grinding titanium-containing blast furnace slag, and then grinding with an auxiliary agent NH 4 Cl mixing, wherein the auxiliary NH 4 The adding amount of Cl is 0.3 times of the mass of the titanium-containing blast furnace slag, and the roasting sand is obtained under the conditions that the roasting temperature is 400 ℃, the heating rate is 8 ℃/min and the roasting time is 2 hours after the adding amount of Cl and the titanium-containing blast furnace slag are uniformly mixed.
Leaching: leaching the calcine under the following conditions: adding water to leach at 80 ℃ for 1h, wherein the liquid-solid ratio is 10mL:1g, obtaining a first leaching solution and a first leaching residue, drying the first leaching residue, and leaching again under the following leaching conditions: leaching temperature is 90 ℃, sulfuric acid concentration is 150g/L, time is 1h, liquid-solid ratio is 10mL to 1g, and titaniferous leaching residue and second leaching solution are obtained. At this time, the leaching rate of calcium was 74%, the leaching rate of aluminum was 92%, and the leaching rate of magnesium was 94%.
Acidolysis-water leaching of titanium-containing leaching residues: the acidolysis conditions are as follows: adding concentrated sulfuric acid with the concentration of 80-95 wt% into the titanium-containing leaching slag, wherein the mass ratio of the concentrated sulfuric acid to the titanium-containing leaching slag is 0.8, and the acidolysis time is 5 hours; the water immersion conditions are as follows: the liquid-solid ratio of water to acidolysis slag is 3mL:1g, the leaching temperature is 50 ℃, the leaching time is 2h, and at the moment, the TiO in the obtained titanium liquid is 2 The content is 65.4g/L.
Element recovery and auxiliary agent regeneration of leaching liquid: introducing gas generated by roasting into the second leaching solution, regulating the pH of the leaching solution to 5, precipitating iron and aluminum, filtering, continuously introducing gas to regulate the pH of the filtrate to 10, filtering magnesium precipitate, and adding ammonium sulfate into the filtrateWherein the addition amount of ammonium sulfate is 0.7 times of the mass of the titanium-containing blast furnace slag, calcium precipitation is filtered to obtain a solution after iron-removing aluminum magnesium calcium, and NH is obtained after evaporation concentration 4 Cl。
Comparative example 1
In the treatment method of the titanium-containing blast furnace slag provided in the comparative example, in the roasting process, the auxiliary agent selected is (NH) 4 ) 2 SO 4 The method specifically comprises the following steps:
roasting: grinding titanium-containing blast furnace slag, and then adding an auxiliary agent (NH) 4 ) 2 SO 4 Mixing, wherein the auxiliary agent (NH) 4 ) 2 SO 4 The adding amount of the catalyst is 15 times of the mass of the titanium-containing blast furnace slag, and the calcined sand is obtained under the conditions that the roasting temperature is 450 ℃, the heating rate is 8 ℃/min and the roasting time is 2 hours after the titanium-containing blast furnace slag and the titanium-containing blast furnace slag are uniformly mixed.
Leaching: leaching the calcine under the following conditions: the temperature is 80 ℃, the acid leaching is carried out for 1h, the liquid-solid ratio is 10mL to 1g, and the leaching solution and leaching slag are obtained, and TiO in the leaching solution 2 The content is 14g/L.
Comparative example 2
In the treatment method of the titanium-containing blast furnace slag provided in the comparative example, the titanium-containing blast furnace slag is directly leached by hydrochloric acid with the concentration of 400g/L without roasting, and specifically comprises the following steps:
leaching: grinding titanium-containing blast furnace slag, and leaching under the following conditions: the temperature is 90 ℃, the hydrochloric acid concentration is 400g/L, the time is 4 hours, the liquid-solid ratio is 10mL to 1g, and the leaching solution and leaching slag are obtained, and TiO in the leaching solution 2 The content is 12g/L.
In comparative example 1, after roasting by using ammonium sulfate, leaching by water directly to obtain an titanyl sulfate solution, in comparative example 2, directly leaching by using high-concentration hydrochloric acid to obtain an titanyl chlorate solution, and then directly obtaining titanium dioxide through a series of processes such as concentration, purification, hydrolysis and the like. Although the process flows of comparative examples 1 and 2 are shorter than those of examples 1 to 4, the consumption of the reagents used is huge, and the reagents are difficult to recycle and the treatment cost is too high.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, any of the above-described claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for treating titanium-containing blast furnace slag is characterized by comprising the following steps:
mixing and roasting titanium-containing blast furnace slag and an auxiliary agent to obtain calcine;
leaching the calcine to obtain leaching liquid and titanium-containing leaching slag;
and (3) introducing the gas generated by roasting into the leaching solution, regulating the pH value, and carrying out solid-liquid separation to obtain filtrate and filter residues containing aluminum and magnesium.
2. The method for treating titanium-containing blast furnace slag according to claim 1, wherein at least one of the following conditions is satisfied:
a. the auxiliary agent comprises NH 4 Cl、CH 3 COONH 4 、(NH 4 ) 3 PO 4 、(NH 4 ) 2 HPO 4 、NH 4 H 2 PO 4 At least one of (a) and (b);
b. the mass ratio of the titanium-containing blast furnace slag to the auxiliary agent is 1 (0.1-1);
c. the roasting temperature is 200-900 ℃, the heating rate is 2-15 ℃/min, and the roasting time is 0.5-5 h.
3. The method for treating titanium-containing blast furnace slag according to claim 1, wherein at least one of the following conditions is also satisfied:
d. the leaching treatment is normal pressure leaching;
e. the leaching treatment comprises: mixing water or acid liquor with the calcine according to a liquid-solid ratio of (2-20) mL: mixing 1g, leaching for 0.5-6 h at 20-100 ℃ and carrying out solid-liquid separation;
f. in the leaching treatment process, the acid concentration of a leaching system is not more than 150g/L;
g. TiO in the titanium-containing leaching slag 2 The content is more than 30wt%.
4. The method for treating titanium-containing blast furnace slag according to claim 3, wherein the acid in said acid solution comprises HCl, CH 3 COOH、H 3 PO 4 At least one of H2SO 4.
5. The method for treating titanium-containing blast furnace slag according to claim 1, wherein said method further comprises:
mixing the titanium-containing leaching residues with sulfuric acid, and reacting to obtain acidolysis residues;
and leaching the acidolysis slag with water, and carrying out solid-liquid separation to obtain titanium liquid and silicon-rich slag.
6. The method for treating titanium-containing blast furnace slag according to claim 1, wherein said adjusting pH comprises:
introducing the gas into the leaching solution, regulating the pH value of the system to 3-7, and carrying out solid-liquid separation to obtain a separation liquid and aluminum-containing filter residues;
and regulating the pH value of the separation liquid to 10-12, and carrying out solid-liquid separation to obtain filtrate and magnesium-containing filter residues.
7. The method for treating titanium-containing blast furnace slag according to claim 1, wherein after said filtrate is obtained, further comprising:
adding ammonium sulfate into the filtrate, and carrying out precipitation separation to obtain calcium-containing precipitate and a precipitate-containing liquid;
evaporating and concentrating the precipitated liquid to obtain the auxiliary agent.
8. The method for treating titanium-containing blast furnace slag according to claim 7, wherein the mass of said ammonium sulfate is 0.1 to 1.0 times the mass of said titanium-containing blast furnace slag.
9. The method for treating a titanium-containing blast furnace slag according to claim 7, wherein said auxiliary agent obtained after said evaporation and concentration is mixed with said titanium-containing blast furnace slag and roasted to obtain said calcine.
10. The method for treating a titanium-containing blast furnace slag according to any one of claims 1 to 9, wherein said titanium-containing blast furnace slag contains titanium, aluminum, calcium, magnesium and silicon.
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