WO2023043095A1 - Method for extracting waste denitrification catalyst-containing valuable metals - Google Patents
Method for extracting waste denitrification catalyst-containing valuable metals Download PDFInfo
- Publication number
- WO2023043095A1 WO2023043095A1 PCT/KR2022/013031 KR2022013031W WO2023043095A1 WO 2023043095 A1 WO2023043095 A1 WO 2023043095A1 KR 2022013031 W KR2022013031 W KR 2022013031W WO 2023043095 A1 WO2023043095 A1 WO 2023043095A1
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- WO
- WIPO (PCT)
- Prior art keywords
- vanadium
- solution
- titanium
- tungsten
- hydrochloric acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 84
- 239000002184 metal Substances 0.000 title claims abstract description 84
- 150000002739 metals Chemical class 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 103
- 238000002386 leaching Methods 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 253
- 239000000243 solution Substances 0.000 claims description 209
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 182
- 239000010936 titanium Substances 0.000 claims description 142
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 138
- 229910052719 titanium Inorganic materials 0.000 claims description 137
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 110
- 239000004408 titanium dioxide Substances 0.000 claims description 107
- 229910052720 vanadium Inorganic materials 0.000 claims description 107
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 claims description 93
- 239000010937 tungsten Substances 0.000 claims description 83
- 229910052721 tungsten Inorganic materials 0.000 claims description 83
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 82
- 239000013078 crystal Substances 0.000 claims description 74
- 239000003960 organic solvent Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 229910001868 water Inorganic materials 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- 239000003125 aqueous solvent Substances 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000000605 extraction Methods 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 230000007062 hydrolysis Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 41
- 238000000465 moulding Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 46
- 238000000926 separation method Methods 0.000 description 39
- 239000002245 particle Substances 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 28
- 239000002253 acid Substances 0.000 description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000012633 leachable Substances 0.000 description 11
- 238000000638 solvent extraction Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- -1 tungsten (W) Chemical class 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 235000012489 doughnuts Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010415 TiO(OH) Inorganic materials 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by 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
- 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
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
-
- 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
Definitions
- the present invention relates to a method for extracting valuable metals containing a spent denitrification catalyst.
- Nitrogen oxides in the atmosphere cause photochemical smog and acid rain, and have a serious impact on global warming by destroying ozone in the stratosphere. Recognizing the harmfulness of nitrogen oxides to the global environment and human body, developed countries have newly applied strict nitrogen oxide emission standards every year over the past 20 years. Various technologies are being actively developed to meet these nitrogen oxide emission standards.
- One of the representative technologies is to install a selective catalytic reduction (SCR) in an exhaust system to remove nitrogen oxides contained in exhaust gas generated from a thermal power plant.
- SCR selective catalytic reduction
- the selective reduction catalyst is used for about 20,000 hours, after which it is discarded after several regenerations and becomes a waste denitrification catalyst.
- the problem is that the waste denitrification catalyst that solved the nitrogen oxide problem becomes secondary waste.
- the waste denitrification catalyst contains approximately 70 to 75 wt% of TiO 2 , 5 to 10 wt% of WO 3 and 1 to 3 wt% of V 2 O 5 , although there are slight differences for each product.
- expensive valuable metals such as titanium (Ti), tungsten (W), and vanadium (V) included in the spent denitrification catalyst are recovered, secondary waste caused by the spent denitrification catalyst can be minimized.
- more than 400,000 tons of spent denitrification catalysts are generated annually worldwide, and when valuable metals are extracted from them, the economic value is so great that about 1.3 trillion won is reached.
- the alkali roasting method is a method in which waste denitrification catalyst and sodium carbonate are mixed and reacted in a rotary kiln at about 600 ⁇ 800 °C. way to react.
- the alkaline roasting method has a problem in that the leaching rate of tungsten is only 80 to 90% and that of vanadium is only 40 to 50%, so the leaching rate is low.
- the alkali melting method has a high leaching rate of 10 to 98% for tungsten and 10 to 99% for vanadium.
- alkali melting method is performed at a high temperature of over 1000 ° C, alkali agents such as sodium carbonate are consumed in a side reaction with the crucible, making it difficult to select materials, and about 5% of raw material loss occurs due to scattering of powder by internal convection. .
- calcium chloride (CaCl 2 ) is used as a precipitant in a vanadium-tungsten-containing solution, and calcium chloride selectively precipitates tungsten or vanadium according to pH in a strong alkaline leachate.
- a conventional method is difficult to operate stably in the field. Not only is it not easy to control the pH in the strong alkali range, but the precipitation reaction using calcium chloride is sensitive to pH, so vanadium and tungsten co-precipitate when the pH is out of the proper range. By co-precipitation, the separation of vanadium and tungsten is lowered, and the extraction rate is also lowered.
- the waste denitrification catalyst contains titanium.
- the crystalline form of titanium dioxide becomes rutile or anatase, depending on the method used.
- Rutile type titanium dioxide is industrially mainly used as a white pigment.
- Rutile-type titanium dioxide is produced by the chlorine method.
- the chlorine method refers to a method of reacting heated steam of TiCl 4 with heated oxygen to form TiO 2 particles in a high-temperature gas phase.
- the chlorine method produces only rutile-type titanium dioxide. do.
- Anatase-type titanium dioxide is used in a variety of industries, such as pigments, denitrification catalysts, and photocatalysts, and is more universally used than rutile-type titanium dioxide.
- Anatase-type titanium dioxide is produced by the sulfuric acid method.
- the sulfuric acid method is a method of obtaining titanium dioxide of a desired size after firing and growing anatase-type titanium dioxide particles, which are precipitates obtained by thermally hydrolyzing an aqueous solution of TiOSO 4 , at 800 ⁇ 1000 °C. am.
- anatase-type or rutile-type titanium dioxide can be selectively produced by controlling the addition of seeds.
- the chlorine method not only requires advanced equipment, but can only produce rutile-type titanium dioxide.
- the sulfuric acid method can selectively produce anatase-type or rutile-type titanium dioxide, in order to produce rutile-type titanium dioxide, firing at a temperature of about 900 ° C. for 3 to 8 hours is required, as well as particle aggregation during the firing process. A process of micronization is required.
- One object of the present invention is to provide a method for extracting valuable metals containing a spent denitrification catalyst, in which the leaching rate of valuable metals is remarkably improved compared to the prior art.
- Another object of the present invention is to provide a new way to control the crystal shape or particle/granular shape of titanium dioxide extracted from the spent denitrification catalyst.
- a method for extracting valuable metals containing a spent denitrification catalyst comprises the steps of compressing and sintering a mixture of a spent denitrification catalyst powder and an alkali agent to prepare an alkali sintered molded body; and leaching the valuable metal from the alkali sintered molded body.
- the alkali sintered molded body in the step of leaching the valuable metal from the alkali sintered molded body, is reacted with water to extract a vanadium-tungsten-containing solution, the alkali sintered molded body is reacted with water, and then filtered to separate the solids It may be characterized by extracting a titanium-containing hydrochloric acid solution using hydrochloric acid from.
- the step of separating vanadium-tungsten in the extracted vanadium-tungsten-containing solution after extracting the vanadium-tungsten-containing solution is performed, and the step of separating vanadium-tungsten in the vanadium-tungsten-containing solution (a -1) converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution; (a-2) reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution; (a-3) separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent; (a-4) extracting tungsten from the organic solvent; (a-5) reconverting the ionic state of vanadium in the aqueous solvent; (a-6) reacting by adding an extractant to the aqueous medium containing vanadium; and (a-7) extracting vanadium contained in the organic solvent.
- the step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution is performed, and the step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution is (b-1) first titanium-containing hydrochloric acid preparing a solution and a second titanium-containing hydrochloric acid solution having the same composition as or a different composition from the first titanium-containing hydrochloric acid solution; (b-2) preparing a first mixed solution by adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution, and adding water to the first mixed solution to prepare a titanium seed solution; (b-3) preparing a mixed solution by adding a crystal selector to the second titanium-containing hydrochloric acid solution to convert the titanium seed solution and the resulting titanium dioxide into an anatase crystal form; and (b-4) forming anatase-type titanium dioxide through hydrolysis by adding water to the mixed solution.
- the step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution is performed, and the step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution, (c-1) preparing a first titanium-containing hydrochloric acid solution and a second titanium-containing hydrochloric acid solution having the same composition as or different from the first titanium-containing hydrochloric acid solution; (c-2) adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution to prepare a first mixed solution, and adding water to the first mixed solution to prepare a titanium seed solution; (c-3) preparing a mixed solution by adding the titanium seed solution to the second titanium-containing hydrochloric acid solution, selecting a crystalline form of titanium dioxide to be produced by a crystal selector; and (c-4) hydrolyzing the mixed solution to form anatase-type titanium dioxide, wherein in step (c-3), rutile-type titanium dioxide is formed by not adding a crystal selector, and It is characterized
- an alkali sintered molded body is prepared by mixing, molding, and sintering spent denitrification catalyst powder and an alkali agent, and then tungsten, vanadium, and titanium are extracted from the alkali sintered body to obtain tungsten.
- the leaching rate of vanadium and vanadium is 99% or more, and the leaching rate of titanium is also 95% or more.
- the method for extracting valuable metals containing waste denitrification catalysts manufactures alkali sintered molded bodies and uses them to extract valuable metals from waste denitrification catalysts. About 5% of raw material loss due to powder generation can be prevented. Moreover, since valuable metals are extracted from the manufactured alkali sintered molded body by the leaching method, it is possible to fundamentally solve the problem of high-temperature alkali corrosion (side reaction), which is a problem in the alkali melting method, and energy consumption is significantly lower than that of the alkali melting method. There are low advantages.
- titanium dioxide is produced through silver hydrolysis, but anatase-type titanium dioxide is produced by using a crystal selector in the manufacturing process, or
- the crystalline form of titanium dioxide produced can be selected as a rutile form or an anatase form, and furthermore, the ratio of the rutile form and anatase form in the produced titanium dioxide can be controlled by using the addition amount of the crystal selector.
- FIG. 1 is a schematic flowchart of a method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention.
- FIG. 5 is a schematic flow chart of a method for separating vanadium-tungsten in a vanadium-tungsten-containing solution according to an embodiment of the present invention.
- FIG. 6 is a schematic configuration diagram of a vanadium-tungsten separation system according to another embodiment of the present invention.
- FIG. 10 is a schematic flow chart of a method for preparing anatase-type titanium dioxide using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention.
- FIG. 11 is a schematic flow chart of a titanium dioxide crystal control method using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention.
- FIG. 12 is an XRD measurement result of titanium dioxide when a crystal selector is not added in the process of hydrolysis using a titanium-containing hydrochloric acid solution
- FIG. 13 is an XRD measurement result when a crystal selector is added.
- 14 and 15 are results of measuring the particle size of titanium dioxide according to the amount of the crystal selector (type 2) in the process of hydrolysis using a titanium-containing hydrochloric acid solution.
- 16 to 20 are photographs taken of the particle shape of titanium dioxide according to the amount of the crystal selector (type 2) in the process of hydrolysis using a titanium-containing hydrochloric acid solution.
- FIG. 21 is a SEM image of titanium dioxide particles generated when no seeds are added
- FIG. 22 is a SEM image of titanium dioxide particles when 4 wt% of seeds are added.
- the first is to extract valuable metals from the spent denitrification catalyst and improve the leaching rate of the valuable metals by using an alkali sintered molded product.
- the third method is to form anatase-type titanium dioxide in a hydrochloric acid solution containing titanium extracted from the solid obtained after water leaching from the spent denitrification catalyst using hydrochloric acid.
- An object of the method for extracting valuable metals containing a waste denitrification catalyst according to an embodiment of the present invention is to create added value by extracting valuable metals from a waste denitrification catalyst that has been previously disposed of. ‘Utilizing waste denitrification catalysts that have reached the end of their lifespan after use in thermal power plants, etc., valuable metals are extracted, separated, and refined to make them into materials.
- the alkali sintered molded body of the present invention it is significant that the mass productivity of the method for extracting valuable metals containing a spent denitrification catalyst is secured.
- the composition of the spent denitrification catalyst varies from product to product, but generally contains 70 to 75 wt% of TiO 2 , 8 to 10 wt% of SiO 2 , 5 to 10 wt% of WO 3 , and 1 to 3 wt% of V 2 O. 5 , 2-5 wt% of CaO, 2-5 wt% of Al 2 O 3 , 2-5 wt% of SO 3 , and 0.2-0.4 wt% of Fe 2 O 3 .
- tungsten (W), vanadium (V), and titanium (Ti) are rare metals and are required in various industries.
- the present invention extracts valuable metals such as tungsten (W), vanadium (V) and titanium (Ti) from spent denitrification catalysts.
- the valuable metals contained in the spent denitrification catalyst must be converted into leachable forms, and each valuable metal must be separated and leached using a leaching method suitable for each valuable metal.
- a method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention relates to a technology for converting valuable metals contained in a spent denitrification catalyst into a leachable form, which has improved mass productivity and process efficiency compared to conventional technologies. There are advantages.
- the conventional alkali roasting method and alkali melting method for leaching valuable metals from waste denitrification catalysts have limitations in their application to mass production. Specifically, the alkaline roasting method has a problem in that the leaching rate of valuable metals is too low. In addition, the alkali melting method is not suitable for mass production because the energy consumption is high, the process difficulty is very high because the melt must be handled, and the leaching rate varies greatly depending on the subsequent process. In addition, raw material loss occurs due to scattering of powder by internal heat convection.
- FIG. 1 is a schematic flowchart of a valuable metal extraction method (M100) containing a spent denitrification catalyst according to an embodiment of the present invention that overcomes the limitations of the prior art.
- M100 valuable metal extraction method
- a method for extracting valuable metals containing a spent denitrification catalyst (M100) includes preparing an alkali sintered molded body (S10) and leaching valuable metals from the alkali sintered molded body (S30).
- the step of preparing an alkali sintered molded body (S10) includes preparing a waste denitrification catalyst powder by pulverizing and drying the spent denitrification catalyst powder (S11), preparing a mixture by mixing the spent denitrification catalyst powder and an alkali agent (S12), the mixture and forming a temporary molded body by compression molding (S13) and forming an alkali sintered molded body by sintering the temporary molded body (S14).
- the spent denitrification catalyst collected from a thermal power plant is crushed and dried in an oven to remove moisture.
- the average particle size of the spent denitrification catalyst powder may be 250 ⁇ m or less, more preferably 212 ⁇ m or less.
- the average particle size of the spent denitrification catalyst powder exceeds 212 ⁇ m, the reactivity with alkali agents decreases, and the leaching rate of valuable metals tends to decrease slightly.
- the waste denitrification catalyst is mixed with an alkali agent to prepare a mixture (S12).
- sodium carbonate (Na 2 CO 3 ) or sodium hydroxide (NaOH) may be selected.
- the amount of the alkali agent included in the mixture may be 0.6 kg to 1.2 kg, preferably 0.8 kg to 1.0 kg, per 1 kg of spent denitrification catalyst powder.
- the amount of alkali agent is less than 0.6 kg, the amount of alkali agent in which valuable metals contained in waste denitrification catalyst cannot be changed into leachable form increases due to lack of alkali agent. It acts as an impurity and causes side reactions in the later process, and economical efficiency is lowered due to unnecessary consumption of alkali agent.
- the mixture is compression molded using a press to form a temporary molded body (S13).
- the process of forming the temporary molded body may be performed at room temperature, and the molding pressure may be 500 kgf/cm 2 or more.
- the shape of the temporary body may be a donut columnar shape, a circular columnar shape or a quadrangular columnar shape, preferably a donut columnar shape (see FIG. 4).
- a process of sintering the temporary body at a high temperature is performed.
- heat is evenly transferred to the center and the outside of the donut, so that sintering can be performed more efficiently.
- the temperature rises by about 40 to 60 ° C. as heat is generated by the pressure.
- the reaction efficiency between the waste denitrification catalyst powder and the alkali agent is increased.
- scattering powder between processes is reduced by the compression molding process.
- the caustic molded body is sintered to form an alkali sintered molded body (S14).
- the valuable metals contained in the denitrification waste are converted into leachable sodium salt form.
- the reaction performed in the alkali sintered molded body is as follows.
- Tungsten and vanadium by the above reaction are converted into a form that can be leached by water, and titanium is converted into a form that can be easily leached by acid.
- the leaching rate of each valuable metal is proportional to how much the valuable metal contained in the denitrification waste is converted into a leachable form in the process of forming the alkali sintered molded body.
- the reaction efficiency between the waste denitration catalyst powder and an alkali agent is increased in the process of forming a false body, thereby forming an alkali sintered molded body.
- more valuable metals contained in the denitrification waste are converted into leachable forms. Accordingly, the leaching rate of each valuable metal increases.
- the temperature for sintering the temporary body may be 800 to 900 ° C, and the sintering time may be 30 to 90 minutes. If the sintering temperature is less than 800 °C, the temperature is low, so the valuable metal contained in the denitrification waste is not sufficiently converted into a leachable form. Thereby, there is a problem that the leaching rate is rather lowered and the recovery rate is lowered because some melting occurs. In the present invention, the leaching rate can be maximized by setting the sintering temperature to 800 to 900 ° C. to produce an alkali sintered molded body.
- the leaching rate of vanadium and tungsten is 95%, and the leaching rate of titanium is lowered to less than 50%.
- the sintering temperature exceeds 900 ° C., the caustic mold is melted and the problems occurring in the alkali melting process are reproduced, and when it is discharged as a melt, it is difficult to recover and causes alkali corrosion to the crucible or tray. Therefore, when the sintering temperature of the temporary body is 800 °C, the leaching rate of vanadium and tungsten rises to 95% or more, and the leaching rate of titanium rises to 50% or more. The leaching rate of can also be increased to 90% or more.
- the leaching rate of tungsten and vanadium is 99% or more, and the leaching rate of titanium is 95% or more.
- the waste denitrification catalyst contains CaO at a content of 2-5%, and CaTiO 3 that is insoluble in acid is formed by the reaction between CaO-TiO 2 during sintering. becomes the upper limit. That is, when using the present invention, tungsten, vanadium, and titanium can be leached to a degree close to the upper limit.
- a step (S30) of leaching valuable metals from the alkali sintered molded body is performed.
- the alkali sintered molded body is pulverized to have an average particle size of about 45 to 125 ⁇ m.
- Valuable metal is leached from the prepared alkali sintered molded body (S30).
- a vanadium-tungsten separation method in a vanadium-tungsten-containing solution described later may be used.
- a step (S31) of extracting vanadium and tungsten from the alkali sintered molded body is performed.
- a vanadium-tungsten containing solution can be obtained by performing the step of extracting vanadium and tungsten from the alkali sintered molded body (S31). Specifically, it is as follows.
- Water leaching is performed by adding 40 to 60 parts by weight of the alkali sintered molded body with respect to 100 parts by weight of water, and the temperature of the water at which water leaching is performed is preferably 70 to 90 °C. After water leaching, the solids are filtered to separate the leachate and solids.
- a precipitating agent is then added to the leachate.
- Calcium chloride (CaCl 2 ) may be used as a precipitant.
- Calcium chloride can selectively precipitate tungsten or vanadium by controlling the leaching rate of tungsten and vanadium through calcium in a strong alkaline leachate. That is, calcium metavanadate may be precipitated by adding potassium hydroxide as a pH adjusting agent to adjust the pH above 13, and calcium tungstate may be precipitated by adjusting the pH to 13 or less.
- the precipitation process may be performed by stirring for 30 minutes to 2 hours at 200 to 600 rpm through an agitator.
- a hydrochloric acid solution containing titanium may be obtained by performing the step of extracting titanium from the alkali sintered molded body (S32). Specifically, it is as follows.
- Acid leaching is performed by adding hydrochloric acid to the solid. Acid leaching may be performed at 50 to 60 °C for 2 to 3 hours.
- sodium hydroxide is added to the acid leachate obtained through acid leach.
- the hydrated TiO 2 is calcined to recover titanium dioxide.
- the calcination process may be performed at a temperature of about 400 to 600 ° C. or more for 1 to 5 hours, and thus titanium dioxide (rutile or anatase) may be recovered.
- the step of leaching the valuable metal from the alkali sintered molded body (S30) can be performed in a new method.
- a step (S31) of extracting vanadium and tungsten from the alkali sintered molded body is performed.
- the quality of vanadium (V 2 O 5 ) and tungsten (WO 3 ) finally obtained can be improved by improving the separation between vanadium and tungsten by the method proposed here.
- Water leaching is performed by adding 40 to 60 parts by weight of the alkali sintered molded body with respect to 100 parts by weight of water, and the temperature of the water at which water leaching is performed is preferably 70 to 90 °C. After water leaching, the solids are filtered to separate the leachate and solids.
- a step of pre-treating the leachate to convert the vanadate ion state is performed.
- an inorganic acid eg, sulfuric acid, hydrochloric acid, etc.
- a pre-treatment agent is added to reduce vanadium acid ions (VO 3 - ) in the leachate to obtain an amine-based It is converted into a state that is not extracted by the extractant.
- VO 3 - in the leachate is converted into VO 2+ by lowering the pH of the leachate, and converted into VO 2+ by adding a pretreatment agent .
- pH for converting VO 3 - in leachate to VO 2 + may be determined by the concentration of vanadium, and is shown in Table 1 below.
- sodium hydrogen sulfite (NaHSO 3 ) and/or sodium sulfide (Na 2 S) may be used as the pretreatment agent.
- the amount of the pretreatment agent is added from 1 to 2 equivalents to 1 equivalent of vanadium based on the concentration of vanadium.
- An extractant is added to the pretreated leachate.
- An amine-based extractant may be used as the extractant, and specifically, Alamine 336 may be used.
- tungstate ions WO 4 2-
- converted vanadate ions VO 2+
- a step of separating the first organic solvent and the first aqueous solvent is performed. At this time, tungsten moves into the first organic solvent, and vanadium moves into the first aqueous solvent. Therefore, tungsten and vanadium can be separated from each other by separating the first organic solvent and the first aqueous solvent. Separation of the first organic solvent and the second aqueous solvent may use a centrifugal solvent extraction device.
- washing is performed on the separated first organic solvent, and an ammonia (NH 3 ) solution is introduced.
- NH 3 ammonia
- the ammonia solution is added to the first organic solvent, the contained tungsten is converted to APT (Ammonium Paratungstate) and moved to the second aqueous solvent.
- APT Ammonium Paratungstate
- the second aqueous solvent is separated from the first organic solvent again, and APT in the second aqueous solvent is crystallized to obtain.
- the obtained APT is recovered as WO 3 through calcination after solid-liquid filtration.
- the purity of WO 3 recovered in this way is 99.8% or more.
- ammonia or ammonia solution is added to the separated first aqueous solvent.
- the contained vanadium is converted into AMV (Ammonium Meta-Vanadate).
- AMV is precipitated in the first aqueous solution, and AMV is obtained by separating the precipitate through solid-liquid filtration.
- the obtained AMV is recovered as V 2 O 5 through sintering.
- the purity of V 2 O 5 recovered in this way is 99.8% or more.
- a step (S32) of extracting titanium from the alkali sintered molded body is performed.
- the method proposed here has the advantage of being able to control whether titanium crystals are anatase or rutile even by hydrolysis, while titanium is extracted by the hydrochloric acid method.
- Acid leaching is performed by adding hydrochloric acid to the solid. Acid leaching may be performed at 50 to 60 °C for 2 to 3 hours.
- the seed solution is prepared by mixing 0.3 to 0.7 kg of caustic soda per 1 kg of acid leachate at room temperature, and mixing 65 to 85 parts by weight of water with 100 parts by weight of the mixture at 65 to 85 ° C. for 25 to 35 minutes.
- a step of hydrolysis is performed by adding the prepared seed solution to acid leachate. Adding the prepared seed solution to acid leachate and hydrolyzing it is performed at 80 to 110 ° C for 150 to 210 minutes.
- the seed solution is added in an amount of 3 to 4 parts by weight based on 100 parts by weight of acid leachate.
- a crystal selector may be added to the seed solution together with the seed solution, and the crystal form of titanium obtained by the crystal selector is determined whether it is anatase or rutile.
- a crystal selector is added in a certain amount or more, the crystalline form of titanium to be produced becomes anatase, and when not added, the crystalline form of titanium to be produced becomes rutile.
- the crystal selector is sulfuric acid
- 10 parts by weight or more of sulfuric acid is added to 100 parts by weight of acid leachate
- the crystalline form of the titanium produced becomes anatase.
- the crystal form of titanium produced becomes anatase. become anatase.
- the precipitate is separated and calcined to recover titanium dioxide.
- the calcination process may be performed for 2 to 5 hours at a temperature of about 400 to 600 ° C., thereby recovering titanium dioxide (rutile or anatase).
- the spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst.
- the particle size of the spent denitrification catalyst powder was ⁇ 212 ⁇ m.
- a mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder.
- the mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 500 kgf/cm 2 or more using a crank-type press. It was confirmed that the temperature of 50 °C was increased by heat generation during the manufacturing process of the pseudo-shaped body.
- the prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
- the alkali sintered compact was pulverized, and valuable metals were leached therefrom.
- Water leaching was sufficiently performed by adding 50 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water. The temperature of the water subjected to water leaching was 80 °C. After performing water leaching, the solids were filtered to separate the leachate and the solids. Sulfuric acid was added to the separated leachate to lower the pH to 1, and sodium sulfite (NaHSO 3 ) as a vanadium ion state conversion agent was added in an amount of 1.5 equivalents per 1 equivalent of vanadium. Alamine 336 was added as an extractant to the pretreated leachate. Thereafter, the first organic solvent and the first aqueous solvent were mixed with each other using a centrifugal solvent extraction unit, and then the first organic solvent and the first aqueous solvent were separated from each other by centrifugal force.
- NaHSO 3 sodium sulfite
- the separated first organic solvent was washed, and the washed first organic solvent was separated using a centrifugal solvent extraction unit. Ammonia solution was added to the washed first organic solvent, and the first organic solvent and the second aqueous solvent were separated again using a centrifugal solvent extraction unit. Thereafter, APT was crystallized from the second aqueous solvent, and WO 3 was recovered by solid-liquid filtration and calcining of the obtained APT.
- Ammonia was added to the separated first aqueous solvent.
- AMV was precipitated as ammonia was added to the first aqueous solvent, and AMV was obtained by separating the precipitate through solid-liquid filtration. The obtained AMV was calcined to recover V 2 O 5 .
- Acid leaching was performed by adding hydrochloric acid to the solid. Acid leaching was carried out at 60 °C for 3 hours. A seed solution was prepared using some of the acid leachate. The seed solution was mixed with 0.5 kg of caustic soda per 1 kg of acid leachate to prepare mixed water, and 0.75 kg of water was added per 1.5 kg of mixed water. After stirring at 70 °C for 30 minutes to prepare a seed solution. 4 wt% of the prepared seed solution was added to the acid leachate, and reacted at 100 ° C. for 180 minutes. The precipitate precipitated in the reaction process was separated and calcined at 600 ° C. for 5 hours to recover titanium dioxide (rutile).
- rutile titanium dioxide
- the leaching rate of each valuable metal in Example 1 is shown in Table 2 below.
- Each valuable metal was extracted in the same manner as in Example 1, but the waste denitrification catalyst was mixed with an alkali agent to prepare a mixture, and samples were prepared by changing the content of the alkali agent.
- the leaching rate of each valuable metal was measured for each sample, and the leaching rate of valuable metal according to the composition of the alkali sintered molded article is shown in FIG. 2 .
- the amount of the alkali agent when the amount of the alkali agent is 0.8 kg or less for 1 kg of the spent denitrification catalyst, the amount of the valuable metal contained in the spent denitrification catalyst that cannot be changed into a leachable form increases due to insufficient alkali agent, and 1.2 kg If it is exceeded, the alkali agent acts as an impurity and becomes a burden in the subsequent process, and economical efficiency is lowered due to unnecessary consumption of the alkali agent.
- the amount of alkali agent for 1 kg of spent denitrification catalyst is less than 0.7 kg, there is a problem in that the leaching rate of titanium is lowered, and when it exceeds 1.0 kg, it can be confirmed that it does not contribute to the increase in leaching rate.
- Samples were prepared by extracting each valuable metal in the same manner as in Example 1, but changing the sintering temperature in the process of sintering the pseudo-form.
- the leaching rate of each valuable metal was measured for each sample, and the leaching rate of the valuable metal according to the sintering temperature is shown in FIG. 3 .
- the leaching rate is rather low.
- FIG. 5 is a schematic flow chart of a method for separating vanadium-tungsten in a vanadium-tungsten-containing solution according to an embodiment of the present invention.
- vanadium-tungsten separation method in a vanadium-tungsten-containing solution according to an embodiment of the present invention (hereinafter referred to as “vanadium-tungsten separation method”) will be described. Meanwhile, it is noted in advance that the vanadium-tungsten separation method M200 according to an embodiment of the present invention may be performed by a vanadium-tungsten separation system 100 (see FIG. 6) to be described later.
- the vanadium-tungsten-containing solution formed by water leaching from the above-mentioned spent denitrification catalyst may be used.
- the vanadium-tungsten separation method (M200) in a vanadium-tungsten-containing solution according to an embodiment of the present invention is largely divided into two routes. The first is the tungsten extraction route, and the second is the vanadium extraction route.
- the purpose of the tungsten extraction route in the present invention is to separate tungsten and vanadium and to concentrate tungsten at the same time.
- a feature of the tungsten extraction route of the present invention is that only tungsten is selectively extracted by converting vanadium into an ionic form in which vanadium is not extracted using a pretreatment agent, and furthermore, the concentration of tungsten is concentrated through the extraction-cleaning-separation process.
- the main purpose of the vanadium extraction route of the present invention is the concentration of vanadium. That is, vanadium having an ionic form that was not extracted by the extractant is separated from tungsten and then converted into a form to be extracted again, and then extracted and concentrated through the extractant. Below, this will be explained in detail.
- a vanadium-tungsten-containing solution is pretreated to reduce vanadium in the solution (S210), and an extractant is added to the pretreated vanadium-tungsten-containing solution. and reacting (S220), separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent (S230), extracting tungsten from the organic solvent (S240), and extracting vanadium from the aqueous solvent ( S250).
- a step of converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution (S210) is performed.
- the vanadium-tungsten-containing solution may be prepared by pulverizing denitrification waste, mixing with an alkali agent (eg, sodium carbonate), reacting at high temperature, and then leaching with water.
- the vanadium-tungsten-containing solution may contain vanadate ions (VO 3 - ) and tungstate ions (WO 4 2- ) in water.
- the purpose of converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution (S210) is to convert the vanadium in the solution to a state that is not extracted by the extractant.
- the VO 3 - ions are converted to VO 2+ ions.
- the pH of the vanadium-tungsten-containing solution is adjusted to 3 or less using hydrochloric acid, nitric acid, or sulfuric acid.
- the pH of the vanadium-tungsten-containing solution may be determined by the concentration of vanadium in the vanadium-tungsten-containing solution, and is shown in Table 3 below.
- VO 3 - ions included in the vanadium-tungsten-containing solution are first converted into VO 2 + ions.
- a step (S212) of adding a pretreatment agent to the vanadium-tungsten-containing solution whose pH is adjusted is performed (S212), and the VO 2 + ions contained in the vanadium-tungsten-containing solution whose pH is adjusted by the pretreatment agent are VO 2+ converted into ions VO 2+ ions are not extracted by extractants, more specifically amine-based extractants.
- pretreatment agent those having the property of binding to oxygen in the solution while dissolving may be used, such as
- At least one of sodium hydrogen sulfite (NaHSO 3 ), sodium sulfite (Na 2 SO 3 ), and sodium sulfide (Na 2 S) may be used.
- the amount of the pretreatment agent is added from 1 to 2 equivalents to 1 equivalent of vanadium based on the concentration of vanadium. If the amount of the pretreatment agent is less than 1 equivalent per 1 equivalent of vanadium, there is a problem that VO 2+ ions that are not converted to VO 2+ ions remain, and if the amount exceeds 2 equivalents, the pretreatment agent does not contribute to the pretreatment anymore and rather impurities do.
- the temperature is raised to 40 ⁇ 80 °C, and maintained for 1 ⁇ 4 hours to react.
- a step of reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution is performed.
- An amine-based extractant may be used as the extractant, and specifically, Alamine 336 or Trioctylamine (TOA) may be used.
- the extraction temperature is carried out at 40 ⁇ 60 °C.
- the amine-based extractant can extract both vanadium and tungsten, but when vanadium exists as VO 2+ ions in a vanadium-tungsten-containing solution through a pretreatment process, vanadium is not extracted by the amine-based extractant. Therefore, in the step of reacting by adding an extractant to the vanadium-tungsten-containing solution (S220), tungsten is transferred to the organic solvent, and vanadium remains in the aqueous solvent.
- the amount of the extractant may be 10 to 100 parts by weight based on 100 parts by weight of the pretreated vanadium-tungsten-containing solution. If the amount of the extractant is less than 10 parts by weight with respect to 100 parts by weight of the pretreated vanadium-tungsten-containing solution, there is a problem that tungsten remains in the aqueous solvent, and if it exceeds 100 parts by weight, the ability to extract impurities is improved and impurities in the solvent There is a problem that the concentration of
- a step of separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent is performed.
- a solvent extraction type centrifugal separation unit may be used, but the vanadium-tungsten separation method of the present invention is not limited thereto.
- tungsten and vanadium are completely separated from each other by separating the organic solvent and the aqueous solvent.
- Extracting tungsten from an organic solvent (S240) and extracting vanadium from an aqueous solvent (S250) are performed. These two steps can be performed in parallel with each other.
- the step of extracting tungsten from the organic solvent (S240) is a step of washing (S241), adding an ammonia solution to the organic solvent to convert tungsten contained in the organic solvent into APT (Ammonium Para-Tungstate) (S242), Separating the organic solvent and the aqueous solvent containing APT (S243), crystallizing APT from the aqueous solvent containing APT (S244), and solid-liquid filtration and calcining the crystallized APT to recover WO 3 (S245). ) is performed.
- the washing step (S241) is performed by repeating the process of mixing the separated organic solvent with the washing liquid and separating it again one or more times. Impurities other than tungsten contained in the organic solvent are removed through the cleaning step (S241). Impurities other than tungsten include SO 4 2- and VO 2+ , and a cleaning step removes them.
- the washing solution to be added is ultrapure water, and the amount of ultrapure water may be 30 to 100 parts by weight based on 100 parts by weight of the organic solvent.
- a step (S42) of converting tungsten contained in the organic solvent into APT (Ammonium Para-Tungstate) by adding an ammonia solution to the organic solvent is performed.
- APT Ammonium Para-Tungstate
- ammonia solution is added to the organic solvent that has been cleaned, tungsten is converted into APT (Ammonium Para-Tungstate). Since APT is soluble in aqueous solvent, this process causes tungsten to migrate from organic solvent to aqueous solvent.
- As the ammonia solution to be added 5 to 9 wt.% of ammonia dissolved in water may be used.
- the amount of the ammonia solution may be included in 50 to 100 parts by weight based on 100 parts by weight of the organic solvent.
- a step of separating the organic solvent and the aqueous solvent containing APT (S243) is performed.
- a solvent extraction type centrifugal separation unit may also be used in this step.
- a step of crystallizing APT in an aqueous solvent containing APT (S244) is performed, solid-liquid filtration of the crystallized APT is performed, and WO 3 is recovered by calcining (S245).
- Known methods can be used for crystallizing APT and recovering WO 3 by calcining APT.
- the step of extracting vanadium from the aqueous solvent (S250) is as follows.
- Reconverting the ionic state of vanadium in aqueous solvent (S251), reacting by adding an extractant to the vanadium solution (S252), separating into an organic solvent and an aqueous solvent after the reaction (S253), organic containing vanadium Adding an ammonia solution to the solvent and reacting (S54), separating the organic solvent and the aqueous solvent after the reaction (S255), adding ammonia to the aqueous solvent to precipitate as AMV (S256), and solid-liquid filtration to form AMV Separating (S257), and firing the separated AMV to recover V 2 O 5 (S258) are performed.
- a step of reconverting the ionic state of vanadium from VO 2+ to VO 2+ in an aqueous solvent (S251) is performed.
- hydrogen peroxide is used as an additive, and the amount of the additive is 1 to 2 equivalents per 1 equivalent of vanadium based on the concentration of vanadium.
- the reaction is maintained at a temperature of 40 to 60 degrees for 1 hour to 2 hours.
- a step of reacting by adding an extractant to the reconverted vanadium solution is performed.
- An amine-based extractant is used as the extractant, and specifically, Alamine336 or Trioctylamine (TOA) may be used.
- the amount of the extractant may be included in 10 to 40 parts by weight based on 100 parts by weight of the vanadium solution. This step causes vanadium to migrate from the aqueous solvent to the organic solvent.
- a step of separating the organic solvent and the aqueous solvent (S253) is performed.
- a solvent extraction type centrifugal separation unit may be used, but the vanadium extraction method of the present invention is not limited thereto.
- vanadium is included in the organic solvent and sodium and sulfate ions remain in the aqueous solvent, only vanadium is selectively extracted and separated by separating the organic solvent and the aqueous solvent.
- a step of transferring vanadium contained in the organic solvent to the aqueous solvent by adding an ammonia solution to the organic solvent is performed.
- an ammonia solution to be added 1.0 to 1.8 wt% of ammonia dissolved in water may be used.
- the amount of the ammonia solution may be included in an amount of 30 to 50 parts by weight based on 100 parts by weight of the organic solvent.
- a step of separating the organic solvent and the aqueous solvent containing vanadium (S255) is performed, and a solvent extraction type centrifugal separation unit can also be used in this step.
- Ammonia is additionally added to the aqueous solvent containing vanadium to precipitate as AMV (Ammonium Meta-Vanadate) (S256), and AMV is separated through solid-liquid filtration (S257). The separated AMV is fired to recover V 2 O 5 (S258).
- AMV Ammonium Meta-Vanadate
- S257 solid-liquid filtration
- S258 solid-liquid filtration
- known methods can be used.
- the purity of the recovered WO 3 and the purity of the recovered V 2 O 5 are both 99.8% or higher.
- the above-described vanadium-tungsten separation method M200 according to an embodiment of the present invention may be performed by the vanadium-tungsten separation system 100 (see FIG. 6).
- FIG. 6 is a schematic configuration diagram of a vanadium-tungsten separation system 100 according to another embodiment of the present invention.
- the vanadium-tungsten separation system 100 includes a first extraction unit 11, a cleaning unit 12, a first removal unit 13, a second extraction unit 22, and a second removal unit 23.
- Each unit uses a centrifugal separation unit capable of separating the organic solvent (O) and the aqueous medium (A) from each other by centrifugal force after the organic solvent and the aqueous medium are mixed by rotational force.
- a vanadium solution treatment reactor 21 is further included.
- the pretreated vanadium-tungsten-containing solution and the extractant are introduced into the first extraction unit 11 .
- the pretreated vanadium-tungsten-containing solution is a solution containing VO 2+ ions and WO 4 2- ions
- an extractant is an amine-based extractant (eg, Alamine 336).
- the vanadium-tungsten-containing solution and the extraction agent are mixed with each other, and the organic solvent and the aqueous solvent are separated and discharged respectively by centrifugal force. At this time, tungsten is discharged into an organic solvent, and vanadium is discharged into an aqueous solvent.
- the organic solvent discharged from the first extraction unit 11 flows into the cleaning unit 12 .
- the cleaning liquid is introduced into the cleaning unit 12, and the organic solvent and the cleaning liquid are mixed in the cleaning unit 12, separated from each other again by centrifugal force, and discharged. In this process, impurities other than tungsten are removed from the first extraction unit 11 .
- the organic solvent including tungsten from which impurities are removed by the cleaning unit 12 flows into the first stripping unit.
- the organic solvent containing tungsten and the ammonia liquid are mixed, separated from each other by centrifugal force, and discharged.
- tungsten is converted into an APT solution and moved to an aqueous solvent to be discharged.
- the discharged APT solution is subjected to solid-liquid filtration and calcining of APT obtained after crystallization to recover WO 3 .
- the vanadium ion state is reconverted in the reactor 21, it is introduced into the second extraction unit 22 together with the extractant.
- the aqueous solvent and the extractant are mixed with each other in the second extraction unit 21, and are separated from each other and discharged by centrifugal force.
- the organic solvent containing vanadium discharged from the second extraction unit 22 flows into the second separation unit 23 .
- the organic solvent containing vanadium and the ammonia solution are mixed, separated from each other by centrifugal force, and discharged.
- vanadium moves to the aqueous solvent and is discharged.
- the discharged vanadium solution is precipitated as AMV by additionally adding ammonia, and after precipitation, it is recovered as V 2 O 5 through solid-liquid filtration and sintering.
- the vanadium-tungsten separation system 100 occupies less space per unit area and has a faster processing speed compared to a conventional mixtaker, which is very advantageous for productivity improvement and operation, and is suitable for mass production. Above all, since it is operated as a closed system, it has the advantage of minimizing volatilization of the solvent during the process.
- the spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst.
- the particle size of the spent denitrification catalyst powder was ⁇ 212 ⁇ m.
- a mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder.
- the mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 500 kgf/cm 2 or more using a crank-type press. It was confirmed that the temperature of 50 °C was increased by heat generation during the manufacturing process of the pseudo-shaped body.
- the prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
- the alkali sintered compact was pulverized, and valuable metals were leached therefrom.
- Water leaching was sufficiently performed by adding 50 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water.
- the water temperature for water leaching was 50 °C.
- the solids were filtered to separate the leachate and the solids.
- the leachate becomes a vanadium-tungsten containing solution.
- Trioctylamine was used as an extractant.
- the APT solution obtained from the vanadium-tungsten separation system was crystallized, and the APT recovered after solid-liquid filtration was calcined to obtain WO 3 .
- AMV was precipitated from the vanadium solution obtained from the vanadium-tungsten separation system, followed by solid-liquid filtration, and the obtained AMV was calcined to obtain V 2 O 5 .
- FIG. 7 shows the extraction results of vanadium and tungsten in the tungsten extraction route, it can be seen that the extraction rate of tungsten is high and the extraction rate of vanadium is low, resulting in increased separation between tungsten and vanadium.
- the vanadium extraction rate in the tungsten extraction route increases, the vanadium extraction rate inevitably decreases based on the entire vanadium-tungsten separation method in the vanadium-tungsten containing solution of the present invention. This is the same in FIGS. 8 and 9 below.
- the extraction rate of vanadium increases in the tungsten extraction route at pH 2 or higher. It is not converted to 2+ ion. That is, when the vanadium concentration is about 0.01 M, the conversion rate of vanadium ions gradually decreases at pH 1.2 or higher. In the case of tungsten, it shows an extraction rate of 99.9% or more at pH 1-2, and the extraction ability decreases at pH 0.5 or less or pH 3 or more. This is related to the tungsten extraction characteristics of Alamine336 Trioctylamine (TOA), and it is generally known that the extractant has a high tungsten extraction ability at pH 1-2.
- TOA Alamine336 Trioctylamine
- the vanadium-tungsten separation was performed in the same manner as in Example 4, but the amount of the pretreatment agent was adjusted in the pretreatment process, and the effect thereof is shown in FIG. 8 .
- the titanium-containing hydrochloric acid solution used herein can be regarded as obtained by acid leaching from a waste denitrification catalyst, but the present invention is not limited thereto.
- FIG. 10 is a schematic flow chart of a method for producing anatase-type titanium dioxide (M300) using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention.
- the method for producing anatase-type titanium dioxide (M300) includes preparing a titanium seed solution (S310), adding the titanium seed solution and a crystal selector to a titanium-containing hydrochloric acid solution and mixing them.
- the prepared titanium-containing hydrochloric acid solution contains 8 to 12 wt% of titanium and has a hydrochloric acid molar concentration of 8 to 10 M.
- a titanium seed solution is prepared using some of the prepared titanium-containing hydrochloric acid solution (S310).
- the titanium-containing hydrochloric acid solution used to prepare the titanium seed solution is defined as the first titanium-containing hydrochloric acid solution.
- To prepare a titanium seed solution first, 30 to 70 parts by weight of sodium hydroxide is added to 100 parts by weight of the first titanium-containing hydrochloric acid solution and mixed at room temperature to prepare a seed mixture solution. Then, 30 to 70 parts by weight of water is mixed with 100 parts by weight of the seed mixture solution at 60 to 80 ° C. for 25 to 35 minutes to prepare a titanium seed solution.
- the method for producing anatase-type titanium dioxide of the present invention produces titanium dioxide by hydrolysis. When a titanium seed solution is used, the time required for preparing titanium dioxide can be significantly reduced, and the particle size of the titanium dioxide produced can be significantly reduced. Quality, such as purity, is increased.
- the process of preparing the titanium seed solution is performed by the following Reaction Scheme 2.
- the titanium seed solution contains metatitanic acid, which is a hydrate form of titanium dioxide.
- a step of preparing a mixed solution using the prepared titanium seed solution (S320) is performed.
- the time required for the process can be shortened by preparing a large amount of the titanium seed solution in advance and using some of it in the step of preparing a mixed solution (S320).
- the titanium seed solution and the crystal selector are added to the titanium-containing hydrochloric acid solution and mixed.
- the titanium-containing hydrochloric acid solution used in the step of preparing the mixed solution (S320) may be defined as a second titanium-containing hydrochloric acid solution.
- the content of the titanium seed solution may be 1 to 4 parts by weight based on 100 parts by weight of the second titanium-containing hydrochloric acid solution.
- the content of the titanium seed solution is less than 1 part by weight based on 100 parts by weight of the second titanium-containing hydrochloric acid solution, the effect of using the titanium seed solution is insignificant, and when it exceeds 4 parts by weight, the particle size of the titanium dioxide produced increases.
- the seed induces a homogeneous reaction by providing crystal nuclei in the reaction, and thus serves to suppress the overgrowth of specific particles.
- anatase-type titanium dioxide manufacturing method (M300) to manufacture anatase-type titanium dioxide, a crystal selector is added to a titanium-containing hydrochloric acid solution and mixed.
- the crystal selector serves to make the crystal form of titanium dioxide produced into an anatase form.
- the crystal selector may be any one selected from the group consisting of sulfuric acid, phosphoric acid, and disodium hydrogen phosphate, or a mixture thereof.
- sulfuric acid can be classified as a type 1 crystal selector
- phosphoric acid and disodium hydrogen phosphate can be classified as a type 2 crystal selector.
- the first-type crystal selector serves to make the produced titanium dioxide anatase-type
- the second-type crystal selector serves to make the produced titanium dioxide anatase-type and controls the particle size and particle shape to be produced.
- the content of the crystal selector In order to control the resulting anatase-type titanium dioxide to be 99 wt%, the content of the crystal selector must be adjusted.
- the crystal selector when the crystal selector is sulfuric acid, the crystal selector is added in an amount of 10 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution, and when the crystal selector is phosphoric acid, the crystal selector is 100 parts by weight of the second titanium-containing hydrochloric acid solution. 0.4 part by weight or more, and when the crystal selector is disodium hydrogen phosphate, the crystal selector is added in an amount of 0.5 part by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution.
- the crystal selection agent is less than the upper limit, the anatase type and the rutile type are mixed in the titanium dioxide produced. When no crystal selector is added, more than 99 wt% of the titanium dioxide produced is in the rutile form.
- phosphate is included, and phosphate is adsorbed on the surface of titanium dioxide as shown in Scheme 3 below.
- the phosphate anion (H 2 PO 4 - ) is strongly adsorbed to the protonated Ti oxide to form a spherical complex.
- phosphate anions (H 2 PO 4 - ) strongly adsorbed on the surface of Ti oxide hinder aggregation and thus hinder particle growth. Accordingly, the particle shape of the anatase-type titanium dioxide is made to be close to a sphere, and the particle size is reduced.
- a step of hydrolyzing the mixed solution to form anatase-type titanium dioxide is performed.
- the step of hydrolyzing to form anatase-type titanium dioxide is performed by adding water and at 90 to 110° C. for 150 to 210 minutes. At this time, sodium hydroxide may be further included together with water.
- the amount of water added may include 25 to 40 parts by weight based on 100 parts by weight of the mixed solution.
- the amount of sodium hydroxide added may include 2 to 6 parts by weight based on 100 parts by weight of the mixed solution.
- the product obtained after hydrolysis is calcined to produce anatase-type titanium dioxide. Calcining may be performed at 600 to 900 °C.
- FIG. 11 is a schematic flow chart of a titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention.
- the titanium dioxide crystal control method (M400) includes preparing a titanium seed solution (S410), adding the titanium seed solution to a titanium-containing hydrochloric acid solution to prepare a mixed solution A step (S420) and a step of hydrolyzing the mixed solution to form anatase-type titanium dioxide (S430).
- the titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention the same part as the anatase titanium dioxide manufacturing method (M300) using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention described above Omit the description of .
- the titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention forms rutile-type titanium dioxide by not adding a crystal selector in the step of preparing a mixed solution (S430), Anatase-type titanium dioxide is formed by adding a crystal selector.
- the crystal selector is sulfuric acid
- the crystal selector is added in an amount of 10 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution
- the crystal selector is In the case of phosphoric acid
- the crystal selector is added in an amount of 0.4 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution. Add more than one part by weight.
- the crystal selection agent is less than the upper limit, the anatase type and the rutile type are mixed in the titanium dioxide produced.
- the ratio of the rutile type and the anatase type in the formed titanium dioxide is adjusted by controlling the addition amount of the crystal selector.
- the crystal selector when no crystal selector is added, more than 99 wt% of the titanium dioxide produced is in the rutile type.
- the spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst.
- the particle size of the spent denitrification catalyst powder was ⁇ 212 ⁇ m.
- a mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder.
- the mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 1500 kgf/cm 2 using a crank-type press. It was confirmed that the temperature of 50 ° C. was increased by exotherm during the manufacturing process of the pseudo-shaped body.
- the prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
- the alkali sintered compact was pulverized, and valuable metals were leached therefrom.
- Water leaching was sufficiently performed by adding 30 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water. The temperature of the water subjected to water leaching was 80 °C. After performing water leaching, the solids were filtered to separate the leachate and the solids.
- Acid leaching was performed by adding 30 parts by weight of solids to 100 parts by weight of hydrochloric acid. Acid leaching was carried out at 60 °C for 3 hours. As a result of acid leaching, a titanium-containing hydrochloric acid solution containing 10 wt.% of titanium and having a molar concentration of 9 M hydrochloric acid was prepared.
- a titanium seed solution was prepared using some of the titanium-containing hydrochloric acid solution.
- the titanium seed solution was prepared by mixing 0.5 kg of 20 wt.% sodium hydroxide per 1 kg of the titanium-containing hydrochloric acid solution to prepare a seed mixture solution, and 0.75 kg of water was added per 1.5 kg of the seed mixture solution. After stirring at 70 °C for 30 minutes to prepare a titanium seed solution.
- the precipitate precipitated in the reaction process of the first to third samples was separated and calcined at 600 ° C. for 1 hour to recover titanium dioxide.
- FIG. 12 is an XRD measurement result of titanium dioxide when a crystal selector is not added in the process of hydrolysis using a titanium-containing hydrochloric acid solution
- FIG. 13 is an XRD measurement result when a crystal selector is added.
- the crystalline form of the prepared titanium dioxide is a rutile form, but as shown in FIG. 12, when the crystal selector is not added, the crystalline form of the prepared titanium dioxide is a rutile form, but as shown in FIG.
- Titanium dioxide was prepared in the same manner as in Example 8, but phosphoric acid was used as a crystal selector, and the crystal form of titanium dioxide according to the phosphoric acid content was investigated and shown in Table 4.
- the content of phosphoric acid is based on 100 parts by weight of titanium-containing hydrochloric acid solution.
- Crystal selection agent content (wt.%) 0 0.2 0.3 0.4 0.5 Anatase type (%) ⁇ 1 66 90 96 99 ⁇ Rutile type (%) 99 ⁇ 34 10 4 ⁇ 1
- titanium dioxide produced when phosphoric acid is not added has a rutile type in nature, and the amount of anatase type titanium dioxide increases as the phosphoric acid content increases. Then, when the content of phosphoric acid exceeds the upper limit (0.5 parts by weight), the prepared titanium dioxide is in fact anatase type.
- Titanium dioxide was prepared in the same manner as in Example 8, but phosphoric acid was used as a crystal selector, and the particle size and particle shape of titanium dioxide according to the content of phosphoric acid were investigated and shown in FIGS. 14 to 20.
- the content of phosphoric acid is based on 100 parts by weight of titanium-containing hydrochloric acid solution.
- FIGS. 16 to 20 are titanium-containing hydrochloric acid
- FIG. 16 is the result of SEM analysis when phosphoric acid is not added
- FIG. 17 is the result of SEM analysis when 0.2 part by weight of phosphoric acid is added
- FIG. 18 is the result of SEM analysis when 0.3 part by weight of phosphoric acid is added
- FIG. 19 is a SEM analysis result when 0.4 parts by weight of phosphoric acid is added
- FIG. 20 is a SEM analysis result when 0.5 parts by weight of phosphoric acid is added.
- the particle size of the prepared titanium dioxide decreases in proportion as the content of phosphoric acid gradually increases.
- Titanium dioxide was prepared in the same manner as in Example 8, but the effect was investigated by comparing the presence or absence of the addition of seeds, and shown in FIGS. 21, 22 and 23.
- FIG. 21 is a SEM image of titanium dioxide particles generated when no seeds are added
- FIG. 22 is a SEM image of titanium dioxide particles when 2 wt% of seeds are added. Comparing FIG. 21 and FIG. 22, it can be seen that the crystals are not constant and the particle size is large when no seeds are added. On the other hand, when seeds are added, it can be seen that the shape is the same as that of a grain of rice, and the particle size and shape between single particles are relatively similar.
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Abstract
The invention relates to a method for extracting waste denitrification catalyst-containing valuable metals and, more specifically, to a method for extracting waste denitrification catalyst-containing valuable metals, wherein a process of compressively molding and sintering a mixture of an alkali and a raw material is employed, thereby improving an economic benefit as well as valuable metal leaching rates.
Description
본 발명은 탈질폐촉매 함유 유가금속의 추출방법에 관한 것이다. The present invention relates to a method for extracting valuable metals containing a spent denitrification catalyst.
최근 산업과 연구, 개발의 화두는 "친환경"이다. 인류는 수십년만에 지난 수천년동안의 변화를 뛰어넘었다. 그 부작용으로 환경오염이 심각한 문제로 대두되었다. Recently, the topic of industry, research, and development is “eco-friendly”. Humanity has surpassed the changes of the last few thousand years in just a few decades. As a side effect, environmental pollution has emerged as a serious problem.
여러가지 환경문제 중 하나로 화력발전소에서 발생되는 배가스에 포함된 질소산화물(NOx)이 있다. 대기중의 질소산화물은 광화학 스모그(Photochemical smog) 및 산성비의 원인이 되며 성층권의 오존파괴로 지구온난화에 심각한 영향을 미친다. 질소산화물의 지구환경 및 인체에 대한 유해성을 인식해 선진국들을 중심으로 지난 20여년에 걸쳐 매년 엄격한 질소산화물 배출량 허용기준치가 새로이 적용되고 있다. 이러한 질소산화물 배출량 허용기준치를 충족하기 위해 여러가지 기술들이 활발히 개발되고 있다. One of the various environmental problems is nitrogen oxides (NO x ) contained in flue gas generated from thermal power plants. Nitrogen oxides in the atmosphere cause photochemical smog and acid rain, and have a serious impact on global warming by destroying ozone in the stratosphere. Recognizing the harmfulness of nitrogen oxides to the global environment and human body, developed countries have newly applied strict nitrogen oxide emission standards every year over the past 20 years. Various technologies are being actively developed to meet these nitrogen oxide emission standards.
대표적인 기술 중 하나로 화력발전소에서 발생되는 배가스에 포함된 질소산화물을 제거하기 위해 배기장치에 선택적 환원 촉매(SCR: Selective Catalytic Reduction)을 설치하는 것이 있다. One of the representative technologies is to install a selective catalytic reduction (SCR) in an exhaust system to remove nitrogen oxides contained in exhaust gas generated from a thermal power plant.
그런데 선택적 환원 촉매는 사용시간이 약 20,000 시간이며, 그 이후에는 몇번의 재생 이후 폐기되어 탈질폐촉매가 되어 폐기된다. 문제는 질소산화물 문제를 해결한 탈질폐촉매가 2차 폐기물이 된다는 점이다.However, the selective reduction catalyst is used for about 20,000 hours, after which it is discarded after several regenerations and becomes a waste denitrification catalyst. The problem is that the waste denitrification catalyst that solved the nitrogen oxide problem becomes secondary waste.
탈질폐촉매가 2차 폐기물이 되어 또 다른 환경오염의 원인이 되는것을 최대한 방지하기 위해서는 탈질폐촉매를 활용할 수 있는 방안이 필요하다. In order to prevent the waste denitrification catalyst from becoming a secondary waste and causing another environmental pollution as much as possible, a plan to utilize the spent denitrification catalyst is needed.
탈질폐촉매는 제품마다 약간의 차이는 있으나 대략 70 ~ 75 wt%의 TiO2, 5~10 wt%의 WO3와 1~3 wt%의 V2O5가 포함되어 있다. 이러한 탈질폐촉매에 포함되어 있는 타이타늄(Ti), 텅스텐(W) 및 바나듐(V) 등의 고가의 유가금속을 회수할 경우 탈질폐촉매로 인한 2차 폐기물을 최소화할 수 있다. 또한, 탈질폐촉매는 세계적으로 연 40만톤 이상이 발생하고 있는 실정이며, 이로부터 유가금속을 추출할 경우 그 경제적 가치는 약 1조 3천억원이 이를 정도로 크다. The waste denitrification catalyst contains approximately 70 to 75 wt% of TiO 2 , 5 to 10 wt% of WO 3 and 1 to 3 wt% of V 2 O 5 , although there are slight differences for each product. When expensive valuable metals such as titanium (Ti), tungsten (W), and vanadium (V) included in the spent denitrification catalyst are recovered, secondary waste caused by the spent denitrification catalyst can be minimized. In addition, more than 400,000 tons of spent denitrification catalysts are generated annually worldwide, and when valuable metals are extracted from them, the economic value is so great that about 1.3 trillion won is reached.
탈질폐촉매로부터 유가금속을 추출하는 방법으로는 알칼리 배소법과 알칼리 공융법이 있다. 알칼리 배소법은 탈질폐촉매와 탄산나트륨을 혼합하여 로터리킬른에서 약 600 ~ 800 ℃에서 반응시키는 방법이며, 알칼리 용융법은 탈질폐촉매와 탄산나트륨 혼합분말을 반응로에 투입하여 1,000 ℃ ~ 1,100 ℃에서 공융시켜 반응시키는 방법이다. 알칼리배소법은 텅스텐의 침출율이 80~90% 수준, 바나듐의 침출율이 40 ~ 50% 수준에 불과하여 침출율이 낮다는 문제가 있다. 알칼리 용융법은 텅스텐의 침출율이 10 ~ 98% 수준, 바나듐의 침출율이 10~99% 수준으로 침출율의 상한선은 높지만 용융물의 후처리 방법에 따라 침출율 편차가 과도하게 크다는 문제가 있다. 또한, 알칼리 용융법은 1000 ℃가 넘는 고온에서 수행되기 때문에 탄산나트륨과 같은 알칼리제가 도가니와 부반응으로 소모되어 재질 선택에 어려움이 있고, 내부 대류에 의한 분말의 비산으로 원료 손실이 약 5% 가량 발생한다. As methods for extracting valuable metals from waste denitrification catalysts, there are an alkali roasting method and an alkali eutectic method. The alkali roasting method is a method in which waste denitrification catalyst and sodium carbonate are mixed and reacted in a rotary kiln at about 600 ~ 800 ℃. way to react. The alkaline roasting method has a problem in that the leaching rate of tungsten is only 80 to 90% and that of vanadium is only 40 to 50%, so the leaching rate is low. The alkali melting method has a high leaching rate of 10 to 98% for tungsten and 10 to 99% for vanadium. In addition, since the alkali melting method is performed at a high temperature of over 1000 ° C, alkali agents such as sodium carbonate are consumed in a side reaction with the crucible, making it difficult to select materials, and about 5% of raw material loss occurs due to scattering of powder by internal convection. .
선행발명 "In-Hyeok Choi et al., "Spent V2O5-WO3/TiO2 catalyst processing for valuable metals by soda roasting-water leaching", Hydrometallurgy Volume 175, January 2018, Pages 292-299"에 개시되어 있는 것과 같이 탈질폐촉매에 존재하는 바나듐과 텅스텐을 수침출이 가능한 상태로 변화시키고, 물을 이용해 탈질폐촉매로부터 바나듐과 텅스텐을 침출시켜 바나듐-텅스텐 함유 용액을 마련한다. 그 다음 바나듐-텅스텐 함유 용액에서 바나듐과 텅스텐을 서로 분리한다. 종래에는 바나듐-텅스텐 함유 용액에 침전제로 염화칼슘(CaCl2)를 이용하는데, 염화칼슘은 강알칼리인 침출액 내에서 pH에 따라 텅스텐 또는 바나듐을 선택적으로 침전시킨다. 그런데 이와 같은 종래의 방법은 현장에서 안정적으로 조업하기에 어려움이 있다. 강알칼리 영역에서의 pH제어가 쉽지 않을 뿐만 아니라 염화칼슘을 이용한 침전 반응은 pH에 예민하여 적정 pH를 벗어날 경우 바나듐과 텅스텐이 함께 공침하게 된다. 공침에 의해 바나듐과 텅스텐은 분리도가 낮아지고, 추출율도 낮아진다.Prior invention "In-Hyeok Choi et al., "Spent V 2 O 5 -WO 3 /TiO 2 catalyst processing for valuable metals by soda roasting-water leaching", Hydrometallurgy Volume 175, January 2018, Pages 292-299" As described above, vanadium and tungsten present in the waste denitrification catalyst are changed into a state in which water leaching is possible, and vanadium and tungsten are leached from the spent denitrification catalyst using water to prepare a vanadium-tungsten containing solution. The vanadium and tungsten are then separated from each other in the vanadium-tungsten containing solution. Conventionally, calcium chloride (CaCl 2 ) is used as a precipitant in a vanadium-tungsten-containing solution, and calcium chloride selectively precipitates tungsten or vanadium according to pH in a strong alkaline leachate. However, such a conventional method is difficult to operate stably in the field. Not only is it not easy to control the pH in the strong alkali range, but the precipitation reaction using calcium chloride is sensitive to pH, so vanadium and tungsten co-precipitate when the pH is out of the proper range. By co-precipitation, the separation of vanadium and tungsten is lowered, and the extraction rate is also lowered.
한편, 탈질폐촉매에는 타이타늄이 포함되어 있다. 탈질폐촉매에 포함되어 있는 타이타늄을 추출할 경우 이용하는 방법에 따라 이산화타이타늄의 결정형이 루타일(Rutile) 또는 아나타제(Anatase)가 된다. 루타일형 이산화타이타늄은 산업적으로 주로 백색안료로 사용된다. 루타일형 이산화타이타늄은 염소법에 의해 제조되는데, 염소법은 TiCl4의 가열증기를 가열산소와 반응시켜 고온 기상에서 TiO2입자를 형성시키는 방법을 의미한다, 염소법으로는 루타일형 이산화타이타늄만 제조된다. 아나타제형 이산화타이타늄은 안료, 탈질촉매, 광촉매 등 산업적으로 다양한 곳에 사용되며, 루타일형 이산화타이타늄에 비해 범용적으로 사용된다. 아나타제형 이산화타이타늄은 황산법에 의해 제조되는데, 황산법은 TiOSO4의 수용액을 열가수분해해서 얻어진 침전물인 아나타제형 이산화타이타늄 미립자를 800~1000 °C로 소성하여 성장시킨 후 원하는 크기의 이산화타이타늄을 얻는 방법이다. 황산법으로는 씨드의 첨가 조절에 의해 아나타제형 또는 루타일형 이산화타이타늄을 선택적으로 제조할 수 있다. 염소법은 고도화된 설비가 필요할 뿐만 아니라 루타일형 이산화타이타늄만 제조할 수 있다. 황산법은 아나타제형 또는 루타일형 이산화타이타늄을 선택적으로 제조할 수는 있지만, 루타일형 이산화타이타늄을 제조하기 위해서는 약 900 ℃의 온도에서 3 ~ 8시간 동안 소성이 필요할 뿐만 아니라 소성 과정에서 입자 응집으로 인해 추가 미분화하는 공정이 필요하다. Meanwhile, the waste denitrification catalyst contains titanium. When titanium contained in the spent denitrification catalyst is extracted, the crystalline form of titanium dioxide becomes rutile or anatase, depending on the method used. Rutile type titanium dioxide is industrially mainly used as a white pigment. Rutile-type titanium dioxide is produced by the chlorine method. The chlorine method refers to a method of reacting heated steam of TiCl 4 with heated oxygen to form TiO 2 particles in a high-temperature gas phase. The chlorine method produces only rutile-type titanium dioxide. do. Anatase-type titanium dioxide is used in a variety of industries, such as pigments, denitrification catalysts, and photocatalysts, and is more universally used than rutile-type titanium dioxide. Anatase-type titanium dioxide is produced by the sulfuric acid method. The sulfuric acid method is a method of obtaining titanium dioxide of a desired size after firing and growing anatase-type titanium dioxide particles, which are precipitates obtained by thermally hydrolyzing an aqueous solution of TiOSO 4 , at 800 ~ 1000 °C. am. In the sulfuric acid method, anatase-type or rutile-type titanium dioxide can be selectively produced by controlling the addition of seeds. The chlorine method not only requires advanced equipment, but can only produce rutile-type titanium dioxide. Although the sulfuric acid method can selectively produce anatase-type or rutile-type titanium dioxide, in order to produce rutile-type titanium dioxide, firing at a temperature of about 900 ° C. for 3 to 8 hours is required, as well as particle aggregation during the firing process. A process of micronization is required.
본 발명의 일 목적은 종래에 비해 유가금속의 침출율이 현저히 향상된 탈질폐촉매 함유 유가금속 추출방법을 제공하는 것이다. One object of the present invention is to provide a method for extracting valuable metals containing a spent denitrification catalyst, in which the leaching rate of valuable metals is remarkably improved compared to the prior art.
나아가 본 발명의 또 다른 목적은 탈질폐촉매로부터 추출하는 이산화타이타늄의 결정의 형태나 입자 · 입형을 조절할 수 있는 새로운 방안을 제공하는 것이다. Furthermore, another object of the present invention is to provide a new way to control the crystal shape or particle/granular shape of titanium dioxide extracted from the spent denitrification catalyst.
한편, 본 발명의 명시되지 않은 또 다른 목적들은 하기의 상세한 설명 및 그 효과로부터 용이하게 추론할 수 있는 범위 내에서 추가적으로 고려될 것이다.Meanwhile, other unspecified objects of the present invention will be additionally considered within the scope that can be easily inferred from the following detailed description and effects thereof.
이상에서 설명한 문제를 해결하기 위해 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속의 추출방법은 탈질폐촉매 파우더와 알칼리제의 혼합물을 압축 성형 및 소결하여 알칼리 소결 성형체를 제조하는 단계; 및 상기 알칼리 소결 성형체로부터 유가금속을 침출하는 단계를 포함한다. In order to solve the problems described above, a method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention comprises the steps of compressing and sintering a mixture of a spent denitrification catalyst powder and an alkali agent to prepare an alkali sintered molded body; and leaching the valuable metal from the alkali sintered molded body.
일 실시예에 있어서, 상기 알칼리 소결 성형체로부터 유가금속을 침출하는 단계는, 알칼리 소결 성형체를 물에 반응시켜 바나듐-텅스텐 함유 용액을 추출하고, 알칼리 소결 성형체를 물에 반응시킨 후 여과하여 분리한 고형물로부터 염산을 이용하여 타이타늄 함유 염산 용액을 추출하는 것을 특징으로 할 수 있다.In one embodiment, in the step of leaching the valuable metal from the alkali sintered molded body, the alkali sintered molded body is reacted with water to extract a vanadium-tungsten-containing solution, the alkali sintered molded body is reacted with water, and then filtered to separate the solids It may be characterized by extracting a titanium-containing hydrochloric acid solution using hydrochloric acid from.
일 실시예에 있어서, 상기 바나듐-텅스텐 함유 용액을 추출한 후 추출한 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐을 분리하는 단계가 수행되며, 상기 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐을 분리하는 단계는 (a-1) 바나듐-텅스텐 함유 용액에 전처리를 수행하여 용액내 바나듐의 이온 상태를 전환시키는 단계; (a-2) 전처리한 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계; (a-3) 반응시킨 바나듐-텅스텐 함유 용액을 유기 용매와 수 용매로 분리하는 단계; (a-4) 상기 유기 용매에서 텅스텐을 추출하는 단계; (a-5) 상기 수 용매에서 바나듐의 이온 상태를 재전환시키는 단계; (a-6) 바나듐이 포함된 상기 수용매에 추출제를 첨가하여 반응시키는 단계; 및 (a-7) 유기용매에 포함된 바나듐을 추출하는 단계;를 포함한다.In one embodiment, the step of separating vanadium-tungsten in the extracted vanadium-tungsten-containing solution after extracting the vanadium-tungsten-containing solution is performed, and the step of separating vanadium-tungsten in the vanadium-tungsten-containing solution (a -1) converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution; (a-2) reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution; (a-3) separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent; (a-4) extracting tungsten from the organic solvent; (a-5) reconverting the ionic state of vanadium in the aqueous solvent; (a-6) reacting by adding an extractant to the aqueous medium containing vanadium; and (a-7) extracting vanadium contained in the organic solvent.
일 실시예에 있어서, 상기 타이타늄 함유 염산 용액으로부터 아나타제형 이산화타이타늄을 형성하는 단계가 수행되며, 상기 타이타늄 함유 염산 용액으로부터 아나타제형 이산화타이타늄을 형성하는 단계는, (b-1) 제1타이타늄 함유 염산 용액 및 상기 제1타이타늄 함유 염산 용액과 조성이 같거나 다른 제2타이타늄 함유 염산 용액을 마련하는 단계; (b-2) 상기 제1타이타늄 함유 염산 용액에 수산화나트륨을 첨가하고 혼합하여 제1혼합용액을 제조하고, 상기 제1혼합용액에 물을 첨가하여 타이타늄 씨드용액을 제조하는 단계; (b-3) 상기 타이타늄 씨드용액과 생성되는 이산화타이타늄의 결정형을 아나타제형으로 만드는 결정 선택제를 상기 제2타이타늄 함유 염산 용액에 첨가하여 혼합 용액을 제조하는 단계; 및 (b-4) 상기 혼합 용액에 물을 첨가하여 가수분해를 통해 아나타제형 이산화타이타늄을 형성하는 단계;를 포함하는 것을 특징으로 한다. In one embodiment, the step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution is performed, and the step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution is (b-1) first titanium-containing hydrochloric acid preparing a solution and a second titanium-containing hydrochloric acid solution having the same composition as or a different composition from the first titanium-containing hydrochloric acid solution; (b-2) preparing a first mixed solution by adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution, and adding water to the first mixed solution to prepare a titanium seed solution; (b-3) preparing a mixed solution by adding a crystal selector to the second titanium-containing hydrochloric acid solution to convert the titanium seed solution and the resulting titanium dioxide into an anatase crystal form; and (b-4) forming anatase-type titanium dioxide through hydrolysis by adding water to the mixed solution.
일 실시예에 있어서, 상기 타이타늄 함유 염산 용액으로부터 형성되는 이산화타이타늄의 결정형을 제어하는 단계가 수행되며, 상기 타이타늄 함유 염산 용액으로부터 형성되는 이산화타이타늄의 결정형을 제어하는 단계는, (c-1) 제1타이타늄 함유 염산 용액 및 상기 제1타이타늄 함유 염산 용액과 조성이 같거나 다른 제2타이타늄 함유 염산 용액을 마련하는 단계; (c-2) 상기 제1타이타늄 함유 염산 용액에 수산화나트륨을 첨가하고 혼합하여 제1혼합용액을 제조하고, 상기 제1혼합용액에 물을 첨가하여 타이타늄 씨드용액을 제조하는 단계; (c-3) 상기 타이타늄 씨드용액을 상기 제2타이타늄 함유 염산 용액에 첨가하여 혼합 용액을 제조하되, 결정 선택제에 의해 제조할 이산화타이타늄의 결정형을 선택하는 단계; 및 (c-4) 상기 혼합 용액을 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계;를 포함하고, 상기 (c-3) 단계에서 결정 선택제를 첨가하지 않음으로써 루타일형 이산화타이타늄을 형성하고, 결정 선택제를 첨가함으로써 아나타제형 이산화타이타늄을 형성하는 것을 특징으로 한다. In one embodiment, the step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution is performed, and the step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution, (c-1) preparing a first titanium-containing hydrochloric acid solution and a second titanium-containing hydrochloric acid solution having the same composition as or different from the first titanium-containing hydrochloric acid solution; (c-2) adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution to prepare a first mixed solution, and adding water to the first mixed solution to prepare a titanium seed solution; (c-3) preparing a mixed solution by adding the titanium seed solution to the second titanium-containing hydrochloric acid solution, selecting a crystalline form of titanium dioxide to be produced by a crystal selector; and (c-4) hydrolyzing the mixed solution to form anatase-type titanium dioxide, wherein in step (c-3), rutile-type titanium dioxide is formed by not adding a crystal selector, and It is characterized by forming anatase-type titanium dioxide by adding a selective agent.
본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법은 탈질폐촉매 파우더와 알칼리제를 혼합, 성형 및 소결하여 알칼리 소결 성형체를 제조한 뒤에 알칼리 소결 성형체로부터 텅스텐, 바나듐 및 타이타늄을 추출함으로써 텅스텐과 바나듐의 침출율이 99% 이상이 되며, 타이타늄의 침출율도 95% 이상이 되는 효과가 있다.In the method for extracting valuable metals containing a waste denitrification catalyst according to an embodiment of the present invention, an alkali sintered molded body is prepared by mixing, molding, and sintering spent denitrification catalyst powder and an alkali agent, and then tungsten, vanadium, and titanium are extracted from the alkali sintered body to obtain tungsten. The leaching rate of vanadium and vanadium is 99% or more, and the leaching rate of titanium is also 95% or more.
또한, 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법은 알칼리 소결 성형체를 제조하고, 이를 이용하여 탈질폐촉매로부터 유가금속을 추출하기 때문에 공정 간 비산 분말이 발생하는 것을 최소화 하여 비산 분말 발생으로 인한 약 5%의 원료 손실을 방지할 수 있다. 더욱이 제조된 알칼리 소결 성형체로부터 침출법으로 유가금속을 추출하기 때문에 알칼리 용융법에서 문제되는 고온 알칼리 부식(부반응) 문제를 근본적으로 해결할 수 있으며, 알칼리 용융법보다 에너지 소모가 현저히 낮고, 공정 구현 난이도가 낮은 장점이 있다.In addition, the method for extracting valuable metals containing waste denitrification catalysts according to an embodiment of the present invention manufactures alkali sintered molded bodies and uses them to extract valuable metals from waste denitrification catalysts. About 5% of raw material loss due to powder generation can be prevented. Moreover, since valuable metals are extracted from the manufactured alkali sintered molded body by the leaching method, it is possible to fundamentally solve the problem of high-temperature alkali corrosion (side reaction), which is a problem in the alkali melting method, and energy consumption is significantly lower than that of the alkali melting method. There are low advantages.
본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법은 은 가수분해를 통해 이산화타이타늄을 생성하되, 제조과정에서 결정 선택제를 이용함으로써 아나타제형 이산화타이타늄을 제조하거나, 제조과정에서 결정 선택제의 첨가 여부에 의해 제조되는 이산화타이타늄의 결정형을 루타일형 또는 아나타제형으로 선택할 수 있으며, 나아가 결정 선택제의 첨가량을 이용하여 제조되는 이산화타이타늄 중 루타일형 및 아나타제형의 비를 제어할 수 있다. In the method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention, titanium dioxide is produced through silver hydrolysis, but anatase-type titanium dioxide is produced by using a crystal selector in the manufacturing process, or The crystalline form of titanium dioxide produced can be selected as a rutile form or an anatase form, and furthermore, the ratio of the rutile form and anatase form in the produced titanium dioxide can be controlled by using the addition amount of the crystal selector.
여기에서 명시적으로 언급되지 않은 효과라 하더라도, 본 발명의 기술적 특징에 의해 기대되는 이하의 명세서에서 기재된 효과 및 그 잠정적인 효과는 본 발명의 명세서에 기재된 것과 같이 취급됨을 첨언한다.It is added that even if the effects are not explicitly mentioned here, the effects described in the following specification expected by the technical features of the present invention and their provisional effects are treated as described in the specification of the present invention.
도 1은 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법의 개략적 플로우 차트이다.1 is a schematic flowchart of a method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법에서 이용되는 알칼리 소결 성형체의 조성에 따른 유가금속의 침출율을 측정한 결과이다. 2 is a result of measuring the leaching rate of valuable metals according to the composition of an alkali sintered molded article used in the method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention.
도 3는 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법에서 이용되는 알칼리 소결 성형체의 소결 온도에 따른 유가금속의 침출율을 측정한 결과이다. 3 is a result of measuring the leaching rate of valuable metals according to the sintering temperature of an alkali-sintered molded body used in the method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법에서 이용되는 알칼리 소결 성형체의 여러가지 형태를 개략적으로 도시한 것이다. 4 schematically illustrates various types of alkali sintered molded articles used in the method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법의 개략적 플로우 차트이다.5 is a schematic flow chart of a method for separating vanadium-tungsten in a vanadium-tungsten-containing solution according to an embodiment of the present invention.
도 6은 본 발명의 다른 실시예에 따른 바나듐-텅스텐 분리 시스템의 개략적 구성도이다. 6 is a schematic configuration diagram of a vanadium-tungsten separation system according to another embodiment of the present invention.
도 7은 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법에서 전처리시 pH에 따른 텅스텐 용매 추출루트에서의 바나듐과 텅스텐의 추출율을 측정한 결과이다. 7 is a result of measuring the extraction rate of vanadium and tungsten in a tungsten solvent extraction route according to pH during pretreatment in a vanadium-tungsten separation method in a vanadium-tungsten-containing solution according to an embodiment of the present invention.
도 8은 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법에서 전처리시 전처리제의 함량에 따른 텅스텐 용매 추출루트에서의 바나듐과 텅스텐의 추출율을 측정한 결과이다. 8 is a result of measuring the extraction rate of vanadium and tungsten in the tungsten solvent extraction route according to the content of the pretreatment agent during the pretreatment in the vanadium-tungsten separation method in the vanadium-tungsten containing solution according to an embodiment of the present invention.
도 9는 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법에서 추출제의 함량에 따른 텅스텐 용매 추출루트에서의 바나듐과 텅스텐의 추출율을 측정한 결과이다. 9 is a result of measuring the extraction rate of vanadium and tungsten in the tungsten solvent extraction route according to the content of the extractant in the vanadium-tungsten separation method in the vanadium-tungsten containing solution according to an embodiment of the present invention.
도 10은 본 발명의 일 실시예에 따른 타이타늄 함유 염산용액을 이용한 아나타제형 이산화타이타늄 제조 방법의 개략적 플로우 차트이다.10 is a schematic flow chart of a method for preparing anatase-type titanium dioxide using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention.
도 11은 본 발명의 다른 실시예에 따른 타이타늄 함유 염산용액을 이용한 이산화타이타늄 결정 제어 방법의 개략적 플로우 차트이다.11 is a schematic flow chart of a titanium dioxide crystal control method using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention.
도 12는 타이타늄 함유 염산용액을 이용하여 가수분해 하는 과정에 결정 선택제를 첨가하지 않은 경우의 이산화타이타늄의 XRD 측정 결과이며, 도13은 결정 선택제를 첨가한 경우의 XRD 측정 결과이다. 12 is an XRD measurement result of titanium dioxide when a crystal selector is not added in the process of hydrolysis using a titanium-containing hydrochloric acid solution, and FIG. 13 is an XRD measurement result when a crystal selector is added.
도 14 및 도 15는 타이타늄 함유 염산용액을 이용하여 가수분해 하는 과정에 결정 선택제(제2형)의 양에 따른 이산화타이타늄의 입도를 측정한 결과이다. 14 and 15 are results of measuring the particle size of titanium dioxide according to the amount of the crystal selector (type 2) in the process of hydrolysis using a titanium-containing hydrochloric acid solution.
도 16 내지 도 20은 타이타늄 함유 염산용액을 이용하여 가수분해 하는 과정에 결정 선택제(제2형)의 양에 따른 이산화타이타늄의 입형을 촬영한 사진이다. 16 to 20 are photographs taken of the particle shape of titanium dioxide according to the amount of the crystal selector (type 2) in the process of hydrolysis using a titanium-containing hydrochloric acid solution.
도 21으 씨드를 첨가하지 않은 경우의 생성되는 이산화타이타늄 입자의 SEM 이미지이며, 도 22는 씨드를 4wt% 첨가한 경우의 이산화타이타늄 입자의 SEM 이미지이다.21 is a SEM image of titanium dioxide particles generated when no seeds are added, and FIG. 22 is a SEM image of titanium dioxide particles when 4 wt% of seeds are added.
도 23은 시간에 따른 가수분해율을 측정한 결과로서 씨드의 유무에 따른 영향을 비교한 것이다.23 compares the effect of the presence or absence of seeds as a result of measuring the hydrolysis rate over time.
첨부된 도면은 본 발명의 기술사상에 대한 이해를 위하여 참조로서 예시된 것임을 밝히며, 그것에 의해 본 발명의 권리범위가 제한되지는 아니한다.It is revealed that the accompanying drawings are illustrated as references for understanding the technical idea of the present invention, and thereby the scope of the present invention is not limited thereto.
이하, 도면을 참조하여 본 발명의 다양한 실시예가 안내하는 본 발명의 구성과 그 구성으로부터 비롯되는 효과에 대해 살펴본다. 본 발명을 설명함에 있어서 관련된 공지기능에 대하여 이 분야의 기술자에게 자명한 사항으로서 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략한다.Hereinafter, with reference to the drawings, look at the configuration of the present invention guided by various embodiments of the present invention and the effects resulting from the configuration. In the description of the present invention, if it is determined that a related known function may unnecessarily obscure the subject matter of the present invention as an obvious matter to those skilled in the art, the detailed description thereof will be omitted.
아래에서는 본 발명을 3가지 관점에서 설명한다. 첫번째는 탈질폐촉매로부터 유가금속을 추출하되, 알칼리 소결 성형체를 이용하여 유가금속의 침출율을 향상시킬 수 있는 방안이며, 두번째는 탈질폐촉매로부터 수침출하여 얻은 바나듐-텅스텐 함유 용액에서 바나듐과 텅스텐을 높은 분리도를 가지도록 분리하기 위한 방안이며, 세번째는 탈질폐촉매로부터 수침출한 후 수득한 고형물로부터 염산을 이용하여 추출한 타이타늄 함유 염산 용액에서 아나타제형 이산화티탄을 형성하는 방안이다. Below, the present invention will be described from three perspectives. The first is to extract valuable metals from the spent denitrification catalyst and improve the leaching rate of the valuable metals by using an alkali sintered molded product. The third method is to form anatase-type titanium dioxide in a hydrochloric acid solution containing titanium extracted from the solid obtained after water leaching from the spent denitrification catalyst using hydrochloric acid.
1. 일칼리 소결 성형체를 이용한 탈질폐촉매 함유 유가금속 추출 1. Extraction of valuable metals containing waste denitrification catalyst using Ilkali sintered molding
본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법은 기존에 폐기처리되던 탈질폐촉매로부터 유가금속을 추출하여 부가가치를 창출하는 것에 목적이 있다. ‘화력발전소 등에서 사용 후 수명을 다한 탈질 폐촉매를 활용하여 유가금속을 추출, 분리, 정제하여 소재화 하는 것이다. 특히, 본 발명의 알칼리 소결 성형체를 이용함으로써, 탈질폐촉매 함유 유가금속 추출방법의 양산성을 확보했다는 것에 의의가 있다. An object of the method for extracting valuable metals containing a waste denitrification catalyst according to an embodiment of the present invention is to create added value by extracting valuable metals from a waste denitrification catalyst that has been previously disposed of. ‘Utilizing waste denitrification catalysts that have reached the end of their lifespan after use in thermal power plants, etc., valuable metals are extracted, separated, and refined to make them into materials. In particular, by using the alkali sintered molded body of the present invention, it is significant that the mass productivity of the method for extracting valuable metals containing a spent denitrification catalyst is secured.
탈질폐촉매의 조성은 제품마다 차이가 있으나, 일반적으로 70 ~ 75 wt%의 TiO2, 8~10 wt%의 SiO2, 5~10 wt%의 WO3, 1~3 wt%의 V2O5, 2~5 wt%의 CaO, 2~5 wt%의 Al2O3, 2~5 wt%의 SO3, 0.2~0.4 wt%의 Fe2O3의 조성을 가진다. 탈질폐촉매에 포함된 여러가지 금속 중에 텅스텐(W), 바나듐(V) 및 타이타늄(Ti)은 희귀금속으로 다양한 산업에서 요구되고 있다. 본 발명은 탈질폐촉매로부터 텅스텐(W), 바나듐(V) 및 타이타늄(Ti)과 같은 유가금속을 추출한다.The composition of the spent denitrification catalyst varies from product to product, but generally contains 70 to 75 wt% of TiO 2 , 8 to 10 wt% of SiO 2 , 5 to 10 wt% of WO 3 , and 1 to 3 wt% of V 2 O. 5 , 2-5 wt% of CaO, 2-5 wt% of Al 2 O 3 , 2-5 wt% of SO 3 , and 0.2-0.4 wt% of Fe 2 O 3 . Among various metals included in the spent denitrification catalyst, tungsten (W), vanadium (V), and titanium (Ti) are rare metals and are required in various industries. The present invention extracts valuable metals such as tungsten (W), vanadium (V) and titanium (Ti) from spent denitrification catalysts.
탈질폐촉매로부터 유가금속을 추출하기 위해서는 탈질폐촉매에 포함되어 있는 유가금속을 침출가능한 형태로 변환하고, 각각의 유가금속에 맞는 침출방법을 이용하여 각 유가금속을 분리하여 침출하여야 한다. In order to extract valuable metals from the spent denitrification catalyst, the valuable metals contained in the spent denitrification catalyst must be converted into leachable forms, and each valuable metal must be separated and leached using a leaching method suitable for each valuable metal.
유가금속의 높은 침출율을 이루기 위해서는 어떠한 침출방법을 이용하는지 여부도 중요하지만, 그 전 단계인 탈질폐촉매에 포함되어 있는 유가금속을 침출가능한 형태로 변환시키는 것이 중요하다. 탈질폐촉매에 포함되어 있는 유가금속이 침출가능한 형태가 되지 않는다면, 그 후속 단계에서 아무리 뛰어난 기술이 적용되더라도 침출할 수 있는 유가금속에 한계가 있을 수밖에 없다. 예컨대, 용융, 배소, 소결 등의 전처리가 전혀 없이 탈질폐촉매로부터 바나듐 및 텅스텐을 직접 침출할 경우 침출율은 50 ~ 70%에 그친다. 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법은 탈질폐촉매에 함유된 유가금속을 침출가능한 형태로 변환시키는 기술에 관한 것인데, 종래의 기술들에 비해 양산성과 공정 효율을 향상시켰다는 장점이 있다.In order to achieve a high leaching rate of valuable metals, it is important which leaching method is used, but it is important to convert the valuable metals contained in the waste denitrification catalyst, which is the previous step, into a leachable form. If the valuable metals contained in the waste denitrification catalyst are not in a leachable form, there is no choice but to limit the valuable metals that can be leached no matter how excellent technology is applied in the subsequent step. For example, when vanadium and tungsten are directly leached from the spent denitrification catalyst without any pretreatment such as melting, roasting, or sintering, the leaching rate is only 50 to 70%. A method for extracting valuable metals containing a spent denitrification catalyst according to an embodiment of the present invention relates to a technology for converting valuable metals contained in a spent denitrification catalyst into a leachable form, which has improved mass productivity and process efficiency compared to conventional technologies. There are advantages.
어떠한 기술이 양산성을 갖추기 위해서는 대량생산을 하더라도 경제성이 유지되어야 하고, 일정 이상의 품질이 보장되어야 한다. 그런데 탈질폐촉매에서 유가금속을 침출하기 위한 종래의 알칼리 배소법과 알칼리 용융법은 양산에 적용하기에 한계가 있다. 구체적으로 알칼리 배소법은 유가금속의 침출율이 너무 낮다는 문제가 있다. 또한 알칼리 용융법은 에너지 소비가 크고, 용융물을 다루어야 하기 때문에 공정난이도가 매우 높으며, 후공정에 따라 침출율의 편차가 너무 크기 때문에 양산에 적합하지 않다. 그리고 내부 열 대류에 의한 분말의 비산으로 원료손실이 발생한다.In order for any technology to have mass production, economic feasibility must be maintained even during mass production, and quality above a certain level must be guaranteed. However, the conventional alkali roasting method and alkali melting method for leaching valuable metals from waste denitrification catalysts have limitations in their application to mass production. Specifically, the alkaline roasting method has a problem in that the leaching rate of valuable metals is too low. In addition, the alkali melting method is not suitable for mass production because the energy consumption is high, the process difficulty is very high because the melt must be handled, and the leaching rate varies greatly depending on the subsequent process. In addition, raw material loss occurs due to scattering of powder by internal heat convection.
도 1은 이와 같은 종래기술의 한계를 극복한 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법(M100)의 개략적 플로우 차트이다.1 is a schematic flowchart of a valuable metal extraction method (M100) containing a spent denitrification catalyst according to an embodiment of the present invention that overcomes the limitations of the prior art.
본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법(M100)은 알칼리 소결 성형체를 제조하는 단계(S10) 및 알칼리 소결 성형체로부터 유가금속을 침출하는 단계(S30)로 구성된다. A method for extracting valuable metals containing a spent denitrification catalyst (M100) according to an embodiment of the present invention includes preparing an alkali sintered molded body (S10) and leaching valuable metals from the alkali sintered molded body (S30).
알칼리 소결 성형체를 제조하는 단계(S10)는 탈질폐촉매를 분쇄 및 건조하여 탈질폐촉매 파우더를 마련하는 단계(S11), 탈질폐촉매 파우더와 알칼리제를 혼합하여 혼합물을 마련하는 단계(S12), 혼합물을 압축성형하여 가성형체를 형성하는 단계(S13) 및 가성형체를 소결하여 알칼리 소결 성형체를 형성하는 단계(S14)를 포함한다. The step of preparing an alkali sintered molded body (S10) includes preparing a waste denitrification catalyst powder by pulverizing and drying the spent denitrification catalyst powder (S11), preparing a mixture by mixing the spent denitrification catalyst powder and an alkali agent (S12), the mixture and forming a temporary molded body by compression molding (S13) and forming an alkali sintered molded body by sintering the temporary molded body (S14).
탈질폐촉매 파우더를 마련하는 단계(S11)는 화력발전소 등에서 수거한 탈질폐촉매를 파쇄하고 수분을 제거하기 위해 오븐에서 건조한다. In the step of preparing waste denitrification catalyst powder (S11), the spent denitrification catalyst collected from a thermal power plant is crushed and dried in an oven to remove moisture.
탈질폐촉매 파우더의 평균 입도는 250 μm 이하일 수 있으며, 더욱바람직하게는 212 μm이하일 수 있다. 탈질폐촉매 파우더의 평균 입도가 212 μm를 초과할 경우 알칼리제와의 반응성이 떨어져 유가금속의 침출율이 다소 감소하는 경향을 보인다.The average particle size of the spent denitrification catalyst powder may be 250 μm or less, more preferably 212 μm or less. When the average particle size of the spent denitrification catalyst powder exceeds 212 μm, the reactivity with alkali agents decreases, and the leaching rate of valuable metals tends to decrease slightly.
탈질폐촉매는 알칼리제와 혼합하여 혼합물을 마련한다(S12). The waste denitrification catalyst is mixed with an alkali agent to prepare a mixture (S12).
알칼리제로는 탄산나트륨(Na2CO3) 또는 수산화나트륨(NaOH) 중에 선택될 수 있다. As the alkali agent, sodium carbonate (Na 2 CO 3 ) or sodium hydroxide (NaOH) may be selected.
혼합물에 포함되는 알칼리제의 양은 탈질폐촉매 파우더 1 kg 당 0.6 kg 내지 1.2 kg일 수 있으며, 바람직하게는 0.8 kg 내지 1.0 kg일 수 있다. 1kg의 탈질폐촉매에 대해 알칼리제의 양이 0.6 kg 미만인 경우 알칼리제가 부족하여 탈질폐촉매에 포함되어 있는 유가금속이 침출가능한 형태로 변화하지 못하는 양이 증가되며, 1.2 kg을 초과할 경우에는 알칼리제가 불순물로 작용하여 후 공정에서 부반응을 일으키며, 불필요한 알칼리제 소비로 경제성이 낮아진다. 또한, 1kg의 탈질폐촉매에 대해 알칼리제의 양이 0.6kg 미만인 경우에는 타이타늄의 침출율이 80% 미만으로 낮아지는 문제가 있으며, 1.0 kg을 초과할 경우에는 침출율 증가에 기여하지 못한다. The amount of the alkali agent included in the mixture may be 0.6 kg to 1.2 kg, preferably 0.8 kg to 1.0 kg, per 1 kg of spent denitrification catalyst powder. For 1 kg of waste denitrification catalyst, if the amount of alkali agent is less than 0.6 kg, the amount of alkali agent in which valuable metals contained in waste denitrification catalyst cannot be changed into leachable form increases due to lack of alkali agent. It acts as an impurity and causes side reactions in the later process, and economical efficiency is lowered due to unnecessary consumption of alkali agent. In addition, when the amount of alkali agent for 1 kg of spent denitrification catalyst is less than 0.6 kg, there is a problem in that the leaching rate of titanium is lowered to less than 80%, and when it exceeds 1.0 kg, the leaching rate does not increase.
다음으로 혼합물을 프레스를 이용하여 압축 성형하여 가성형체를 형성한다(S13). Next, the mixture is compression molded using a press to form a temporary molded body (S13).
가성형체를 형성하는 공정은 상온에서 수행될 수 있으며, 성형 압력은 500 kgf/cm2이상일 수 있다. The process of forming the temporary molded body may be performed at room temperature, and the molding pressure may be 500 kgf/cm 2 or more.
가성형체의 형태는 도넛 기둥형, 원 기둥형 또는 사각 기둥형일 수 있으며, 바람직하게는 도넛 기둥형일 수 있다(도 4 참조). 다음 단계에서 가성형체를 고온에서 소결하는 과정이 수행되는데 도넛 기둥형일 경우 열이 도넛의 중앙과 외측으로 고르게 전달되어 보다 효율적으로 소결을 수행할 수 있다. The shape of the temporary body may be a donut columnar shape, a circular columnar shape or a quadrangular columnar shape, preferably a donut columnar shape (see FIG. 4). In the next step, a process of sintering the temporary body at a high temperature is performed. In the case of a donut columnar shape, heat is evenly transferred to the center and the outside of the donut, so that sintering can be performed more efficiently.
혼합물을 프레스를 이용하여 압축 성형할 경우 압력에 의해 발열이 발생되면서 약 40 ~ 60 ℃ 정도 온도가 상승하게 된다. 압축 성형하는 과정에서 탈질폐촉매 파우더와 알칼리제 사이의 반응 효율이 증가된다. 무엇보다 압축성형을 통해 탈질폐촉매 파우더와 알칼리제 사이의 균일 반응이 유도되는 장점이 있다. 또한, 압축 성형 공정에 의해 공정 간 비산분말이 감소된다. When the mixture is compression molded using a press, the temperature rises by about 40 to 60 ° C. as heat is generated by the pressure. In the process of compression molding, the reaction efficiency between the waste denitrification catalyst powder and the alkali agent is increased. Above all, there is an advantage in that a uniform reaction between the waste denitrification catalyst powder and the alkali agent is induced through compression molding. In addition, scattering powder between processes is reduced by the compression molding process.
그 다음 가성형체를 소결하여 알칼리 소결 성형체를 형성한다(S14). Then, the caustic molded body is sintered to form an alkali sintered molded body (S14).
가성형체를 소결하여 알칼리 소결 성형체를 형성하는 과정에서 탈질폐기물 내에 포함되어 있던 유가금속이 침출가능한 나트륨염 형태로 전환된다. In the process of sintering the caustic molded body to form the alkali sintered molded body, the valuable metals contained in the denitrification waste are converted into leachable sodium salt form.
알칼리제가 탄산나트륨인 경우 알칼리 소결 성형체에서 이루어지는 반응은 다음과 같다. When the alkali agent is sodium carbonate, the reaction performed in the alkali sintered molded body is as follows.
[반응식 1] [Scheme 1]
WO3 + Na2CO3 → Na2WO4 + CO2
WO 3 + Na 2 CO 3 → Na 2 WO 4 + CO 2
V2O5 + Na2CO3 → 2NaVO3 + CO2
V 2 O 5 + Na 2 CO 3 → 2 NaVO 3 + CO 2
TiO2 + Na2CO3 → Na2TiO3 + CO2
TiO 2 + Na 2 CO 3 → Na 2 TiO 3 + CO 2
위와 같은 반응에 의한 텅스텐과 바나듐은 수침출이 가능한 형태로 전환되며, 타이타늄의 경우에는 산에 의한 침출이 용이한 형태로 전환된다. 각 유가금속의 침출율은 알칼리 소결 성형체를 형성하는 과정에서 탈질폐기물에 포함되어 있던 유가금속이 얼마나 침출가능한 형태로 전환되는지와 비례한다. 그런데 본 발명의 일 실시예에 따른 탈질폐촉매 함유 유가금속 추출방법(M100)은 가성형체를 형성하는 과정에서 탈질폐촉매 파우더와 알칼리제 사이의 반응 효율이 증가되고, 이에 따라 알칼리 소결 성형체를 형성하는 과정에서 탈질폐기물에 포함되어 있던 유가금속이 침출 가능한 형태로 더 많이 전환된다. 이에 따라 각 유가금속의 침출율이 증가한다. Tungsten and vanadium by the above reaction are converted into a form that can be leached by water, and titanium is converted into a form that can be easily leached by acid. The leaching rate of each valuable metal is proportional to how much the valuable metal contained in the denitrification waste is converted into a leachable form in the process of forming the alkali sintered molded body. However, in the method for extracting valuable metals containing a waste denitrification catalyst (M100) according to an embodiment of the present invention, the reaction efficiency between the waste denitration catalyst powder and an alkali agent is increased in the process of forming a false body, thereby forming an alkali sintered molded body. In the process, more valuable metals contained in the denitrification waste are converted into leachable forms. Accordingly, the leaching rate of each valuable metal increases.
가성형체를 소결하는 온도는 800 내지 900 ℃일 수 있으며, 소결하는 시간은 30 내지 90분 일 수 있다. 소결 온도가 800 ℃ 미만인 경우 온도가 낮아 탈질폐기물에 포함되어 있던 유가금속이 침출가능한 형태로 충분히 전환되지 않으며, 900 ℃를 초과할 경우 알칼리제의 부반응(예를 들어, 도가니 또는 트레이와의 반응 등)에 의해 오히려 침출율이 떨어지고, 일부 용융이 발생하여 회수율이 낮아지는 문제점이 있다. 본 발명은 알칼리 소결 성형체를 제조하기 위해 소결 온도를 800 내지 900 ℃로 함으로써 침출율을 극대화할 수 있다. 구체적으로 소결온도가 800 ℃ 미만인 경우에는 바나듐 및 텅스텐의 침출율은 95% 수준이며, 타이타늄의 침출율은 50% 미만으로 낮아진다. 소결온도가 900 ℃ 초과인 경우에는 가성형체가 용융되면서 알칼리 용융공정에서 발생하는 문제가 재현되며, 또한 용융물로 배출될 경우에는 회수가 어렵고 도가니 또는 트레이에 대한 알칼리 부식을 일으키는 문제가 있다. 따라서 가성형체를 소결하는 온도가 800 ℃일 경우 바나듐 및 텅스텐의 침출율을 95 % 이상, 타이타늄의 침출율도 50% 이상으로 상승되며, 850℃일 경우 바나듐 및 텅스텐의 침출율을 98 % 이상, 타이타늄의 침출율도 90% 이상으로 상승시킬 수 있다. 나아가 가성형체를 900 ℃에서 1시간 소결한 경우 텅스텐과 바나듐의 침출율은 99% 이상이며, 타이타늄의 침출율은 95% 이상이 된다. 한편, 탈질폐촉매에 함량 2~5%로 CaO가 포함되어 있는데, 소결 중 CaO-TiO2 간 반응으로 산에 용해되지 않는 CaTiO3가 형성되는 바, 타이타늄의 침출율은 95~98%인 최대 상한선이 된다. 즉, 본 발명을 이용할 경우 텅스텐, 바나듐 및 타이타늄을 거의 상한에 가까운 정도로 침출할 수 있는 것이다. The temperature for sintering the temporary body may be 800 to 900 ° C, and the sintering time may be 30 to 90 minutes. If the sintering temperature is less than 800 ℃, the temperature is low, so the valuable metal contained in the denitrification waste is not sufficiently converted into a leachable form. Thereby, there is a problem that the leaching rate is rather lowered and the recovery rate is lowered because some melting occurs. In the present invention, the leaching rate can be maximized by setting the sintering temperature to 800 to 900 ° C. to produce an alkali sintered molded body. Specifically, when the sintering temperature is less than 800 ° C., the leaching rate of vanadium and tungsten is 95%, and the leaching rate of titanium is lowered to less than 50%. When the sintering temperature exceeds 900 ° C., the caustic mold is melted and the problems occurring in the alkali melting process are reproduced, and when it is discharged as a melt, it is difficult to recover and causes alkali corrosion to the crucible or tray. Therefore, when the sintering temperature of the temporary body is 800 ℃, the leaching rate of vanadium and tungsten rises to 95% or more, and the leaching rate of titanium rises to 50% or more. The leaching rate of can also be increased to 90% or more. Furthermore, in the case of sintering the temporary molded body at 900 ° C. for 1 hour, the leaching rate of tungsten and vanadium is 99% or more, and the leaching rate of titanium is 95% or more. On the other hand, the waste denitrification catalyst contains CaO at a content of 2-5%, and CaTiO 3 that is insoluble in acid is formed by the reaction between CaO-TiO 2 during sintering. becomes the upper limit. That is, when using the present invention, tungsten, vanadium, and titanium can be leached to a degree close to the upper limit.
알칼리 소결 성형체가 준비되면, 다음으로 알칼리 소결 성형체로부터 유가금속을 침출하는 단계(S30)가 수행된다. 다만, 유가금속의 침출 효율을 높이기 위해 먼저 알칼리 소결 성형체를 분쇄하는 단계(S20)를 수행하는 것이 바람직하다. 알칼리 소결 성형체를 분쇄하는 단계(S20)는 알칼리 소결 성형체를 평균입도 45~125 μm 정도로 분쇄한다. When the alkali sintered molded body is prepared, a step (S30) of leaching valuable metals from the alkali sintered molded body is performed. However, in order to increase the leaching efficiency of valuable metals, it is preferable to first grind the alkali sintered molded body (S20). In the step of pulverizing the alkali sintered molded body (S20), the alkali sintered molded body is pulverized to have an average particle size of about 45 to 125 μm.
준비된 알칼리 소결 성형체로부터 유가금속을 침출한다(S30). Valuable metal is leached from the prepared alkali sintered molded body (S30).
알칼리 소결 성형체로부터 유가금속을 침출하는 방법은 여러가지 방법을 이용할 수 있다. 바람직하게는 후술하는 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법을 이용할 수 있다. Various methods can be used for leaching the valuable metal from the alkali sintered molded body. Preferably, a vanadium-tungsten separation method in a vanadium-tungsten-containing solution described later may be used.
먼저, 알칼리 소결 성형체로부터 바나듐과 텅스텐을 추출하는 단계(S31)를 수행한다. 알칼리 소결 성형체로부터 바나듐과 텅스텐을 추출하는 단계(S31)를 수행함으로써 바나듐-텅스텐 함유 용액을 수득할 수 있다. 구체적으로 살펴보면 다음과 같다. First, a step (S31) of extracting vanadium and tungsten from the alkali sintered molded body is performed. A vanadium-tungsten containing solution can be obtained by performing the step of extracting vanadium and tungsten from the alkali sintered molded body (S31). Specifically, it is as follows.
알칼리 소결 성형체를 물에 투입하면 알칼리 소결 성형체 내에 존재하는 바나듐산나트륨 및 텅스텐산나트륨이 용해된다. 수침출은 물 100 중량부에 대하여 알칼리 소결 성형체 40~60 중량부를 첨가하여 수행되며, 수침출이 수행되는 물의 온도는 70~90 ℃인 것이 바람직하다. 수침출을 수행한 후에 고형물은 여과하여 침출액과 고형물을 분리한다. When the alkali sintered body is put into water, sodium vanadate and sodium tungstate present in the alkali sintered body are dissolved. Water leaching is performed by adding 40 to 60 parts by weight of the alkali sintered molded body with respect to 100 parts by weight of water, and the temperature of the water at which water leaching is performed is preferably 70 to 90 °C. After water leaching, the solids are filtered to separate the leachate and solids.
다음 침출액에 침전제를 첨가한다. 침전제로는 염화칼슘(CaCl2)를 이용할 수 있다. 염화칼슘은 강알칼리인 침출액 내에서 칼슘을 통하여 텅스텐 및 바나듐의 침출율을 조절하여 텅스텐 또는 바나듐을 선택적으로 침전시킬 수 있다. 즉, pH 조절제로 수산화칼륨을 첨가하여 pH13 초과로 조절하여 메타바나듐산칼슘을 침전시킬 수 있으며, pH 13 이하로 조절하여 텅스텐산칼슘을 침전시킬 수 있다. 침전제를 첨가한 이후 교반기를 통해 200 ~ 600 rpm으로 30 분 내지 2시간 동안 교반하여 침전과정이 수행될 수 있다. A precipitating agent is then added to the leachate. Calcium chloride (CaCl 2 ) may be used as a precipitant. Calcium chloride can selectively precipitate tungsten or vanadium by controlling the leaching rate of tungsten and vanadium through calcium in a strong alkaline leachate. That is, calcium metavanadate may be precipitated by adding potassium hydroxide as a pH adjusting agent to adjust the pH above 13, and calcium tungstate may be precipitated by adjusting the pH to 13 or less. After adding the precipitating agent, the precipitation process may be performed by stirring for 30 minutes to 2 hours at 200 to 600 rpm through an agitator.
다음으로 알칼리 소결 성형체로부터 타이타늄을 추출하는 단계(S32)를 수행한다. 알칼리 소결 성형체로부터 타이타늄을 추출하는 단계(S32)를 수행함으로써 타이타늄 함유 염산 용액을 수득할 수 있다. 구체적으로 살펴보면 다음과 같다. Next, a step (S32) of extracting titanium from the alkali sintered molded body is performed. A hydrochloric acid solution containing titanium may be obtained by performing the step of extracting titanium from the alkali sintered molded body (S32). Specifically, it is as follows.
먼저, 고형물에 염산을 첨가하여 산침출을 수행한다. 산침출은 50 ~ 60 ℃에서 2 ~ 3시간동안 수행될 수 있다. First, acid leaching is performed by adding hydrochloric acid to the solid. Acid leaching may be performed at 50 to 60 °C for 2 to 3 hours.
그 다음, 산침출을 통해 수득한 산침출액에 수산화나트륨을 첨가한다. 산침출액에 수산화나트륨을 첨가하면 반응하여 수화된 형태의 TiO2로 침전된다 (TiO2nH2O, n=1 or 2). Then, sodium hydroxide is added to the acid leachate obtained through acid leach. When sodium hydroxide is added to the acid leachate, it reacts and precipitates as a hydrated form of TiO 2 (TiO 2 nH 2 O, n=1 or 2).
마지막으로 수화된 형태의 TiO2를 하소하여 이산화타이타늄을 회수한다. 하소공정은 약 400~600 ℃ 이상의 온도에서 1~5시간동안 수행될 수 있으며, 이에 따라 이산화타이타늄(루타일 또는 아나타제)을 회수할 수 있다. Finally, the hydrated TiO 2 is calcined to recover titanium dioxide. The calcination process may be performed at a temperature of about 400 to 600 ° C. or more for 1 to 5 hours, and thus titanium dioxide (rutile or anatase) may be recovered.
위와 달리 알칼리 소결 성형체로부터 유가금속을 침출하는 단계(S30)는 새로운 방법으로 수행될 수 있다. Unlike the above, the step of leaching the valuable metal from the alkali sintered molded body (S30) can be performed in a new method.
먼저, 알칼리 소결 성형체로부터 바나듐과 텅스텐을 추출하는 단계(S31)를 수행한다. 여기서 제안하는 방법에 의해 바나듐과 텅스텐의 분리도를 향상시켜 최종적으로 획득하는 바나듐(V2O5)과 텅스텐(WO3)의 품질을 향상시킬 수 있다. First, a step (S31) of extracting vanadium and tungsten from the alkali sintered molded body is performed. The quality of vanadium (V 2 O 5 ) and tungsten (WO 3 ) finally obtained can be improved by improving the separation between vanadium and tungsten by the method proposed here.
알칼리 소결 성형체를 물에 투입하면 알칼리 소결 성형체 내에 존재하는 바나듐산나트륨 및 텅스텐산나트륨이 용해된다. 수침출은 물 100 중량부에 대하여 알칼리 소결 성형체 40~60 중량부를 첨가하여 수행되며, 수침출이 수행되는 물의 온도는 70~90 ℃인 것이 바람직하다. 수침출을 수행한 후에 고형물은 여과하여 침출액과 고형물을 분리한다. When the alkali sintered body is put into water, sodium vanadate and sodium tungstate present in the alkali sintered body are dissolved. Water leaching is performed by adding 40 to 60 parts by weight of the alkali sintered molded body with respect to 100 parts by weight of water, and the temperature of the water at which water leaching is performed is preferably 70 to 90 °C. After water leaching, the solids are filtered to separate the leachate and solids.
다음으로 침출수를 전처리하여 바나듐산 이온상태를 전환시키는 단계가 수행된다. 침출수를 전처리하는 단계에서는 무기산(예를 들어, 황산, 염산 등)을 첨가하여 침출수의 pH를 0.5 내지 3으로 낮추고, 전처리제를 첨가함으로써 침출수 내의 바나듐산 이온(VO3
-)을 환원시켜 아민계 추출제에 의해 추출되지 않는 상태로 전환한다. 구체적으로 침출수의 pH 를 낮춰 침출 수 내의 VO3
-를 VO2
+로 전환하고, 전처리제를 첨가하여 VO2+로 전환한다. Next, a step of pre-treating the leachate to convert the vanadate ion state is performed. In the step of pre-treating the leachate, an inorganic acid (eg, sulfuric acid, hydrochloric acid, etc.) is added to lower the pH of the leachate to 0.5 to 3, and a pre-treatment agent is added to reduce vanadium acid ions (VO 3 - ) in the leachate to obtain an amine-based It is converted into a state that is not extracted by the extractant. Specifically, VO 3 - in the leachate is converted into VO 2+ by lowering the pH of the leachate, and converted into VO 2+ by adding a pretreatment agent .
이때 침출수 내의 VO3
-를 VO2
+로 전환하기 위한 pH는 바나듐의 농도에 의해 결정될 수 있으며, 다음의 표 1 과 같다.At this time, pH for converting VO 3 - in leachate to VO 2 + may be determined by the concentration of vanadium, and is shown in Table 1 below.
| [V], mol/L[V], mol/L | ≤ 10-4 ≤ 10 -4 | 10-4 < [V] ≤ 10-2 10 -4 < [V] ≤ 10 -2 | 10-2 < [V] ≤ 10-1 10 -2 < [V] ≤ 10 -1 |
| pHpH | 1.0 ~ 3.01.0 to 3.0 | 1.0 ~ 1.21.0 to 1.2 | < 1.0< 1.0 |
전처리제로는 아황산수소나트륨(NaHSO3) 및/또는 황화나트륨(Na2S)를 이용할 수 있다. 전처리제의 양은 바나듐에 농도를 기준으로 하여 바나듐 1당량에 1 내지 2 당량 첨가된다. As the pretreatment agent, sodium hydrogen sulfite (NaHSO 3 ) and/or sodium sulfide (Na 2 S) may be used. The amount of the pretreatment agent is added from 1 to 2 equivalents to 1 equivalent of vanadium based on the concentration of vanadium.
전처리가 완료된 침출수에 추출제를 첨가한다. 추출제로는 아민계 추출제를 이용할 수 있으며, 구체적으로 Alamine 336을 이용할 수 있다. 침출수에 추출제를 첨가하게 되면 텅스텐산 이온(WO4
2-)은 추출되지만, 전환된 바나듐산 이온(VO2+)는 추출되지 않는다.An extractant is added to the pretreated leachate. An amine-based extractant may be used as the extractant, and specifically, Alamine 336 may be used. When an extractant is added to leachate, tungstate ions (WO 4 2- ) are extracted, but converted vanadate ions (VO 2+ ) are not extracted.
추출제를 첨가한 후에는 제1유기용매와 제1수용매를 분리하는 단계가 수행된다. 이때, 텅스텐은 제1유기용매로 이동하고, 바나듐은 제1수용매로 이동한다. 그러므로 제1유기용매와 제1수용매를 분리함으로써 텅스텐과 바나듐을 서로 분리할 수 있다. 제1유기용매와 제2수용매의 분리는 원심분리형 용매추출장치를 이용할 수 있다. After adding the extractant, a step of separating the first organic solvent and the first aqueous solvent is performed. At this time, tungsten moves into the first organic solvent, and vanadium moves into the first aqueous solvent. Therefore, tungsten and vanadium can be separated from each other by separating the first organic solvent and the first aqueous solvent. Separation of the first organic solvent and the second aqueous solvent may use a centrifugal solvent extraction device.
분리된 제1유기용매에 대해 세정을 수행하고, 암모니아(NH3) 액을 투입한다. 제1유기용매에 암모니아액을 첨가하면, 포함되어 있던 텅스텐이 APT(Ammonium Paratungstate)로 전환되어 제2수용매로 이동하게 된다. 이후 제2수용매를 제1유기용매로부터 다시 분리하고, 제2수용매 내에 있는 APT를 결정화하여 수득한다. 수득한 APT는 고액 여과 후 소성을 통해 WO3로 회수한다. 이와 같은 방법으로 회수한 WO3의 순도는 99.8% 이상이 된다. Washing is performed on the separated first organic solvent, and an ammonia (NH 3 ) solution is introduced. When the ammonia solution is added to the first organic solvent, the contained tungsten is converted to APT (Ammonium Paratungstate) and moved to the second aqueous solvent. Thereafter, the second aqueous solvent is separated from the first organic solvent again, and APT in the second aqueous solvent is crystallized to obtain. The obtained APT is recovered as WO 3 through calcination after solid-liquid filtration. The purity of WO 3 recovered in this way is 99.8% or more.
한편, 분리한 제1수용매에는 암모니아 또는 암모니아액을 투입한다. 제1수용매에 암모니아 또는 암모니아액을 첨가하면, 포함되어 있던 바나듐이 AMV(Ammonium Meta-Vanadate)로 전환된다. AMV는 제1수용액에서 침전되며, 고액 여과를 통해 침전물을 분리하여 AMV를 수득한다. 수득한 AMV는 소성을 통해 V2O5로 회수한다. 이와 같은 방법으로 회수한 V2O5의 순도는 99.8% 이상이 된다.Meanwhile, ammonia or ammonia solution is added to the separated first aqueous solvent. When ammonia or ammonia solution is added to the first aqueous solvent, the contained vanadium is converted into AMV (Ammonium Meta-Vanadate). AMV is precipitated in the first aqueous solution, and AMV is obtained by separating the precipitate through solid-liquid filtration. The obtained AMV is recovered as V 2 O 5 through sintering. The purity of V 2 O 5 recovered in this way is 99.8% or more.
다음으로 알칼리 소결 성형체로부터 타이타늄을 추출하는 단계(S32)를 수행한다. 여기에서 제안하는 방법에 의해 염산법에 의해 타이타늄을 추출하되, 가수분해 방법으로도 타이타늄의 결정을 아나타제 또는 루타일로 할 것인지를 제어할 수 있다는 장점이 있다. Next, a step (S32) of extracting titanium from the alkali sintered molded body is performed. The method proposed here has the advantage of being able to control whether titanium crystals are anatase or rutile even by hydrolysis, while titanium is extracted by the hydrochloric acid method.
먼저, 고형물에 염산을 첨가하여 산침출을 수행한다. 산침출은 50 ~ 60 ℃에서 2 ~ 3시간동안 수행될 수 있다.First, acid leaching is performed by adding hydrochloric acid to the solid. Acid leaching may be performed at 50 to 60 °C for 2 to 3 hours.
그 다음 씨드용액을 제조한다. 씨드용액은 산침출액 1kg 당 0.3 ~ 0.7 kg의 가성소다를 상온에서 혼합하고, 혼합물 100 중량부에 65 ~ 85 중량부의 물을 65 ~ 85 ℃에서 25 ~ 35분간 혼합하여 씨드용액을 제조한다.Then, a seed solution is prepared. The seed solution is prepared by mixing 0.3 to 0.7 kg of caustic soda per 1 kg of acid leachate at room temperature, and mixing 65 to 85 parts by weight of water with 100 parts by weight of the mixture at 65 to 85 ° C. for 25 to 35 minutes.
제조한 씨드용액을 산침출수에 첨가하여 가수분해 반응시키는 단계가 수행된다. 제조한 씨드용액을 산침출수에 첨가하여 가수분해 반응시키는 단계는 80 ~ 110 ℃에서 150 ~ 210분 동안 수행된다. A step of hydrolysis is performed by adding the prepared seed solution to acid leachate. Adding the prepared seed solution to acid leachate and hydrolyzing it is performed at 80 to 110 ° C for 150 to 210 minutes.
씨드용액은 산침출수 100중량부에 대해 3 내지 4 중량부를 첨가한다. The seed solution is added in an amount of 3 to 4 parts by weight based on 100 parts by weight of acid leachate.
이때, 씨드용액과 함께 결정 선택제를 씨드용액에 첨가할 수 있으며, 결정선택제에 의해 수득하는 타이타늄의 결정형이 아나타제인지 루타일인지 정해진다. 결정선택제를 일정 이상의 양으로 첨가할 경우 제조되는 타이타늄의 결정형이 아나타제가 되며, 첨가하지 않을 경우 제조되는 타이타늄의 결정형이 루타일이 된다. 구체적으로 결정선택제가 황산인 경우 황산을 산침출수 100중량부에 대해 10 중량부 이상 첨가한 경우 제조되는 타이타늄의 결정형이 아나타제가 되며, 결정선택제가 인산수소이나트륨인 경우에는 인산수소이나트륨을 산침출수 100중량부에 대해 0.5 중량부 이상 첨가한 경우 제조되는 타이타늄의 결정형이 아나타제가 되고, 결정선택제가 인산인 경우에는 인산을 산침출수 100중량부에 대해 0.4 중량부 이상 첨가한 경우 제조되는 타이타늄의 결정형이 아나타제가 된다. At this time, a crystal selector may be added to the seed solution together with the seed solution, and the crystal form of titanium obtained by the crystal selector is determined whether it is anatase or rutile. When a crystal selector is added in a certain amount or more, the crystalline form of titanium to be produced becomes anatase, and when not added, the crystalline form of titanium to be produced becomes rutile. Specifically, when the crystal selector is sulfuric acid, when 10 parts by weight or more of sulfuric acid is added to 100 parts by weight of acid leachate, the crystalline form of the titanium produced becomes anatase. When 0.5 part by weight or more is added, the crystalline form of titanium produced becomes anatase. become anatase.
반응과정에서 침전물을 분리하여 하소하여 이산화타이타늄을 회수한다. 하소공정은 약 400 ~ 600 ℃ 의 온도에서 2~5시간동안 수행될 수 있으며, 이에 따라 이산화타이타늄(루타일 또는 아나타제)을 회수할 수 있다.During the reaction, the precipitate is separated and calcined to recover titanium dioxide. The calcination process may be performed for 2 to 5 hours at a temperature of about 400 to 600 ° C., thereby recovering titanium dioxide (rutile or anatase).
<실시예 1: 알칼리 소결 성형체를 이용한 탈질폐기물 함유 텅스텐, 바나듐 및 타이타늄 추출><Example 1: Extraction of tungsten, vanadium and titanium containing denitrification waste using alkali sintered molded body>
화력발전소에서 수거한 탈질폐촉매를 분쇄하고, 오븐에서 건조하여 탈질폐촉매 파우더를 제조하였다. 탈질폐촉매 파우더의 입도는 ≤ 212 μm였다. 제조한 탈질폐촉매 파우더 1kg 당 탄산나트륨 0.95 kg을 혼합하여 혼합물을 만들었다. 혼합물은 크랭크형 프레스를 이용하여 500 kgf/cm2 이상의 성형압력으로 단면적 60 cm2, 높이 3.5 cm의 원기둥형의 가성형체를 제조하였다. 가성형체의 제조과정에서 발열에 의해 50 ℃의 온도가 상승됨을 확인할 수 있었다. 제조한 가성형체는 가열로 내에서 900 ℃로 60분간 소결하여 알칼리 소결 성형체를 제조하였다. The spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst. The particle size of the spent denitrification catalyst powder was ≤ 212 μm. A mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder. The mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 500 kgf/cm 2 or more using a crank-type press. It was confirmed that the temperature of 50 ℃ was increased by heat generation during the manufacturing process of the pseudo-shaped body. The prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
알칼리 소결 성형체는 분쇄하였고, 이로부터 유가금속을 침출하였다. The alkali sintered compact was pulverized, and valuable metals were leached therefrom.
분쇄된 알칼리 소결 성형체를 물 100 중량부에 대해 50 중량부 첨가하여 수침출을 충분히 수행하였다. 수침출을 수행한 물의 온도는 80 ℃였다. 수침출을 수행한 후 고형물은 여과하여 침출액과 고형물을 분리하였다. 분리한 침출액에 황산을 첨가하여 pH를 1로 낮추고, 바나듐 이온 상태 전환제로 아황산나트륨(NaHSO3)을 바나듐 1 당량 당 1.5 당량 첨가하였다. 전처리가 완료된 침출수에 추출제로 Alamine 336을 첨가하였다. 그 후 원심분리형 용매추출유닛을 이용하여 제1유기용매와 제1수용매를 서로 혼합하였다가, 원심력에 의해 제1유기용매와 제1수용매를 서로 분리하였다. Water leaching was sufficiently performed by adding 50 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water. The temperature of the water subjected to water leaching was 80 °C. After performing water leaching, the solids were filtered to separate the leachate and the solids. Sulfuric acid was added to the separated leachate to lower the pH to 1, and sodium sulfite (NaHSO 3 ) as a vanadium ion state conversion agent was added in an amount of 1.5 equivalents per 1 equivalent of vanadium. Alamine 336 was added as an extractant to the pretreated leachate. Thereafter, the first organic solvent and the first aqueous solvent were mixed with each other using a centrifugal solvent extraction unit, and then the first organic solvent and the first aqueous solvent were separated from each other by centrifugal force.
분리된 제1유기용매는 세정을 수행하고, 원심분리형 용매추출유닛을 이용하여 세정된 제1유기용매를 분리했다. 세정된 제1유기용매에 암모니아액을 첨가하였으며, 다시 원심분리형 용매추출유닛을 이용하여 제1유기용매와 제2수용매를 분리하였다. 이후 제2수용매로부터 APT를 결정화하고, 수득한 APT를 고액 여과 및 소성하여 WO3를 회수하였다. The separated first organic solvent was washed, and the washed first organic solvent was separated using a centrifugal solvent extraction unit. Ammonia solution was added to the washed first organic solvent, and the first organic solvent and the second aqueous solvent were separated again using a centrifugal solvent extraction unit. Thereafter, APT was crystallized from the second aqueous solvent, and WO 3 was recovered by solid-liquid filtration and calcining of the obtained APT.
분리된 제1수용매에 암모니아를 투입하였다. 제1수용매에 암모니아 투입함에 따라 AMV가 침전되며, 고액 여과를 통해 침전물을 분리하여 AMV를 수득하였다. 수득한 AMV를 소성하여 V2O5를 회수하였다.Ammonia was added to the separated first aqueous solvent. AMV was precipitated as ammonia was added to the first aqueous solvent, and AMV was obtained by separating the precipitate through solid-liquid filtration. The obtained AMV was calcined to recover V 2 O 5 .
고형물에 염산을 첨가하여 산침출을 수행하였다. 산침출은 60 ℃에서 3시간동안 진행되었다. 산침출액 중 일부를 이용하여 씨드용액을 제조하였다. 씨드용액은 산침출액1kg 당 0.5 kg의 가성소다를 혼합하여 혼합수를 제조하고, 혼합수 1.5kg 당 물을 0.75 kg 투입하였다. 이후 70 ℃에서 30분간 교반하여 씨드용액을 제조하였다. 산침출액에 제조된 씨드용액을 4 wt% 첨가하고, 100 ℃에서 180분간 반응시켰다. 반응과정에서 침전된 침전물을 분리하여 600 ℃에서 5시간동안 하소하여 이산화타이타늄(루타일)을 회수하였다,Acid leaching was performed by adding hydrochloric acid to the solid. Acid leaching was carried out at 60 °C for 3 hours. A seed solution was prepared using some of the acid leachate. The seed solution was mixed with 0.5 kg of caustic soda per 1 kg of acid leachate to prepare mixed water, and 0.75 kg of water was added per 1.5 kg of mixed water. After stirring at 70 ℃ for 30 minutes to prepare a seed solution. 4 wt% of the prepared seed solution was added to the acid leachate, and reacted at 100 ° C. for 180 minutes. The precipitate precipitated in the reaction process was separated and calcined at 600 ° C. for 5 hours to recover titanium dioxide (rutile).
실시예 1의 각 유가금속의 침출율은 다음의 표 2와 같다. The leaching rate of each valuable metal in Example 1 is shown in Table 2 below.
| 텅스텐tungsten | 바나듐vanadium |
타이타늄 | |
| 침출율leaching rate | 99%99% | 99%99% | 95% 95% |
<실시예 2: 알칼리 소결 성형체의 조성에 따른 유가금속의 침출율><Example 2: Valuable metal leaching rate according to composition of alkali sintered molded article>
실시예 1과 동일한 방법으로 각 유가금속을 추출하되, 탈질폐촉매는 알칼리제와 혼합하여 혼합물을 마련할 때 알칼리제의 함량을 변화시켜 샘플을 준비하였다. Each valuable metal was extracted in the same manner as in Example 1, but the waste denitrification catalyst was mixed with an alkali agent to prepare a mixture, and samples were prepared by changing the content of the alkali agent.
각 샘플에 대해 각 유가금속의 침출율을 측정하였으며, 알칼리 소결 성형체의 조성에 따른 유가금속의 침출율을 도 2에 나타내었다.The leaching rate of each valuable metal was measured for each sample, and the leaching rate of valuable metal according to the composition of the alkali sintered molded article is shown in FIG. 2 .
도 2를 참조하면, 1kg의 탈질폐촉매에 대해 알칼리제의 양이 0.8 kg 이하인 경우 알칼리제가 부족하여 탈질폐촉매에 포함되어 있는 유가금속이 침출가능한 형태로 변화하지 못하는 양이 증가되며, 1.2 kg을 초과할 경우에는 알칼리제가 불순물로 작용하여 후 공정에 부담이 되며, 불필요한 알칼리제 소비로 경제성이 낮아진다. 또한, 1kg의 탈질폐촉매에 대해 알칼리제의 양이 0.7kg 미만인 경우에는 타이타늄의 침출율이 낮아지는 문제가 있으며, 1.0 kg을 초과할 경우에는 침출율 증가에 기여하지 못함을 확인할 수 있다. Referring to FIG. 2, when the amount of the alkali agent is 0.8 kg or less for 1 kg of the spent denitrification catalyst, the amount of the valuable metal contained in the spent denitrification catalyst that cannot be changed into a leachable form increases due to insufficient alkali agent, and 1.2 kg If it is exceeded, the alkali agent acts as an impurity and becomes a burden in the subsequent process, and economical efficiency is lowered due to unnecessary consumption of the alkali agent. In addition, when the amount of alkali agent for 1 kg of spent denitrification catalyst is less than 0.7 kg, there is a problem in that the leaching rate of titanium is lowered, and when it exceeds 1.0 kg, it can be confirmed that it does not contribute to the increase in leaching rate.
<실시예 3: 알칼리 소결 성형체의 소결 온도에 따른 유가금속의 침출율><Example 3: Valuable metal leaching rate according to sintering temperature of alkali sintered molded body>
실시예 1과 동일한 방법으로 각 유가금속을 추출하되, 가성형체를소결하는 과정에서 소결온도를 변화시켜 샘플을 준비하였다. Samples were prepared by extracting each valuable metal in the same manner as in Example 1, but changing the sintering temperature in the process of sintering the pseudo-form.
각 샘플에 대해 각 유가금속의 침출율을 측정하였으며, 소결 온도에 따른 유가금속의 침출율을 도 3에 나타내었다. The leaching rate of each valuable metal was measured for each sample, and the leaching rate of the valuable metal according to the sintering temperature is shown in FIG. 3 .
도 3을 참조하면, 소결 온도가 800 ℃ 미만인 경우 온도가 낮아 탈질폐촉매 중 유가금속 성분이 침출가능한 형태로 충분히 전환되지 않으며, 900 ℃ 를 초과할 경우 알칼리제의 부반응(예를 들어, 도가니와의 반응 등)에 의해 오히려 침출율이 떨어지는 것을 확인할 수 있다. Referring to FIG. 3, when the sintering temperature is less than 800 ° C, the valuable metal component in the spent denitrification catalyst is not sufficiently converted into a leachable form due to the low temperature, and when the sintering temperature exceeds 900 ° C, a side reaction of the alkali agent (for example, with a crucible reaction, etc.), it can be seen that the leaching rate is rather low.
2. 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법2. Method for Separating Vanadium-Tungsten in a Vanadium-Tungsten Containing Solution
도 5는 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법의 개략적 플로우 차트이다.5 is a schematic flow chart of a method for separating vanadium-tungsten in a vanadium-tungsten-containing solution according to an embodiment of the present invention.
아하, 도 5를 참조하여, 본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법(M200)(이하, "바나듐-텅스텐 분리 방법"이라 한다)에 대해 설명하도록 한다. 한편, 본 발명의 일 실시예에 따른 바나듐-텅스텐 분리 방법(M200)은 후술하는 바나듐-텅스텐 분리 시스템(100, 도 6 참조)에 의해 수행될 수 있음을 미리 밝혀둔다. 바나듐-텅스텐 함유 용액은 전술한 탈질폐촉매로부터 수침출하여 형성된 것을 이용할 수 있다. Aha, with reference to FIG. 5 , a vanadium-tungsten separation method (M200) in a vanadium-tungsten-containing solution according to an embodiment of the present invention (hereinafter referred to as “vanadium-tungsten separation method”) will be described. Meanwhile, it is noted in advance that the vanadium-tungsten separation method M200 according to an embodiment of the present invention may be performed by a vanadium-tungsten separation system 100 (see FIG. 6) to be described later. The vanadium-tungsten-containing solution formed by water leaching from the above-mentioned spent denitrification catalyst may be used.
본 발명의 일 실시예에 따른 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법(M200)은 크게 2가지 루트로 구분된다. 첫번째는 텅스텐 추출 루트이며, 두번째는 바나듐 추출 루트이다. 본 발명에서 텅스텐 추출루트의 목적은 텅스텐과 바나듐의 분리이며, 동시에 텅스텐을 농축하는 것이다. 본 발명의 텅스텐 추출루트의 특징은 전처리제를 사용하여 바나듐이 추출되지 않는 이온 형태로 전환하여 텅스텐만 선택적으로 추출하는 것이며, 나아가 추출-세정-탈거 공정을 거치며 텅스텐의 농도가 농축된다. 본 발명의 바나듐 추출 루트의 주된 목적은 바나듐의 농축이다. 즉, 추출제에 의해 추출되지 않던 이온형태를 가지는 바나듐을 텅스텐으로부터 분리한 후에 다시 추출되는 형태로 전환하여 추출제를 통해 추출 및 농축하게 된다. 아래에서는 이에 대해서 구체적으로 설명하도록 한다. The vanadium-tungsten separation method (M200) in a vanadium-tungsten-containing solution according to an embodiment of the present invention is largely divided into two routes. The first is the tungsten extraction route, and the second is the vanadium extraction route. The purpose of the tungsten extraction route in the present invention is to separate tungsten and vanadium and to concentrate tungsten at the same time. A feature of the tungsten extraction route of the present invention is that only tungsten is selectively extracted by converting vanadium into an ionic form in which vanadium is not extracted using a pretreatment agent, and furthermore, the concentration of tungsten is concentrated through the extraction-cleaning-separation process. The main purpose of the vanadium extraction route of the present invention is the concentration of vanadium. That is, vanadium having an ionic form that was not extracted by the extractant is separated from tungsten and then converted into a form to be extracted again, and then extracted and concentrated through the extractant. Below, this will be explained in detail.
본 발명의 일 실시예에 따른 바나듐-텅스텐 분리 방법(M200)은 바나듐-텅스텐 함유 용액에 전처리를 수행하여 용액내 바나듐을 환원시키는 단계(S210), 전처리한 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계(S220), 반응시킨 바나듐-텅스텐 함유 용액을 유기 용매와 수 용매로 분리하는 단계(S230), 유기 용매에서 텅스텐을 추출하는 단계(S240) 및 수 용매에서 바나듐을 추출하는 단계(S250)를 포함한다. In the vanadium-tungsten separation method (M200) according to an embodiment of the present invention, a vanadium-tungsten-containing solution is pretreated to reduce vanadium in the solution (S210), and an extractant is added to the pretreated vanadium-tungsten-containing solution. and reacting (S220), separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent (S230), extracting tungsten from the organic solvent (S240), and extracting vanadium from the aqueous solvent ( S250).
먼저, 바나듐-텅스텐 함유 용액에 전처리를 수행하여 용액내 바나듐의 이온상태를 전환시키는 단계(S210)가 수행된다.First, a step of converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution (S210) is performed.
바나듐-텅스텐 함유 용액은 탈질폐기물을 분쇄하여 알칼리제(예를들어, 탄산나트륨)를 혼합하여 고온에서 반응시킨 후 수침출하여 마련된 것을 이용할 수 있다. 바나듐-텅스텐 함유 용액은 물에 바나듐산 이온(VO3
-)과 텅스텐산 이온(WO4
2-)이 포함된 것일 수 있다. The vanadium-tungsten-containing solution may be prepared by pulverizing denitrification waste, mixing with an alkali agent (eg, sodium carbonate), reacting at high temperature, and then leaching with water. The vanadium-tungsten-containing solution may contain vanadate ions (VO 3 - ) and tungstate ions (WO 4 2- ) in water.
바나듐-텅스텐 함유 용액에 전처리를 수행하여 용액내 바나듐의 이온상태를 전환시키는 단계(S210)의 목적은 용액 내 바나듐이 추출제에 의해 추출되지 않는 상태로 전환하는 것이다. 이를 위해 바나듐-텅스텐 함유 용액의 pH를 조절하는 단계(S211) 및 pH 가 조절된 바나듐-텅스텐 함유 용액에 전처리제를 첨가하는 단계(S212)를 통해 바나듐-텅스텐 함유 용액에 포함되어 있던 VO3
- 이온이 VO2+이온으로 전환시킨다. The purpose of converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution (S210) is to convert the vanadium in the solution to a state that is not extracted by the extractant. To this end, through the step of adjusting the pH of the vanadium-tungsten-containing solution (S211) and the step of adding a pretreatment agent to the pH-adjusted vanadium-tungsten-containing solution (S212), the VO 3 - ions are converted to VO 2+ ions.
바나듐-텅스텐 함유 용액의 pH를 조절하는 단계(S11)는 염산, 질 산, 황산을 이용하여 바나듐-텅스텐 함유 용액의 pH를 3 이하로 조절한다. 이때, 바나듐-텅스텐 함유 용액의 pH는 바나듐-텅스텐 함유 용액 내의 바나듐의 농도에 의해 결정될 수 있으며, 다음의 표 3과 같다. In the step of adjusting the pH of the vanadium-tungsten-containing solution (S11), the pH of the vanadium-tungsten-containing solution is adjusted to 3 or less using hydrochloric acid, nitric acid, or sulfuric acid. At this time, the pH of the vanadium-tungsten-containing solution may be determined by the concentration of vanadium in the vanadium-tungsten-containing solution, and is shown in Table 3 below.
| [V], mol/L[V], mol/L | ≤ 10-4 ≤ 10 -4 | 10-4 < [V] ≤ 10-2 10 -4 < [V] ≤ 10 -2 | 10-2 < [V] ≤ 10-1 10 -2 < [V] ≤ 10 -1 |
| pHpH | 1.0 ~ 3.01.0 to 3.0 | 1.0 ~ 1.21.0 to 1.2 | < 1.0< 1.0 |
바나듐-텅스텐 함유 용액의 pH를 조절하는 단계(S211)에 의해 먼저 바나듐-텅스텐 함유 용액에 포함되어 있던 VO3
- 이온이 VO2
+이온으로 전환된다.By adjusting the pH of the vanadium-tungsten-containing solution (S211), VO 3 - ions included in the vanadium-tungsten-containing solution are first converted into VO 2 + ions.
그 다음 pH 가 조절된 바나듐-텅스텐 함유 용액에 전처리제를 첨가하는 단계(S212)가 수행되며, 전처리제에 의해 pH 가 조절된 바나듐-텅스텐 함유 용액에 포함되어 있던 VO2
+이온이 VO2+이온으로 전환된다. VO2+ 이온은 추출제, 보다 구체적으로는 아민계 추출제에 의해 추출되지 않는다. Then, a step (S212) of adding a pretreatment agent to the vanadium-tungsten-containing solution whose pH is adjusted is performed (S212), and the VO 2 + ions contained in the vanadium-tungsten-containing solution whose pH is adjusted by the pretreatment agent are VO 2+ converted into ions VO 2+ ions are not extracted by extractants, more specifically amine-based extractants.
전처리제로는 용해되면서 용액 중 산소와 결합하는 성질을 가진 것을 이용할 수 있으며, 예컨대 As the pretreatment agent, those having the property of binding to oxygen in the solution while dissolving may be used, such as
아황산수소나트륨(NaHSO3), 아황산나트륨(Na2SO3), 및 황화나트륨(Na2S) 중 적어도 하나를 이용할 수 있다. 전처리제의 양은 바나듐의 농도를 기준으로 하여 바나듐 1당량에 1 내지 2 당량 첨가된다. 전처리제의 양이 바나듐 1당량에 1 당량 미만인 경우 VO2+이온으로 전환되지 않은 VO2
+이온이 잔류하는 문제가 있으며, 2 당량 초과할 경우에는 전처리제가 전처리에 더 이상 기여하지 못하고 오히려 불순물이 된다. 전처리제를 첨가한 후에는 온도를 40 ~ 80 ℃올리고, 1 ~4 시간 동안 유지하여 반응시킨다. At least one of sodium hydrogen sulfite (NaHSO 3 ), sodium sulfite (Na 2 SO 3 ), and sodium sulfide (Na 2 S) may be used. The amount of the pretreatment agent is added from 1 to 2 equivalents to 1 equivalent of vanadium based on the concentration of vanadium. If the amount of the pretreatment agent is less than 1 equivalent per 1 equivalent of vanadium, there is a problem that VO 2+ ions that are not converted to VO 2+ ions remain, and if the amount exceeds 2 equivalents, the pretreatment agent does not contribute to the pretreatment anymore and rather impurities do. After adding the pretreatment agent, the temperature is raised to 40 ~ 80 ℃, and maintained for 1 ~ 4 hours to react.
다음으로 전처리한 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계(S220)가 수행된다. 추출제로는 아민계 추출제를 이용할 수 있으며, 구체적으로 Alamine336또는 Trioctylamine(TOA)을 이용할 수 있다. 추출 온도는 40 ~ 60 ℃에서 수행된다. 본래 아민계 추출제는 바나듐과 텅스텐 모두를 추출할 수 있으나, 전처리 과정을 통해 바나듐-텅스텐 함유 용액 내 바나듐이 VO2+이온으로 존재할 경우 바나듐은 아민계 추출제에 의해 추출되지 않는다. 그러므로 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계(S220)에서 텅스텐은 유기 용매로 이동하게 되고, 바나듐은 수 용매에 그대로 남아 있게 된다. Next, a step of reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution (S220) is performed. An amine-based extractant may be used as the extractant, and specifically, Alamine 336 or Trioctylamine (TOA) may be used. The extraction temperature is carried out at 40 ~ 60 ℃. Originally, the amine-based extractant can extract both vanadium and tungsten, but when vanadium exists as VO 2+ ions in a vanadium-tungsten-containing solution through a pretreatment process, vanadium is not extracted by the amine-based extractant. Therefore, in the step of reacting by adding an extractant to the vanadium-tungsten-containing solution (S220), tungsten is transferred to the organic solvent, and vanadium remains in the aqueous solvent.
한편, 전처리한 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계에서 추출제의 양은 전처리한 바나듐-텅스텐 함유 용액 100 중량부에 대해 10 내지 100 중량부로 포함될 수 있다. 추출제의 양이 전처리한 바나듐-텅스텐 함유 용액 100 중량부에 대해 10 중량부 미만인 경우 텅스텐이 수 용매에 잔류하게 되는 문제가 있으며, 100 중량부를 초과할 경우에는 불순물의 추출능이 향상되어 용매 중 불순물의 농도가 높아지는 문제가 있다. Meanwhile, in the step of reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution, the amount of the extractant may be 10 to 100 parts by weight based on 100 parts by weight of the pretreated vanadium-tungsten-containing solution. If the amount of the extractant is less than 10 parts by weight with respect to 100 parts by weight of the pretreated vanadium-tungsten-containing solution, there is a problem that tungsten remains in the aqueous solvent, and if it exceeds 100 parts by weight, the ability to extract impurities is improved and impurities in the solvent There is a problem that the concentration of
반응시킨 바나듐-텅스텐 함유 용액을 유기 용매와 수 용매로 분리하는 단계(S230)가 수행된다. 이 단계에서는 용매추출형 원심분리유닛을 이용할 수 있으나, 본 발명의 바나듐-텅스텐 분리 방법이 이에 제한되는 것은 아니다. 반응시킨 바나듐-텅스텐 함유 용액에서 텅스텐은 유기 용매에 포함되어 있고, 바나듐은 수 용매에 그대로 남아 있기 때문에, 유기 용매와 수 용매로 분리함으로써 텅스텐과 바나듐이 서로 완전히 분리된다. A step of separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent (S230) is performed. In this step, a solvent extraction type centrifugal separation unit may be used, but the vanadium-tungsten separation method of the present invention is not limited thereto. In the reacted vanadium-tungsten-containing solution, since tungsten is contained in the organic solvent and vanadium remains in the aqueous solvent, tungsten and vanadium are completely separated from each other by separating the organic solvent and the aqueous solvent.
유기 용매에서 텅스텐을 추출하는 단계(S240) 및 수 용매에서 바나듐을 추출하는 단계(S250)가 수행된다. 이 두 단계는 서로 병렬적으로 수행될 수 있다. Extracting tungsten from an organic solvent (S240) and extracting vanadium from an aqueous solvent (S250) are performed. These two steps can be performed in parallel with each other.
먼저, 유기 용매에서 텅스텐을 추출하는 단계(S240)에 대해 설명하도록 한다. 유기 용매에서 텅스텐을 추출하는 단계(S240)는 세정하는 단계(S241), 유기 용매에 암모니아액을 첨가하여 유기 용매에 포함되어 있던 텅스텐을 APT(Ammonium Para-Tungstate)로 전환시키는 단계(S242), 유기 용매와 APT가 포함된 수 용매를 분리하는 단계(S243), APT가 포함된 수 용매에서 APT를 결정화하는 단계(S244) 및 결정화된 APT를 고액여과 및 소성하여 WO3를 회수하는 단계(S245)가 수행된다. First, the step of extracting tungsten from an organic solvent (S240) will be described. The step of extracting tungsten from the organic solvent (S240) is a step of washing (S241), adding an ammonia solution to the organic solvent to convert tungsten contained in the organic solvent into APT (Ammonium Para-Tungstate) (S242), Separating the organic solvent and the aqueous solvent containing APT (S243), crystallizing APT from the aqueous solvent containing APT (S244), and solid-liquid filtration and calcining the crystallized APT to recover WO 3 (S245). ) is performed.
세정하는 단계(S241)는 분리한 유기 용매를 세정액과 혼합하였다가, 다시 분리하는 과정을 1회 이상 반복하여 수행된다. 세정하는 단계(S241)를 통해 유기 용매에 함유된 텅스텐 이외 불순물을 제거한다. 텅스텐 이외 불순물은 SO4
2- 및 VO2+ 가 포함되며, 세정 단계로 이들을 제거한다. 첨가되는 세정액은 초순수로 초순수의 양은 유기용매 100 중량부에 대해 30 내지 100 중량부 포함될 수 있다.The washing step (S241) is performed by repeating the process of mixing the separated organic solvent with the washing liquid and separating it again one or more times. Impurities other than tungsten contained in the organic solvent are removed through the cleaning step (S241). Impurities other than tungsten include SO 4 2- and VO 2+ , and a cleaning step removes them. The washing solution to be added is ultrapure water, and the amount of ultrapure water may be 30 to 100 parts by weight based on 100 parts by weight of the organic solvent.
유기 용매에 암모니아액을 첨가하여 유기 용매에 포함되어 있던 텅스텐을 APT(Ammonium Para-Tungstate)로 전환시키는 단계(S42)가 수행된다. 세정을 완료한 유기 용매에 암모니아액을 첨가하면 텅스텐이 APT(Ammonium Para-Tungstate)로 전환된다. APT는 수 용매에 용해되므로 이 과정을 통해 텅스텐이 유기 용매에서 수 용매로 이동하게 된다. 첨가되는 암모니아액은 5 ~ 9 wt.% 의 암모니아가 물에 용해된 것을 이용할 수 있다. 암모니아액의 양은 유기 용매 100 중량부에 대해 50 내지 100 중량부 포함될 수 있다.A step (S42) of converting tungsten contained in the organic solvent into APT (Ammonium Para-Tungstate) by adding an ammonia solution to the organic solvent is performed. When ammonia solution is added to the organic solvent that has been cleaned, tungsten is converted into APT (Ammonium Para-Tungstate). Since APT is soluble in aqueous solvent, this process causes tungsten to migrate from organic solvent to aqueous solvent. As the ammonia solution to be added, 5 to 9 wt.% of ammonia dissolved in water may be used. The amount of the ammonia solution may be included in 50 to 100 parts by weight based on 100 parts by weight of the organic solvent.
그 다음 유기 용매와 APT가 포함된 수 용매를 분리하는 단계(S243)를 수행한다. 이 단계도 용매추출형 원심분리유닛을 이용할 수 있다. Then, a step of separating the organic solvent and the aqueous solvent containing APT (S243) is performed. A solvent extraction type centrifugal separation unit may also be used in this step.
APT가 포함된 수 용매에서 APT를 결정화하는 단계(S244)를 수행하고, 결정화된 APT를 고액 여과하고 소성함으로써 WO3를 회수한다(S245). APT를 결정화하는 방법과 APT를 소성하여 WO3를 회수하는 방법은 공지의 방법을 이용할 수 있다. A step of crystallizing APT in an aqueous solvent containing APT (S244) is performed, solid-liquid filtration of the crystallized APT is performed, and WO 3 is recovered by calcining (S245). Known methods can be used for crystallizing APT and recovering WO 3 by calcining APT.
수 용매에서 바나듐을 추출하는 단계(S250)에 대해 살펴보면 다음과 같다. The step of extracting vanadium from the aqueous solvent (S250) is as follows.
수 용매 중 바나듐의 이온 상태를 재전환시키는 단계(S251), 바나듐 용액에 추출제를 첨가하여 반응시키는 단계(S252), 반응 후 유기용매와 수용매로 분리하는 단계(S253), 바나듐을 포함한 유기용매에 암모니아용액을 첨가하여 반응시키는 단계(S54), 반응 후 유기용매와 수용매로 분리하는 단계(S255), 수용매에 암모니아를 추가 첨가하여 AMV로 침전시키는 단계(S256), 고액여과로 AMV를 분리하는 단계(S257), 및 분리한 AMV를 소성하여 V2O5로 회수하는 단계 (S258)가 수행된다.Reconverting the ionic state of vanadium in aqueous solvent (S251), reacting by adding an extractant to the vanadium solution (S252), separating into an organic solvent and an aqueous solvent after the reaction (S253), organic containing vanadium Adding an ammonia solution to the solvent and reacting (S54), separating the organic solvent and the aqueous solvent after the reaction (S255), adding ammonia to the aqueous solvent to precipitate as AMV (S256), and solid-liquid filtration to form AMV Separating (S257), and firing the separated AMV to recover V 2 O 5 (S258) are performed.
먼저, 수 용매 중 바나듐의 이온 상태를 VO2+에서 VO2
+ 로 재전환시키는 단계(S251)가 수행된다. 이 때 첨가제로 과산화수소를 사용하며, 첨가제의 양은 바나듐의 농도를 기준으로 하여 바나듐 1 당량에 1 내지 2 당량 사용한다. 과산화수소 첨가 후 40도 내지 60도 온도에서 1 시간 내지 2 시간 반응을 유지한다. First, a step of reconverting the ionic state of vanadium from VO 2+ to VO 2+ in an aqueous solvent (S251) is performed. At this time, hydrogen peroxide is used as an additive, and the amount of the additive is 1 to 2 equivalents per 1 equivalent of vanadium based on the concentration of vanadium. After adding hydrogen peroxide, the reaction is maintained at a temperature of 40 to 60 degrees for 1 hour to 2 hours.
다음으로 재전환된 바나듐 용액에 추출제를 첨가하여 반응시키는 단계(S252)가 수행된다. 추출제로는 아민계 추출제를 이용하며, 구체적으로 Alamine336 또는 Trioctylamine(TOA)을 이용할 수 있다. 추출제의 양은 바나듐 용액 100 중량부에 대해 10 내지 40 중량부로 포함될 수 있다. 이 단계에 의해 바나듐이 수 용매에서 유기 용매로 이동하게 된다.Next, a step of reacting by adding an extractant to the reconverted vanadium solution (S252) is performed. An amine-based extractant is used as the extractant, and specifically, Alamine336 or Trioctylamine (TOA) may be used. The amount of the extractant may be included in 10 to 40 parts by weight based on 100 parts by weight of the vanadium solution. This step causes vanadium to migrate from the aqueous solvent to the organic solvent.
반응 후 유기용매와 수 용매를 분리하는 단계(S253)가 수행된다. 이 단계에서는 용매추출형 원심분리유닛을 이용할 수 있으나, 본 발명의 바나듐 추출 방법이 이에 제한되는 것은 아니다. 반응시킨 바나듐 용액에서 바나듐은 유기 용매에 포함되고, 수 용매에는 나트륨 및 황산이온이 남아 있기 때문에, 유기 용매와 수 용매로 분리함으로써 바나듐만 선택적으로 추출되어 분리된다.After the reaction, a step of separating the organic solvent and the aqueous solvent (S253) is performed. In this step, a solvent extraction type centrifugal separation unit may be used, but the vanadium extraction method of the present invention is not limited thereto. In the reacted vanadium solution, since vanadium is included in the organic solvent and sodium and sulfate ions remain in the aqueous solvent, only vanadium is selectively extracted and separated by separating the organic solvent and the aqueous solvent.
유기 용매에 암모니아액을 첨가하여 유기 용매에 포함되어 있던 바나듐을 수 용매로 이동시키는 단계(S254)를 수행한다. 첨가되는 암모니아액은 1.0 ~ 1.8 wt%의 암모니아가 물에 용해된 것을 이용할 수 있다. 암모니아액의 양은 유기 용매 100중량부에 대해 30~50 중량부 포함될 수 있다. A step of transferring vanadium contained in the organic solvent to the aqueous solvent by adding an ammonia solution to the organic solvent (S254) is performed. As the ammonia solution to be added, 1.0 to 1.8 wt% of ammonia dissolved in water may be used. The amount of the ammonia solution may be included in an amount of 30 to 50 parts by weight based on 100 parts by weight of the organic solvent.
그 다음 유기 용매와 바나듐이 포함된 수 용매를 분리하는 단계(S255)가 수행되며, 이 단계에도 용매추출형 원심분리유닛을 사용할 수 있다.Then, a step of separating the organic solvent and the aqueous solvent containing vanadium (S255) is performed, and a solvent extraction type centrifugal separation unit can also be used in this step.
바나듐이 포함된 수 용매에 암모니아를 추가 첨가하여 AMV(Ammonium Meta-Vanadate)로 침전하는 단계(S256)를 수행하고, 고액 여과를 통해 AMV를 분리한다(S257). 분리한 AMV를 소성하여 V2O5를 회수한다(S258). 고액 여과와 AMV를 소성하여 V2O5를 회수하는 방법은 공지의 방법을 이용할 수 있다.Ammonia is additionally added to the aqueous solvent containing vanadium to precipitate as AMV (Ammonium Meta-Vanadate) (S256), and AMV is separated through solid-liquid filtration (S257). The separated AMV is fired to recover V 2 O 5 (S258). For solid-liquid filtration and a method for recovering V 2 O 5 by firing AMV, known methods can be used.
회수한 WO3의 순도와 회수한 V2O5의 순도는 모두 99.8% 이상의 고순도이다. The purity of the recovered WO 3 and the purity of the recovered V 2 O 5 are both 99.8% or higher.
상술한 본 발명의 일 실시예에 따른 바나듐-텅스텐 분리 방법(M200)은 바나듐-텅스텐 분리 시스템(100, 도 6 참조)에 의해 수행될 수 있다. The above-described vanadium-tungsten separation method M200 according to an embodiment of the present invention may be performed by the vanadium-tungsten separation system 100 (see FIG. 6).
도 6은 본 발명의 다른 실시예에 따른 바나듐-텅스텐 분리 시스템(100)의 개략적 구성도이다. 6 is a schematic configuration diagram of a vanadium-tungsten separation system 100 according to another embodiment of the present invention.
본 발명의 다른 실시예에 따른 바나듐-텅스텐 분리 시스템(100)은 제1추출유닛(11), 세정유닛(12), 제1탈거유닛(13), 제2추출유닛(22) 및 제2탈거유닛(23)을 포함한다. 각 유닛들은 회전력에 의해 유기용매와 수용매가 혼합되었다가, 원심력에 의해 유기용매(O)와 수용매(A)를 서로 분리할 수 있는 원심분리유닛을 이용한다. 원심분리유닛 외 바나듐용액 처리 반응기(21)가 더 포함된다. The vanadium-tungsten separation system 100 according to another embodiment of the present invention includes a first extraction unit 11, a cleaning unit 12, a first removal unit 13, a second extraction unit 22, and a second removal unit 23. Each unit uses a centrifugal separation unit capable of separating the organic solvent (O) and the aqueous medium (A) from each other by centrifugal force after the organic solvent and the aqueous medium are mixed by rotational force. In addition to the centrifugal separation unit, a vanadium solution treatment reactor 21 is further included.
제1추출유닛(11)으로는 전처리된 바나듐-텅스텐 함유 용액과 추출제가 유입된다. 전처리된 바나듐-텅스텐 함유 용액은 VO2+ 이온과 WO4
2- 이온을 포함하는 용액이며, 추출제는 아민계 추출제(예를 들어, Alamine 336)이다. 텅스텐 추출유닛(11) 내에서 바나듐-텅스텐 함유 용액과 추출제는 서로 혼합되며, 원심력에 의해 유기 용매와 수 용매가 분리되어 각각 배출된다. 이때, 텅스텐은 유기 용매로 배출되고, 바나듐은 수 용매로 배출된다. The pretreated vanadium-tungsten-containing solution and the extractant are introduced into the first extraction unit 11 . The pretreated vanadium-tungsten-containing solution is a solution containing VO 2+ ions and WO 4 2- ions, and an extractant is an amine-based extractant (eg, Alamine 336). In the tungsten extraction unit 11, the vanadium-tungsten-containing solution and the extraction agent are mixed with each other, and the organic solvent and the aqueous solvent are separated and discharged respectively by centrifugal force. At this time, tungsten is discharged into an organic solvent, and vanadium is discharged into an aqueous solvent.
제1추출유닛(11)에서 배출된 유기 용매는 세정유닛(12)으로 유입된다. 세정유닛(12)으로는 세정액이 함께 유입되는데, 세정유닛(12) 내에서 유기 용매와 세정액이 혼합되며, 원심력에 의해 다시 서로 분리되어 각각 배출된다. 이 과정에서 제1추출유닛(11)에서 텅스텐 이외 불순물을 제거한다.The organic solvent discharged from the first extraction unit 11 flows into the cleaning unit 12 . The cleaning liquid is introduced into the cleaning unit 12, and the organic solvent and the cleaning liquid are mixed in the cleaning unit 12, separated from each other again by centrifugal force, and discharged. In this process, impurities other than tungsten are removed from the first extraction unit 11 .
세정 유닛(12)에 의해 불순물이 제거된 텅스텐을 포함한 유기용매는 제 1탈거유닛으로 유입된다. 제1탈거유닛(13) 내에서 텅스텐을 포함하는 유기 용매와 암모니아액이 혼합되며, 원심력에 의해 서로 분리되어 각각 배출된다. 유기 용매와 암모니아액이 혼합되는 과정에서 텅스텐이 APT용액으로 전환되어 수 용매로 이동하여 배출된다. 배출한 APT 용액은 결정화 후 수득한 APT 고액 여과 및 소성을 거쳐 WO3를 회수한다.The organic solvent including tungsten from which impurities are removed by the cleaning unit 12 flows into the first stripping unit. In the first stripping unit 13, the organic solvent containing tungsten and the ammonia liquid are mixed, separated from each other by centrifugal force, and discharged. In the process of mixing the organic solvent and the ammonia solution, tungsten is converted into an APT solution and moved to an aqueous solvent to be discharged. The discharged APT solution is subjected to solid-liquid filtration and calcining of APT obtained after crystallization to recover WO 3 .
반응기(21)에서 바나듐 이온상태를 재전환 처리한 후, 제2추출유닛(22)로 추출제와 함께 유입된다. 제2추출유닛(21) 내에서 수 용매와 추출제가 서로 혼합되며, 원심력에 의해 서로 분리되어 배출된다.After the vanadium ion state is reconverted in the reactor 21, it is introduced into the second extraction unit 22 together with the extractant. The aqueous solvent and the extractant are mixed with each other in the second extraction unit 21, and are separated from each other and discharged by centrifugal force.
제2추출유닛(22)으로부터 배출되는 바나듐 포함 유기용매는 제 2탈거유닛(23)으로 유입된다. 제2탈거유닛(23) 내에서 바나듐을 포함하는 유기 용매와 암모니아액이 혼합되며, 원심력에 의해 서로 분리되어 각각 배출된다. 유기 용매와 암모니아액이 혼합되는 과정에서 바나듐은 수 용매로 이동하여 배출하게 된다. 배출한 바나듐 용액은 암모니아를 추가 첨가하여 AMV로 침전하고, 침전 후 고액 여과 및 소성을 거쳐 V2O5로 회수한다.The organic solvent containing vanadium discharged from the second extraction unit 22 flows into the second separation unit 23 . In the second stripping unit 23, the organic solvent containing vanadium and the ammonia solution are mixed, separated from each other by centrifugal force, and discharged. In the process of mixing the organic solvent and the ammonia solution, vanadium moves to the aqueous solvent and is discharged. The discharged vanadium solution is precipitated as AMV by additionally adding ammonia, and after precipitation, it is recovered as V 2 O 5 through solid-liquid filtration and sintering.
한편, 제1탈거유닛(13) 및 제 2탈거유닛(23)에서 원심력에 의해 수용매와 분리된 유기 용매는 재생하여 다시 추출제로 사용한다.Meanwhile, the organic solvent separated from the aqueous medium by the centrifugal force in the first stripping unit 13 and the second stripping unit 23 is regenerated and used as an extractant again.
본 발명의 다른 실시예에 따른 바나듐-텅스텐 분리 시스템(100)은 종래 자주 이용되던 믹스세틀러에 비해 단위면적당 차지하는 공간이 적고, 처리 속도가 빨라 생산성 향상 및 운영에 매우 유리하여 양산에 적합하다. 무엇보다 폐쇄된 시스템으로 운영되기 때문에 공정 과정에서 용매의 휘발이 최소화 되는 장점이 있다. The vanadium-tungsten separation system 100 according to another embodiment of the present invention occupies less space per unit area and has a faster processing speed compared to a conventional mixtaker, which is very advantageous for productivity improvement and operation, and is suitable for mass production. Above all, since it is operated as a closed system, it has the advantage of minimizing volatilization of the solvent during the process.
<실시예 4: 바나듐-텅스텐 분리의 수행><Example 4: Performance of vanadium-tungsten separation>
1) 바나듐-텅스텐 함유 용액의 준비1) Preparation of vanadium-tungsten containing solution
화력발전소에서 수거한 탈질폐촉매를 분쇄하고, 오븐에서 건조하여 탈질폐촉매 파우더를 제조하였다. 탈질폐촉매 파우더의 입도는 ≤ 212 μm였다. 제조한 탈질폐촉매 파우더 1kg 당 탄산나트륨 0.95 kg을 혼합하여 혼합물을 만들었다. 혼합물은 크랭크형 프레스를 이용하여 500 kgf/cm2이상의 성형압력으로 단면적 60 cm2, 높이 3.5 cm의 원기둥형의 가성형체를 제조하였다. 가성형체의 제조과정에서 발열에 의해 50 ℃의 온도가 상승됨을 확인할 수 있었다. 제조한 가성형체는 가열로 내에서 900 ℃로 60분간 소결하여 알칼리 소결 성형체를 제조하였다. The spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst. The particle size of the spent denitrification catalyst powder was ≤ 212 μm. A mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder. The mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 500 kgf/cm 2 or more using a crank-type press. It was confirmed that the temperature of 50 ℃ was increased by heat generation during the manufacturing process of the pseudo-shaped body. The prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
알칼리 소결 성형체는 분쇄하였고, 이로부터 유가금속을 침출하였다. The alkali sintered compact was pulverized, and valuable metals were leached therefrom.
분쇄된 알칼리 소결 성형체를 물 100 중량부에 대해 50 중량부 첨가하여 수침출을 충분히 수행하였다. 수침출을 수행한 물의 온도는 50 ℃였다. 수침출을 수행한 후 고형물은 여과하여 침출액과 고형물을 분리하였다. Water leaching was sufficiently performed by adding 50 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water. The water temperature for water leaching was 50 °C. After performing water leaching, the solids were filtered to separate the leachate and the solids.
침출액이 바나듐-텅스텐 함유 용액이 된다. The leachate becomes a vanadium-tungsten containing solution.
2) 바나듐-텅스텐 함유 용액의 전처리2) Pretreatment of vanadium-tungsten containing solution
바나듐-텅스텐 함유 용액에 황산을 첨가하여 pH를 1로 낮추고, 바나듐 환원제로 아황산나트륨(NaHSO3)을 바나듐 1 당량 당 1.5 당량 첨가하였다. Sulfuric acid was added to the vanadium-tungsten-containing solution to lower the pH to 1, and 1.5 equivalents of sodium sulfite (NaHSO 3 ) was added per 1 equivalent of vanadium as a vanadium reducing agent.
3) 바나듐과 텅스텐의 분리 3) Separation of vanadium and tungsten
바나듐-텅스텐 분리 시스템에 전처리를 수행한 바나듐-텅스텐 함유 용액을 투입하여 분리를 수행하였다. 추출제로는 Trioctylamine(TOA)을 사용하였다. Separation was performed by introducing the pretreated vanadium-tungsten containing solution into the vanadium-tungsten separation system. Trioctylamine (TOA) was used as an extractant.
바나듐-텅스텐 분리 시스템으로부터 수득한 APT 용액을 결정화하고 고액여과 후 회수한 APT를 소성하여 WO3를 획득하였다. 또한, 바나듐-텅스텐 분리 시스템으로부터 수득한 바나듐 용액으로부터 AMV로 침전시킨 후 고액 여과하고, 수득한 AMV를 소성하여 V2O5를 획득하였다.The APT solution obtained from the vanadium-tungsten separation system was crystallized, and the APT recovered after solid-liquid filtration was calcined to obtain WO 3 . In addition, AMV was precipitated from the vanadium solution obtained from the vanadium-tungsten separation system, followed by solid-liquid filtration, and the obtained AMV was calcined to obtain V 2 O 5 .
4) 결과4) Results
수득한 WO3와 V2O5는 X-ray 회절을 통해 존재를 확인하였으며, 회수한 WO3의 순도와 회수한 V2O5의 순도는 모두 99.8% 이상의 고순도임을 확인할 수 있었다. The existence of the obtained WO 3 and V 2 O 5 was confirmed through X-ray diffraction, and it was confirmed that both the purity of the recovered WO 3 and the purity of the recovered V 2 O 5 were 99.8% or higher.
<실시예 5: 전처리 과정에서 pH의 영향><Example 5: Effect of pH in the pretreatment process>
실시예 4와 동일한 방법으로 바나듐-텅스텐 분리를 수행하되, 전처리 과정에서 pH를 조절하여 그 영향을 도 7에 나타내었다. 도 7은 텅스텐 추출루트에서의 바나듐과 텅스텐의 추출 결과이므로 텅스텐의 추출율은 높고, 바나듐의 추출율이 낮아아 텅스텐과 바나듐의 분리도가 증가한 것으로 볼 수 있다. 한편, 텅스텐 추출루트에서의 바나듐 추출율이 증가하면 본 발명의 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐 분리 방법 전체를 기준으로 바나듐의 추출율은 감소할 수 밖에 없다. 이는 아래의 도 8 및 9에서도 동일하다.The vanadium-tungsten separation was performed in the same manner as in Example 4, but the pH was adjusted in the pretreatment process, and the effect thereof is shown in FIG. 7 . Since FIG. 7 shows the extraction results of vanadium and tungsten in the tungsten extraction route, it can be seen that the extraction rate of tungsten is high and the extraction rate of vanadium is low, resulting in increased separation between tungsten and vanadium. On the other hand, if the vanadium extraction rate in the tungsten extraction route increases, the vanadium extraction rate inevitably decreases based on the entire vanadium-tungsten separation method in the vanadium-tungsten containing solution of the present invention. This is the same in FIGS. 8 and 9 below.
도 7을 참조하면, 용액 중 바나듐 농도는 약 0.01M일 경우 pH 2 이상에서는 텅스텐 추출루트에서 바나듐의 추출율이 증가하는데, 이는 전처리 과정에서 바나듐-텅스텐 함유 용액에 포함되어 있던 VO3
- 이온이 VO2
+이온으로 전환되지 못한 것이다. 즉, 바나듐 농도가 약 0.01M 인 경우 pH 1.2 이상에서는 바나듐 이온의 전환율이 점차 낮아진다. 텅스텐의 경우, pH 1~2 에서 99.9% 이상의 추출율을 나타내며, pH 0.5 이하 또는 pH 3 이상에서는 추출능이 낮아진다. 이는 Alamine336 Trioctylamine(TOA)의 텅스텐 추출특성에 관련 있으며, 일반적으로 상기 추출제는 pH 1~2에서 텅스텐 추출능이 높다고 알려져 있다.Referring to FIG. 7, when the vanadium concentration in the solution is about 0.01 M, the extraction rate of vanadium increases in the tungsten extraction route at pH 2 or higher. It is not converted to 2+ ion. That is, when the vanadium concentration is about 0.01 M, the conversion rate of vanadium ions gradually decreases at pH 1.2 or higher. In the case of tungsten, it shows an extraction rate of 99.9% or more at pH 1-2, and the extraction ability decreases at pH 0.5 or less or pH 3 or more. This is related to the tungsten extraction characteristics of Alamine336 Trioctylamine (TOA), and it is generally known that the extractant has a high tungsten extraction ability at pH 1-2.
<실시예 6: 전처리 과정에서 전처리제의 양의 영향><Example 6: Influence of amount of pretreatment agent in pretreatment process>
실시예 4와 동일한 방법으로 바나듐-텅스텐 분리를 수행하되, 전처리 과정에서 전처리제의 양을 조절하여 그 영향을 도 8에 나타내었다. The vanadium-tungsten separation was performed in the same manner as in Example 4, but the amount of the pretreatment agent was adjusted in the pretreatment process, and the effect thereof is shown in FIG. 8 .
도 8을 참조하면, 전처리제의 양이 바나듐 1당량에 1.25 당량 미만인 경우 VO2+이온으로 전환되지 않은 VO2
+이온이 잔류하여 텅스텐 추출루트에서 바나듐의 추출율이 증가하는 것을 확인할 수 있으며, 1.75 당량을 초과할 경우에는 전처리제가 전처리에 더 이상 기여하지 못해 바나듐의 추출율이 증가하지 않는 것을 확인할 수 있다.Referring to FIG. 8, when the amount of the pretreatment agent is less than 1.25 equivalents to 1 equivalent of vanadium, VO 2+ ions that are not converted to VO 2+ ions remain, and it can be seen that the vanadium extraction rate increases in the tungsten extraction root, and 1.75 When the equivalent weight is exceeded, it can be seen that the pretreatment agent does not contribute to the pretreatment any more and the vanadium extraction rate does not increase.
<실시예 7: 추출과정에서 추출제의 양의 영향 ><Example 7: Influence of the amount of extractant in the extraction process>
실시예 4와 동일한 방법으로 각 유가금속을 추출하되, 추출과정에서 추출제의 양을 변화시켜 그 영향을 도 9에 나타내었다. Each valuable metal was extracted in the same manner as in Example 4, but the amount of the extractant was changed in the extraction process, and the effect thereof is shown in FIG. 9 .
도 9를 참조하면, 추출제의 양이 전처리한 바나듐-텅스텐 함유 용액 100 중량부에 대해 10 중량부 미만인 경우 텅스텐이 수 용매에 잔류하게 되는 문제가 있어 텅스텐의 추출율이 감소하는 것을 확인할 수 있었으며, 50 중량부를 초과할 경우에는 텅스텐 추출루트에서 바나듐의 추출율이 상승하여 바나듐과 텅스텐의 분리도가 낮아지는 현상을 초래한다.Referring to FIG. 9, when the amount of the extractant is less than 10 parts by weight with respect to 100 parts by weight of the pretreated vanadium-tungsten-containing solution, there is a problem that tungsten remains in the aqueous solvent, so it can be confirmed that the extraction rate of tungsten is reduced, If it exceeds 50 parts by weight, the extraction rate of vanadium increases in the tungsten extraction route, resulting in a phenomenon in which the degree of separation between vanadium and tungsten is lowered.
3. 타이타늄 함유 염산 용액을 이용한 아나타제형 이산화타이타늄의 제조3. Preparation of anatase-type titanium dioxide using titanium-containing hydrochloric acid solution
여기에서 이용하는 타이타늄 함유 염산 용액은 탈질폐촉매로부터 산침출하여 수득한 것으로 볼 수 있으나, 본 발명이 이에 제한되는 것은 아니다.The titanium-containing hydrochloric acid solution used herein can be regarded as obtained by acid leaching from a waste denitrification catalyst, but the present invention is not limited thereto.
도 10은 본 발명의 일 실시예에 따른 타이타늄 함유 염산용액을 이용한 아나타제형 이산화타이타늄 제조 방법(M300)의 개략적 플로우 차트이다.10 is a schematic flow chart of a method for producing anatase-type titanium dioxide (M300) using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention.
도 10을 참조하면, 본 발명의 일 실시예에 따른 아나타제형 이산화타이타늄 제조 방법(M300)은 타이타늄 씨드용액을 제조하는 단계(S310), 타이타늄 씨드용액, 결정 선택제를 타이타늄 함유 염산 용액에 첨가해 혼합 용액을 제조하는 단계(S320) 및 혼합 용액을 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계(S330)를 포함한다. Referring to FIG. 10, the method for producing anatase-type titanium dioxide (M300) according to an embodiment of the present invention includes preparing a titanium seed solution (S310), adding the titanium seed solution and a crystal selector to a titanium-containing hydrochloric acid solution and mixing them. A step of preparing a solution (S320) and a step of hydrolyzing the mixed solution to form anatase-type titanium dioxide (S330).
마련한 타이타늄 함유 염산 용액은 8 ~ 12 wt%의 타이타늄을 함유하고 있으며, 8 ~ 10 M의 염산 몰 농도를 가진다.The prepared titanium-containing hydrochloric acid solution contains 8 to 12 wt% of titanium and has a hydrochloric acid molar concentration of 8 to 10 M.
먼저, 마련한 타이타늄 함유 염산 용액 중 일부를 이용하여 타이타늄 씨드용액을 제조한다(S310). 설명의 명확성을 위해 타이타늄 씨드용액을 제조하는데 이용된 타이타늄 함유 염산용액은 제1타이타늄 함유 염산용액으로 정의한다. 타이타늄 씨드용액을 제조하기 위해 먼저 100 중량부의 제1타이타늄 함유 염산 용액에 30 내지 70 중량부의 수산화나트륨을 첨가하고 상온에서 혼합하여 씨드 혼합용액을 제조한다. 그 다음 100중량부의 씨드 혼합용액에 30 내지 70 중량부의 물을 60 ~ 80 ℃에서 25 ~ 35 분간 혼합하여 타이타늄 씨드용액을 제조한다. 후술하는 바와 같이 본 발명의 아나타제형 이산화타이타늄 제조방법은 가수분해에 의해 이산화타이타늄을 제조하게 되는데, 타이타늄 씨드용액을 이용할 경우 이산화타이타늄이 제조하는데 필요한 시간을 현저히 감소시킬 수 있으며 제조되는 이산화타이타늄의 입도나 순도 등의 품질이 증가된다. First, a titanium seed solution is prepared using some of the prepared titanium-containing hydrochloric acid solution (S310). For clarity of explanation, the titanium-containing hydrochloric acid solution used to prepare the titanium seed solution is defined as the first titanium-containing hydrochloric acid solution. To prepare a titanium seed solution, first, 30 to 70 parts by weight of sodium hydroxide is added to 100 parts by weight of the first titanium-containing hydrochloric acid solution and mixed at room temperature to prepare a seed mixture solution. Then, 30 to 70 parts by weight of water is mixed with 100 parts by weight of the seed mixture solution at 60 to 80 ° C. for 25 to 35 minutes to prepare a titanium seed solution. As will be described later, the method for producing anatase-type titanium dioxide of the present invention produces titanium dioxide by hydrolysis. When a titanium seed solution is used, the time required for preparing titanium dioxide can be significantly reduced, and the particle size of the titanium dioxide produced can be significantly reduced. Quality, such as purity, is increased.
타이타늄 씨드용액을 제조하는 과정은 다음과 같은 반응식 2에 의해 수행된다. The process of preparing the titanium seed solution is performed by the following Reaction Scheme 2.
[반응식 2][Scheme 2]
TiOCl2 (Aq.) + 2NaOH (Aq.) → TiO(OH)2 (s) + 2NaCl (Aq.)TiOCl 2 (Aq.) + 2NaOH (Aq.) → TiO(OH) 2 (s) + 2NaCl (Aq.)
반응식 2에서 알 수 있듯이, 타이타늄 씨드용액에는 이산화타이타늄의 수화물 형태인 메타타이타닉 산이 포함된다.As shown in Scheme 2, the titanium seed solution contains metatitanic acid, which is a hydrate form of titanium dioxide.
제조한 타이타늄 씨드용액을 이용하여 혼합용액을 제조하는 단계(S320)를 수행한다. 타이타늄 씨드용액은 미리 대량으로 제조하였다가, 일부를 이용하여 혼합용액을 제조하는 단계(S320)에 이용함으로써 공정에 소요되는 시간을 단축할 수 있다. A step of preparing a mixed solution using the prepared titanium seed solution (S320) is performed. The time required for the process can be shortened by preparing a large amount of the titanium seed solution in advance and using some of it in the step of preparing a mixed solution (S320).
혼합용액을 제조하는 단계(S320)에서는 타이타늄 씨드용액과 결정 선택제를 타이타늄 함유 염산 용액에 첨가하고 혼합하여 수행된다. 혼합용액을 제조하는 단계(S320)에서 이용하는 타이타늄 함유 염산용액은 제2타이타늄 함유 염산용액으로 정의할 수 있다. 다만, 이는 설명의 명확성을 위한 것이며, 제1 및 제2타이타늄 함유 염산용액은 서로 조성이 다른 것을 이용하거나, 동일한 것을 이용하거나 할 수 있다. In the step of preparing the mixed solution (S320), the titanium seed solution and the crystal selector are added to the titanium-containing hydrochloric acid solution and mixed. The titanium-containing hydrochloric acid solution used in the step of preparing the mixed solution (S320) may be defined as a second titanium-containing hydrochloric acid solution. However, this is for clarity of explanation, and the first and second titanium-containing hydrochloric acid solutions may use different compositions or the same ones.
타이타늄 씨드용액의 함량은 제2타이타늄 함유 염산용액 100중량부에 대해 1내지 4중량부 일 수 있다. 타이타늄 씨드용액의 함량이 제2타이타늄 함유 염산용액 100중량부에 대해 1 중량부 미만인 경우 타이타늄 씨드용액을 이용하는 효과가 미미하며, 4 중량부를 초과할 경우 제조되는 이산화타이타늄의 입도가 증가하게 된다. 씨드는 반응에서 결정핵을 제공하여 균질한 반응을 유도하고, 이에 따라 특정 입자의 과성장을 억제하는 역할을 한다. 다만, 씨드를 과량 첨가할 경우 결정핵이 과하게 생성되며, 과하게 생성된 결정핵에 의해 이산화타이타늄의 입자가 응집되고, 응집된 입자는 소성 과정에서 하나의 큰 덩어리로 응결되어 입도가 증가하게 된다. The content of the titanium seed solution may be 1 to 4 parts by weight based on 100 parts by weight of the second titanium-containing hydrochloric acid solution. When the content of the titanium seed solution is less than 1 part by weight based on 100 parts by weight of the second titanium-containing hydrochloric acid solution, the effect of using the titanium seed solution is insignificant, and when it exceeds 4 parts by weight, the particle size of the titanium dioxide produced increases. The seed induces a homogeneous reaction by providing crystal nuclei in the reaction, and thus serves to suppress the overgrowth of specific particles. However, when seeds are added in excess, crystal nuclei are generated excessively, and titanium dioxide particles are agglomerated by the excessively generated crystal nuclei, and the agglomerated particles are condensed into one large lump during the firing process, increasing the particle size.
한편, 아나타제형 이산화타이타늄을 제조하기 위해 본 발명의 일 실시예에 따른 아나타제형 이산화타이타늄 제조 방법(M300)은 결정 선택제를 타이타늄 함유 염산 용액에 첨가하고 혼합한다. 결정 선택제는 생성되는 이산화타이타늄의 결정형을 아나타제형으로 만드는 역할을 한다. On the other hand, in the anatase-type titanium dioxide manufacturing method (M300) according to an embodiment of the present invention to manufacture anatase-type titanium dioxide, a crystal selector is added to a titanium-containing hydrochloric acid solution and mixed. The crystal selector serves to make the crystal form of titanium dioxide produced into an anatase form.
결정 선택제로는 황산, 인산 및 인산수소이나트륨으로 이루어진 군에서 선택되는 어느 하나 또는 이들의 혼합물일 수 있다. 이때, 황산은 제1형 결정 선택제로 분류할 수 있으며, 인산 및 인산수소이나트륨은 제2형 결정 선택제로 분류할 수 있다. 제1형 결정 선택제는 제조되는 이산화타이타늄을 아나타제형이 되도록 하며, 제2형 결정 선택제는 제조되는 이산화타이타늄을 아나타제형이 되도록 하는 것과 제조되는 입도 및 입형을 제어하는 역할을 한다. The crystal selector may be any one selected from the group consisting of sulfuric acid, phosphoric acid, and disodium hydrogen phosphate, or a mixture thereof. At this time, sulfuric acid can be classified as a type 1 crystal selector, and phosphoric acid and disodium hydrogen phosphate can be classified as a type 2 crystal selector. The first-type crystal selector serves to make the produced titanium dioxide anatase-type, and the second-type crystal selector serves to make the produced titanium dioxide anatase-type and controls the particle size and particle shape to be produced.
생성되는 아나타제형 이산화타이타늄이 99 wt%이 되도록 제어하기 위해서는 결정 선택제의 함량을 조절해야 한다. In order to control the resulting anatase-type titanium dioxide to be 99 wt%, the content of the crystal selector must be adjusted.
구체적으로 결정 선택제가 황산인 경우에 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 10 중량부 이상 첨가하며, 결정 선택제가 인산인 경우에 상기 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 0.4 중량부 이상 첨가하며, 결정 선택제가 인산수소이나트륨인 경우에 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 0.5 중량부 이상 첨가한다. 결정 선택제가 상한에 미달할 경우 제조되는 이산화타이타늄에 아나타제형과 루타일형이 혼재한다. 결정 선택제를 전혀 첨가하지 않은 경우 생성되는 이산화타이타늄의 99 wt% 이상이 루타일형이 된다. Specifically, when the crystal selector is sulfuric acid, the crystal selector is added in an amount of 10 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution, and when the crystal selector is phosphoric acid, the crystal selector is 100 parts by weight of the second titanium-containing hydrochloric acid solution. 0.4 part by weight or more, and when the crystal selector is disodium hydrogen phosphate, the crystal selector is added in an amount of 0.5 part by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution. When the crystal selection agent is less than the upper limit, the anatase type and the rutile type are mixed in the titanium dioxide produced. When no crystal selector is added, more than 99 wt% of the titanium dioxide produced is in the rutile form.
한편, 제2형 결정 선택제를 상한을 초과하여 첨가할 경우 제조되는 아나타제형 이산화타이타늄 중 인의 함량이 증가하여 품질을 저하시킨다.On the other hand, when the type 2 crystal selector is added in excess of the upper limit, the content of phosphorus in the anatase-type titanium dioxide produced increases, resulting in deterioration in quality.
제2형 결정 선택제를 첨가할 경우 인산염을 포함하는데, 인산염은 다음의 반응식 3고 같이 이산화타이타늄의 표면에 흡착된다. When the type 2 crystal selector is added, phosphate is included, and phosphate is adsorbed on the surface of titanium dioxide as shown in Scheme 3 below.
[반응식 3][Scheme 3]
O-Ti-OH + H+ + H2PO4
- → O-Ti-PO4H2
- +H2O O-Ti-OH + H + + H 2 PO 4 - → O-Ti-PO 4 H 2 - +H 2 O
즉, 인산염의 음이온(H2PO4
-)이 양성자를 띈 Ti 산화물에 강하게 흡착되어 구 형태의 복합체를 형성한다. 또한, Ti 산화물에 표면에 강하게 흡착된 인산염의 음이온(H2PO4
-)이 응집을 방해하여 입자의 성장을 방해한다. 이에 따라 아나타제형 이산화타이타늄의 입형을 구형에 가깝도록 만들어지며 입도가 작아진다. That is, the phosphate anion (H 2 PO 4 - ) is strongly adsorbed to the protonated Ti oxide to form a spherical complex. In addition, phosphate anions (H 2 PO 4 - ) strongly adsorbed on the surface of Ti oxide hinder aggregation and thus hinder particle growth. Accordingly, the particle shape of the anatase-type titanium dioxide is made to be close to a sphere, and the particle size is reduced.
다음으로 혼합 용액을 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계(S330)가 수행된다. 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계는 물을 첨가하고, 90 ~ 110 ℃에서 150 ~ 210분 동안 수행한다. 이때, 물과 함께 수산화나트륨을 더 포함할 수 있다. Next, a step of hydrolyzing the mixed solution to form anatase-type titanium dioxide (S330) is performed. The step of hydrolyzing to form anatase-type titanium dioxide is performed by adding water and at 90 to 110° C. for 150 to 210 minutes. At this time, sodium hydroxide may be further included together with water.
첨가하는 물의 양은 100중량부의 혼합 용액에 대해서 25 내지 40 중량부를 포함할 수 있다. 수산화나트륨을 더 포함할 경우 첨가되는 수산화나트륨의 양은 100중량부의 혼합 용액에 대해서 2 내지 6 중량부를 포함할 수 있다. 가수분해시 혼합 용액 중에 타이타늄 농도와 산 농도가 높을 경우 가수반응이 억제되는 바, 타이타늄 농도와 산 농도가 높을수록 요구되는 물과 수산화나트륨의 양이 증가된다.The amount of water added may include 25 to 40 parts by weight based on 100 parts by weight of the mixed solution. When sodium hydroxide is further included, the amount of sodium hydroxide added may include 2 to 6 parts by weight based on 100 parts by weight of the mixed solution. When the titanium concentration and the acid concentration in the mixed solution are high during hydrolysis, the hydrolysis reaction is inhibited, and the higher the titanium concentration and the acid concentration, the higher the required amount of water and sodium hydroxide.
한편, 가수분해 후에 수득한 수득물은 하소함으로써 아나타제형 이산화타이타늄을 제조하게 된다. 하소하는 단계는 600 내지 900 ℃에서 수행될 수 있다. On the other hand, the product obtained after hydrolysis is calcined to produce anatase-type titanium dioxide. Calcining may be performed at 600 to 900 °C.
4. 타이타늄 함유 염산 용액을 이용하여 제조되는 아나타제형 이산화타이타늄의 결정 제어 방법4. Crystal control method of anatase-type titanium dioxide produced using titanium-containing hydrochloric acid solution
도 11는 본 발명의 다른 실시예에 따른 타이타늄 함유 염산용액을 이용한 이산화타이타늄 결정 제어 방법(M400)의 개략적 플로우 차트이다.11 is a schematic flow chart of a titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention.
도 11을 참조하면, 본 발명의 다른 실시예에 따른 이산화타이타늄 결정 제어 방법(M400)은 타이타늄 씨드용액을 제조하는 단계(S410), 타이타늄 씨드용액을 타이타늄 함유 염산 용액에 첨가해 혼합 용액을 제조하는 단계(S420) 및 혼합 용액을 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계(S430)를 포함한다. 본 발명의 다른 실시예에 따른 타이타늄 함유 염산용액을 이용한 이산화타이타늄 결정 제어 방법(M400) 중 전술한 본 발명의 일 실시예에 따른 타이타늄 함유 염산용액을 이용한 아나타제 이산화타이타늄 제조방법(M300)과 동일한 부분에 대해서는 설명을 생략하도록 한다. Referring to FIG. 11, the titanium dioxide crystal control method (M400) according to another embodiment of the present invention includes preparing a titanium seed solution (S410), adding the titanium seed solution to a titanium-containing hydrochloric acid solution to prepare a mixed solution A step (S420) and a step of hydrolyzing the mixed solution to form anatase-type titanium dioxide (S430). Among the titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention, the same part as the anatase titanium dioxide manufacturing method (M300) using a titanium-containing hydrochloric acid solution according to an embodiment of the present invention described above Omit the description of .
타이타늄 씨드용액을 타이타늄 함유 염산 용액에 첨가해 혼합 용액을 제조하는 단계(S420)에 있다. It is in the step of preparing a mixed solution by adding the titanium seed solution to the titanium-containing hydrochloric acid solution (S420).
즉, 본 발명의 다른 실시예에 따른 타이타늄 함유 염산용액을 이용한 이산화타이타늄 결정 제어 방법(M400)은 혼합 용액을 제조하는 단계(S430)에서 결정 선택제를 첨가하지 않음으로써 루타일형 이산화타이타늄을 형성하고, 결정 선택제를 첨가함으로써 아나타제형 이산화타이타늄을 형성한다.That is, the titanium dioxide crystal control method (M400) using a titanium-containing hydrochloric acid solution according to another embodiment of the present invention forms rutile-type titanium dioxide by not adding a crystal selector in the step of preparing a mixed solution (S430), Anatase-type titanium dioxide is formed by adding a crystal selector.
구체적으로 생성되는 아나타제형 이산화타이타늄이 99 wt.%이 되도록 제어하기 위해서, 결정 선택제가 황산인 경우에 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 10 중량부 이상 첨가하며, 결정 선택제가 인산인 경우에 상기 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 0.4 중량부 이상 첨가하며, 결정 선택제가 인산수소이나트륨인 경우에 결정 선택제는 제2타이타늄 함유 염산 용액 100중량부에 대해 0.5 중량부 이상 첨가한다. 결정 선택제가 상한에 미달할 경우 제조되는 이산화타이타늄에 아나타제형과 루타일형이 혼재한다. 즉, 결정 선택제의 첨가량을 제어하여 형성되는 이산화타이타늄 내에서 루타일형과 아나타제형의 비율을 조절되는 것이다. 한편, 결정 선택제를 전혀 첨가하지 않은 경우 생성되는 이산화타이타늄의 99 wt% 이상이 루타일형이 된다. Specifically, in order to control the produced anatase-type titanium dioxide to be 99 wt.%, when the crystal selector is sulfuric acid, the crystal selector is added in an amount of 10 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution, and the crystal selector is In the case of phosphoric acid, the crystal selector is added in an amount of 0.4 parts by weight or more based on 100 parts by weight of the second titanium-containing hydrochloric acid solution. Add more than one part by weight. When the crystal selection agent is less than the upper limit, the anatase type and the rutile type are mixed in the titanium dioxide produced. That is, the ratio of the rutile type and the anatase type in the formed titanium dioxide is adjusted by controlling the addition amount of the crystal selector. On the other hand, when no crystal selector is added, more than 99 wt% of the titanium dioxide produced is in the rutile type.
<실시예 8: 아나타제형 이산화타이타늄의 제조><Example 8: Preparation of anatase-type titanium dioxide>
화력발전소에서 수거한 탈질폐촉매를 분쇄하고, 오븐에서 건조하여 탈질폐촉매 파우더를 제조하였다. 탈질폐촉매 파우더의 입도는 ≤ 212 μm였다. 제조한 탈질폐촉매 파우더 1kg 당 탄산나트륨 0.95 kg을 혼합하여 혼합물을 만들었다. 혼합물은 크랭크형 프레스를 이용하여 1500 kgf/cm2의 성형압력으로 단면적 60 cm2, 높이 3.5 cm의 원기둥형의 가성형체를 제조하였다. 가성형체의 제조과정에서 발열에 의해 50 ℃의 온도가 상승됨을 확인할 수 있었다. 제조한 가성형체는 가열로 내에서 900 ℃로 60분간 소결하여 알칼리 소결 성형체를 제조하였다. The spent denitrification catalyst collected from the thermal power plant was pulverized and dried in an oven to prepare a powder of the denitrification waste catalyst. The particle size of the spent denitrification catalyst powder was ≤ 212 μm. A mixture was prepared by mixing 0.95 kg of sodium carbonate per 1 kg of the prepared spent denitrification catalyst powder. The mixture was prepared in a cylindrical shape with a cross-sectional area of 60 cm 2 and a height of 3.5 cm at a molding pressure of 1500 kgf/cm 2 using a crank-type press. It was confirmed that the temperature of 50 ° C. was increased by exotherm during the manufacturing process of the pseudo-shaped body. The prepared temporary molded body was sintered at 900 ° C. for 60 minutes in a heating furnace to prepare an alkali sintered molded body.
알칼리 소결 성형체는 분쇄하였고, 이로부터 유가금속을 침출하였다. The alkali sintered compact was pulverized, and valuable metals were leached therefrom.
분쇄된 알칼리 소결 성형체를 물 100 중량부에 대해 30 중량부 첨가하여 수침출을 충분히 수행하였다. 수침출을 수행한 물의 온도는 80 ℃였다. 수침출을 수행한 후 고형물은 여과하여 침출액과 고형물을 분리하였다. Water leaching was sufficiently performed by adding 30 parts by weight of the pulverized alkali sintered molded body to 100 parts by weight of water. The temperature of the water subjected to water leaching was 80 °C. After performing water leaching, the solids were filtered to separate the leachate and the solids.
고형물을 염산 100 중량부에 대해 30 중량부 첨가하여 산침출을 수행하였다. 산침출은 60 ℃에서 3시간동안 진행되었다. 산침출 결과 10 wt.%의 타이타늄을 함유하고 있으며, 9 M의 염산 몰 농도를 가지는 타이타늄 함유 염산 용액을 마련하였다. Acid leaching was performed by adding 30 parts by weight of solids to 100 parts by weight of hydrochloric acid. Acid leaching was carried out at 60 °C for 3 hours. As a result of acid leaching, a titanium-containing hydrochloric acid solution containing 10 wt.% of titanium and having a molar concentration of 9 M hydrochloric acid was prepared.
타이타늄 함유 염산 용액 중 일부를 이용하여 타이타늄 씨드용액을 제조하였다. 타이타늄 씨드용액은 타이타늄 함유 염산 용액1kg 당 0.5 kg의 20 wt.% 수산화나트륨을 혼합하여 씨드 혼합용액를 제조하고, 씨드 혼합용액 1.5kg 당 물을 0.75 kg 투입하였다. 이후 70 ℃에서 30분간 교반하여 타이타늄 씨드용액을 제조하였다.A titanium seed solution was prepared using some of the titanium-containing hydrochloric acid solution. The titanium seed solution was prepared by mixing 0.5 kg of 20 wt.% sodium hydroxide per 1 kg of the titanium-containing hydrochloric acid solution to prepare a seed mixture solution, and 0.75 kg of water was added per 1.5 kg of the seed mixture solution. After stirring at 70 ℃ for 30 minutes to prepare a titanium seed solution.
타이타늄 함유 염산 용액 100중량부에 제조된 타이타늄 씨드용액을 4 중량부 첨가하고 3개의 샘플로 나누었다. 제1샘플에는 결정 선택제로 황산을 타이타늄 함유 염산 용액 100중량부에 대해 10 중량부 첨가하였으며, 제2샘플에는 결정 선택제로 인산을 타이타늄 함유 염산 용액 100중량부에 대해 0.4 중량부 첨가였으며, 제3샘플에는 인산수소이나트륨을 타이타늄 함유 염산 용액 100중량부에 대해 0.5 중량부 첨가하였다. 그 다음 각 샘플에 물을 타이타늄 함유 염산 용액 100 중량부에 대해 30 중량부 첨가하였으며, 수산화나트륨을 타이타늄 함유 염산 용액 100 중량부에 대해 2.5중량부 첨가하여 100 ℃에서 180분간 반응시켰다. 4 parts by weight of the titanium seed solution prepared in 100 parts by weight of the titanium-containing hydrochloric acid solution was added and divided into three samples. In the first sample, 10 parts by weight of sulfuric acid was added as a crystal selector based on 100 parts by weight of the titanium-containing hydrochloric acid solution, and in the second sample, 0.4 parts by weight of phosphoric acid was added as a crystal selector based on 100 parts by weight of the titanium-containing hydrochloric acid solution. To the sample, 0.5 parts by weight of disodium hydrogen phosphate was added to 100 parts by weight of the titanium-containing hydrochloric acid solution. Then, 30 parts by weight of water was added to each sample based on 100 parts by weight of the titanium-containing hydrochloric acid solution, and 2.5 parts by weight of sodium hydroxide was added to 100 parts by weight of the titanium-containing hydrochloric acid solution, followed by reaction at 100 ° C. for 180 minutes.
제1샘플 내지 제3샘플의 반응과정에서 침전된 침전물을 분리하여 600 ℃에서 1시간동안 하소하여 이산화타이타늄을 회수하였다,The precipitate precipitated in the reaction process of the first to third samples was separated and calcined at 600 ° C. for 1 hour to recover titanium dioxide.
도 12는 타이타늄 함유 염산용액을 이용하여 가수분해 하는 과정에 결정 선택제를 첨가하지 않은 경우의 이산화타이타늄의 XRD 측정 결과이며, 도13는 결정 선택제를 첨가한 경우의 XRD 측정 결과이다. 12 is an XRD measurement result of titanium dioxide when a crystal selector is not added in the process of hydrolysis using a titanium-containing hydrochloric acid solution, and FIG. 13 is an XRD measurement result when a crystal selector is added.
도 12를 보면 결정 선택제를 첨가하지 않은 경우 제조된 이산화타이타늄의 결정형이 루타일형이지만, 도 13에서 보는 바와 같이 결정 선택제를 첨가한 샘플 1 내지 3은 결정형이 아나타제형임을 확인할 수 있다. Referring to FIG. 12, when the crystal selector is not added, the crystalline form of the prepared titanium dioxide is a rutile form, but as shown in FIG.
<실시예 9: 제조되는 이산화타이타늄의 결정 제어><Example 9: Crystal control of manufactured titanium dioxide>
실시예 8과 동일한 방법으로 이산화타이타늄을 제조하되, 결정 선택제로 인산을 이용하였고, 인산의 함량에 따른 이산화타이타늄의 결정형을 조사하여 표 4에 나타내었다. 인산의 함량은 타이타늄 함유 염산 용액 100중량부를 기준으로 한다. Titanium dioxide was prepared in the same manner as in Example 8, but phosphoric acid was used as a crystal selector, and the crystal form of titanium dioxide according to the phosphoric acid content was investigated and shown in Table 4. The content of phosphoric acid is based on 100 parts by weight of titanium-containing hydrochloric acid solution.
| 결정선택제 함량(wt.%)Crystal selection agent content (wt.%) | 00 | 0.20.2 | 0.30.3 | 0.40.4 | 0.50.5 |
| 아나타제형(%)Anatase type (%) | ≤ 1≤ 1 | 6666 | 9090 | 9696 | 99 ≤99 ≤ |
| 루타일형(%)Rutile type (%) | 99 ≤99 ≤ | 3434 | 1010 | 44 | ≤ 1≤ 1 |
표 4를 참조하면, 인산을 첨가하지 않은 경우에 제조되는 이산화타이타늄은 사실상 루타일형을 가지며, 인산의 함량이 증가함에 따라 아나타제형 이산화타이타늄의 양이 증가한다. 그러다가 인산의 함량이 상한(0.5 중량부) 이상이 되면 제조되는 이산화타이타늄은 사실상 아나타제형이 된다. Referring to Table 4, titanium dioxide produced when phosphoric acid is not added has a rutile type in nature, and the amount of anatase type titanium dioxide increases as the phosphoric acid content increases. Then, when the content of phosphoric acid exceeds the upper limit (0.5 parts by weight), the prepared titanium dioxide is in fact anatase type.
<실시예 10: 제2형 결정선택제의 함량에 따른 영향><Example 10: Effect of content of type 2 crystal selector>
실시예 8과 동일한 방법으로 이산화타이타늄을 제조하되, 결정 선택제로 인산을 이용하였고, 인산의 함량에 따른 이산화타이타늄의 입도 및 입형을 조사하여 도 14 내지 도 20에 나타내었다. 인산의 함량은 타이타늄 함유 염산 용액 100 중량부를 기준으로 한다.Titanium dioxide was prepared in the same manner as in Example 8, but phosphoric acid was used as a crystal selector, and the particle size and particle shape of titanium dioxide according to the content of phosphoric acid were investigated and shown in FIGS. 14 to 20. The content of phosphoric acid is based on 100 parts by weight of titanium-containing hydrochloric acid solution.
도 14 및 도 15는 타이타늄 함유 염산용액을 이용하여 가수분해하는 과정에 결정 선택제(제2형: 인산)의 양에 따른 이산화타이타늄의 입도를 측정한 결과이며, 도 16 내지 도 20은 타이타늄 함유 염산용액을 이용하여 가수분해 하는 과정에 결정 선택제(제2형: 인산)의 양에 따른 이산화타이타늄의 입형을 촬영한 사진이다. 구체적으로 도 16는 인산을 첨가하지 않은 경우의 SEM 분석 결과이며, 도 17은 인산을 0.2 중량부 첨가한 경우의 SEM 분석 결과이며, 도18은 인산을 0.3 중량부 첨가한 경우의 SEM 분석 결과이며, 도 19는 인산을 0.4 중량부 첨가한 경우의 SEM 분석 결과이며, 도 20은 인산을 0.5 중량부 첨가한 경우의 SEM 분석 결과이다.14 and 15 are the results of measuring the particle size of titanium dioxide according to the amount of the crystal selector (type 2: phosphoric acid) in the process of hydrolysis using a titanium-containing hydrochloric acid solution, and FIGS. 16 to 20 are titanium-containing hydrochloric acid This is a photograph of the particle shape of titanium dioxide according to the amount of the crystal selector (type 2: phosphoric acid) in the process of hydrolysis using a solution. Specifically, FIG. 16 is the result of SEM analysis when phosphoric acid is not added, FIG. 17 is the result of SEM analysis when 0.2 part by weight of phosphoric acid is added, and FIG. 18 is the result of SEM analysis when 0.3 part by weight of phosphoric acid is added. , FIG. 19 is a SEM analysis result when 0.4 parts by weight of phosphoric acid is added, and FIG. 20 is a SEM analysis result when 0.5 parts by weight of phosphoric acid is added.
도 14 및 도 15를 참조하면, 인산의 함량이 점차 증가할수록 제조되는 이산화타이타늄의 입도가 비례하여 작아지는 것을 확인할 수 있다.Referring to FIGS. 14 and 15 , it can be seen that the particle size of the prepared titanium dioxide decreases in proportion as the content of phosphoric acid gradually increases.
또한, 도 16 내지 도 20을 참조하면, 인산의 함량이 점차 증가할수록 제조되는 이산화타이타늄의 입형이 구형에 가까워지는 것을 확인할 수 있다.In addition, referring to FIGS. 16 to 20 , it can be seen that as the phosphoric acid content gradually increases, the particle shape of the prepared titanium dioxide approaches a spherical shape.
<실시예 11: 씨드의 영향에 대한 조사><Example 11: Investigation of the influence of seeds>
실시예 8과 동일한 방법으로 이산화타이타늄을 제조하되, 씨드 첨가의 유무를 비교하여 그 효과를 조사하여 도 21, 도 22 및 도 23에 나타내었다. Titanium dioxide was prepared in the same manner as in Example 8, but the effect was investigated by comparing the presence or absence of the addition of seeds, and shown in FIGS. 21, 22 and 23.
도 21은 씨드를 첨가하지 않은 경우의 생성되는 이산화타이타늄 입자의 SEM 이미지이며, 도 22는 씨드를 2wt% 첨가한 경우의 이산화타이타늄 입자의 SEM 이미지이다. 도 21와 도 22를 비교해보면, 씨드를 첨가하지 않았을 때는 결정이 일정하지 않고, 입도가 큰 것 확인할 수 있다. 반면에 씨드를 첨가하였을 경우, 쌀알 형상과 같으며 단일 입자 간의 입도와 형상이 비교적 유사한 것을 확인할 수 있다.FIG. 21 is a SEM image of titanium dioxide particles generated when no seeds are added, and FIG. 22 is a SEM image of titanium dioxide particles when 2 wt% of seeds are added. Comparing FIG. 21 and FIG. 22, it can be seen that the crystals are not constant and the particle size is large when no seeds are added. On the other hand, when seeds are added, it can be seen that the shape is the same as that of a grain of rice, and the particle size and shape between single particles are relatively similar.
도 23은 시간에 따른 가수분해율을 측정한 결과로서 씨드의 유무에 따른 영향을 비교한 것이다. 도 23을 참조하면 씨드를 포함할 경우 가수분해 속도 및 가수분해율이 현저히 향상되는 것을 확인할 수 있다. 23 compares the effect of the presence or absence of seeds as a result of measuring the hydrolysis rate over time. Referring to FIG. 23, it can be seen that the hydrolysis rate and hydrolysis rate are significantly improved when seeds are included.
본 발명의 보호범위가 이상에서 명시적으로 설명한 실시예의 기재와 표현에 제한되는 것은 아니다. 또한, 본 발명이 속하는 기술분야에서 자명한 변경이나 치환으로 말미암아 본 발명이 보호범위가 제한될 수도 없음을 다시 한번 첨언한다.The protection scope of the present invention is not limited to the description and expression of the embodiments explicitly described above. In addition, it is added once again that the scope of protection of the present invention cannot be limited due to obvious changes or substitutions in the technical field to which the present invention belongs.
Claims (5)
- 탈질폐촉매 파우더와 알칼리제의 혼합물을 압축 성형 및 소결하여 알칼리 소결 성형체를 제조하는 단계; 및 preparing an alkali sintered molded body by compression molding and sintering a mixture of spent denitrification catalyst powder and an alkali agent; and상기 알칼리 소결 성형체로부터 유가금속을 침출하는 단계;를 포함하는 탈질폐촉매 함유 유가금속의 추출방법. A method of extracting valuable metals containing a waste denitrification catalyst comprising leaching valuable metals from the alkali sintered molded body.
- 제1항에 있어서,According to claim 1,상기 알칼리 소결 성형체로부터 유가금속을 침출하는 단계는, The step of leaching the valuable metal from the alkali sintered molded body,알칼리 소결 성형체를 물에 반응시켜 바나듐-텅스텐 함유 용액을 추출하고, 알칼리 소결 성형체를 물에 반응시킨 후 여과하여 분리한 고형물로부터 염산을 이용하여 타이타늄 함유 염산 용액을 추출하는 것을 특징으로 하는 탈질폐촉매 함유 유가금속의 추출방법.A waste denitrification catalyst characterized by extracting a vanadium-tungsten-containing solution by reacting the alkali sintered molded body with water, and extracting a titanium-containing hydrochloric acid solution using hydrochloric acid from the solids separated by filtering after reacting the alkali sintered molded body with water. Extraction method of containing valuable metals.
- 제2항에 있어서, According to claim 2,상기 바나듐-텅스텐 함유 용액을 추출한 후 추출한 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐을 분리하는 단계가 수행되며, 상기 바나듐-텅스텐 함유 용액 내 바나듐-텅스텐을 분리하는 단계는, After extracting the vanadium-tungsten-containing solution, a step of separating vanadium-tungsten in the extracted vanadium-tungsten-containing solution is performed. In the step of separating vanadium-tungsten in the vanadium-tungsten-containing solution,(a-1) 바나듐-텅스텐 함유 용액에 전처리를 수행하여 용액내 바나듐의 이온 상태를 전환시키는 단계; (a-1) converting the ionic state of vanadium in the solution by performing a pretreatment on the vanadium-tungsten-containing solution;(a-2) 전처리한 바나듐-텅스텐 함유 용액에 추출제를 첨가하여 반응시키는 단계; (a-2) reacting by adding an extractant to the pretreated vanadium-tungsten-containing solution;(a-3) 반응시킨 바나듐-텅스텐 함유 용액을 유기 용매와 수 용매로 분리하는 단계; (a-3) separating the reacted vanadium-tungsten-containing solution into an organic solvent and an aqueous solvent;(a-4) 상기 유기 용매에서 텅스텐을 추출하는 단계; (a-4) extracting tungsten from the organic solvent;(a-5) 상기 수 용매에서 바나듐의 이온 상태를 재전환시키는 단계; (a-5) reconverting the ionic state of vanadium in the aqueous solvent;(a-6) 바나듐이 포함된 상기 수용매에 추출제를 첨가하여 반응시키는 단계; 및 (a-6) reacting by adding an extractant to the aqueous medium containing vanadium; and(a-7) 유기용매에 포함된 바나듐을 추출하는 단계;를 포함하는 것을 특징으로 하는 탈질폐촉매 함유 유가금속의 추출방법.(a-7) extracting vanadium contained in the organic solvent; a method for extracting valuable metals containing a waste denitrification catalyst, comprising
- 제2항에 있어서, According to claim 2,상기 타이타늄 함유 염산 용액으로부터 아나타제형 이산화타이타늄을 형성하는 단계가 수행되며, 상기 타이타늄 함유 염산 용액으로부터 아나타제형 이산화타이타늄을 형성하는 단계는, The step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution is performed, and the step of forming anatase-type titanium dioxide from the titanium-containing hydrochloric acid solution,(b-1) 제1타이타늄 함유 염산 용액 및 상기 제1타이타늄 함유 염산 용액과 조성이 같거나 다른 제2타이타늄 함유 염산 용액을 마련하는 단계; (b-1) preparing a first titanium-containing hydrochloric acid solution and a second titanium-containing hydrochloric acid solution having the same composition as or different from the first titanium-containing hydrochloric acid solution;(b-2) 상기 제1타이타늄 함유 염산 용액에 수산화나트륨을 첨가하고 혼합하여 제1혼합용액을 제조하고, 상기 제1혼합용액에 물을 첨가하여 타이타늄 씨드용액을 제조하는 단계; (b-2) preparing a first mixed solution by adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution, and adding water to the first mixed solution to prepare a titanium seed solution;(b-3) 상기 타이타늄 씨드용액과 생성되는 이산화타이타늄의 결정형을 아나타제형으로 만드는 결정 선택제를 상기 제2타이타늄 함유 염산 용액에 첨가하여 혼합 용액을 제조하는 단계; 및 (b-3) preparing a mixed solution by adding a crystal selector to the second titanium-containing hydrochloric acid solution to convert the titanium seed solution and the resulting titanium dioxide into an anatase crystal form; and(b-4) 상기 혼합 용액에 물을 첨가하여 가수분해를 통해 아나타제형 이산화타이타늄을 형성하는 단계;를 포함하는 것을 특징으로 하는 탈질폐촉매 함유 유가금속의 추출방법.(b-4) adding water to the mixed solution to form anatase-type titanium dioxide through hydrolysis;
- 제2항에 있어서, According to claim 2,상기 타이타늄 함유 염산 용액으로부터 형성되는 이산화타이타늄의 결정형을 제어하는 단계가 수행되며, 상기 타이타늄 함유 염산 용액으로부터 형성되는 이산화타이타늄의 결정형을 제어하는 단계는, The step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution is performed, and the step of controlling the crystalline form of titanium dioxide formed from the titanium-containing hydrochloric acid solution,(c-1) 제1타이타늄 함유 염산 용액 및 상기 제1타이타늄 함유 염산 용액과 조성이 같거나 다른 제2타이타늄 함유 염산 용액을 마련하는 단계; (c-1) preparing a first titanium-containing hydrochloric acid solution and a second titanium-containing hydrochloric acid solution having the same composition as or different from the first titanium-containing hydrochloric acid solution;(c-2) 상기 제1타이타늄 함유 염산 용액에 수산화나트륨을 첨가하고 혼합하여 제1혼합용액을 제조하고, 상기 제1혼합용액에 물을 첨가하여 타이타늄 씨드용액을 제조하는 단계; (c-2) adding and mixing sodium hydroxide to the first titanium-containing hydrochloric acid solution to prepare a first mixed solution, and adding water to the first mixed solution to prepare a titanium seed solution;(c-3) 상기 타이타늄 씨드용액을 상기 제2타이타늄 함유 염산 용액에 첨가하여 혼합 용액을 제조하되, 결정 선택제에 의해 제조할 이산화타이타늄의 결정형을 선택하는 단계; 및 (c-3) preparing a mixed solution by adding the titanium seed solution to the second titanium-containing hydrochloric acid solution, selecting a crystalline form of titanium dioxide to be produced by a crystal selector; and(c-4) 상기 혼합 용액을 가수분해하여 아나타제형 이산화타이타늄을 형성하는 단계;를 포함하고, (c-4) hydrolyzing the mixed solution to form anatase-type titanium dioxide;상기 (c-3) 단계에서 결정 선택제를 첨가하지 않음으로써 루타일형 이산화타이타늄을 형성하고, 결정 선택제를 첨가함으로써 아나타제형 이산화타이타늄을 형성하는 것을 특징으로 하는 탈질폐촉매 함유 유가금속의 추출방법.In step (c-3), rutile-type titanium dioxide is formed by not adding a crystal selector, and anatase-type titanium dioxide is formed by adding a crystal selector.
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| KR1020210122885A KR102411274B1 (en) | 2021-09-15 | 2021-09-15 | Vanadium-tungsten separation method in vanadium-tungsten containing solutions |
| KR1020210122881A KR102445476B1 (en) | 2021-09-15 | 2021-09-15 | Method of extracting valuable metals containing denitrification waste catalyst using an alkali sintered body |
| KR1020210122887A KR102411275B1 (en) | 2021-09-15 | 2021-09-15 | Method for producing anatase-type titanium dioxide using titanium-containing hydrochloric acid solution and titanium dioxide crystal control method using titanium-contained hydrochloric acid solution |
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| CN107922994B (en) * | 2015-06-04 | 2019-07-16 | 克里斯特尔美国有限公司 | Tungsten and vanadium separation |
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| JP2003507300A (en) * | 1999-06-24 | 2003-02-25 | アルテア ナノマテリアルズ インコーポレイテッド | Method for producing ultrafine titanium dioxide from aqueous titanium chloride solution |
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| KR20140131998A (en) * | 2012-03-05 | 2014-11-14 | 선샤인 카이디 뉴 에너지 그룹 컴퍼니 리미티드 | PROCESS FOR THE COMPREHENSIVE RECOVERY OF METAL COBALT, RUTHENIUM AND ALUMINUM FROM WASTE CATALYST Co-Ru/Al2O3 IN FISCHER-TROPSCH SYNTHESIS |
| CN107922994B (en) * | 2015-06-04 | 2019-07-16 | 克里斯特尔美国有限公司 | Tungsten and vanadium separation |
| CN105861829A (en) * | 2016-04-18 | 2016-08-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for separating vanadium and chromium solution and recycling vanadium and chromium |
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