CN115322087B - Method for extracting high-purity niobium pentoxide from waste niobium-containing glass - Google Patents
Method for extracting high-purity niobium pentoxide from waste niobium-containing glass Download PDFInfo
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- CN115322087B CN115322087B CN202210868556.7A CN202210868556A CN115322087B CN 115322087 B CN115322087 B CN 115322087B CN 202210868556 A CN202210868556 A CN 202210868556A CN 115322087 B CN115322087 B CN 115322087B
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000010955 niobium Substances 0.000 title claims abstract description 160
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 157
- 239000011521 glass Substances 0.000 title claims abstract description 95
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims abstract description 63
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000746 purification Methods 0.000 claims abstract description 19
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000013049 sediment Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 14
- XTTKJDYDBXPBDJ-UHFFFAOYSA-N niobium;oxalic acid Chemical compound [Nb].OC(=O)C(O)=O XTTKJDYDBXPBDJ-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 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 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000011775 sodium fluoride Substances 0.000 description 7
- 235000013024 sodium fluoride Nutrition 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 235000010469 Glycine max Nutrition 0.000 description 6
- 244000068988 Glycine max Species 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000005304 optical glass Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WWRVXNGTXLEFLL-UHFFFAOYSA-N [Ta].[Nb].[Fe] Chemical compound [Ta].[Nb].[Fe] WWRVXNGTXLEFLL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for extracting high-purity niobium oxalate and niobium pentoxide from waste niobium-containing glass. The invention aims to provide a method for extracting high-purity niobium pentoxide from waste niobium-containing glass, which changes waste niobium-containing glass into valuable, not only can obtain the high-purity niobium pentoxide, but also can reduce the production and preparation links of the niobium pentoxide and the pollution of the waste niobium-containing glass to the environment. The invention extracts niobium from the niobium-containing glass through a unique multi-stage impurity removal process, and an inorganic chemical reagent (oxalic acid is decomposed into carbon dioxide at high temperature and is harmless to the environment) is used in the niobium purification process.
Description
Technical Field
The invention relates to a preparation method of niobium pentoxide, in particular to a method for extracting high-purity niobium pentoxide from waste niobium-containing glass.
Background
Niobium pentoxide is a main raw material of high-end special optical glass, and is expensive up to 250-350 yuan per kilogram. The traditional niobium pentoxide preparation method comprises the process steps of dissolving tantalum-niobium-iron ore, extracting organic matters, pickling, removing impurities and the like, and has great environmental pollution.
As the yield of the high-end special optical glass containing niobium is relatively low, several to more than ten tons of waste glass containing niobium are produced each year, the proportion of niobium pentoxide in the waste glass containing niobium is high (the content of niobium pentoxide in some glass is as high as 44 percent) and is higher than that in the tantalum-niobium iron ore, and the waste glass containing niobium has great pollution to the environment.
Disclosure of Invention
The invention aims to provide a method for extracting high-purity niobium pentoxide from waste niobium-containing glass, which changes waste niobium-containing glass into valuable, not only can obtain the high-purity niobium pentoxide, but also can reduce the production and preparation links of the niobium pentoxide and the pollution of the waste niobium-containing glass to the environment.
The technical scheme of the invention is as follows:
the method for extracting niobium oxalate from waste niobium-containing glass is characterized by comprising the following steps of:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into niobium-containing glass powder;
step 2, preparing mixed acid
Mixing hydrofluoric acid with the mass fraction of 50-55% and analytically pure nitric acid in the mass ratio of 9-10:1, and uniformly stirring to obtain mixed acid; the acid with the main function in the mixed acid is hydrofluoric acid, and nitric acid is used as a catalyst, so that the main function is to improve the acidity and prevent the phosphoric acid converted from phosphorus pentoxide from being digested poorly;
step 3, preparing niobium-containing solution
Step 3.1, preheating the mixed acid, and adding the niobium-containing glass powder into the preheated mixed acid for reaction to obtain a crude niobium-containing solution; the main reaction equation is: siO (SiO) 2 +6HF=H 2 SiF 6 +2H 2 O；Nb 2 O 5 +12HF=2HNbF 6 +5H 2 O；Na 2 O+2HF→2NaF+H 2 O；Li 2 O+2HF→2LiF+H 2 O；
Step 3.2, filtering the crude niobium-containing solution, mainly removing indissolvable titanium dioxide, lithium fluoride and sodium fluoride generated by the reaction in step 3.1, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-time purification
Adding ammonia water into the niobium-containing solution, adjusting the pH to 8.5-9 (preferably 8.8), settling, removing supernatant, centrifuging liquid-solid separation of bottom sediment to obtain a filter cake, washing the filter cake with water until the pH value is 6.7-7.2 (preferably 7.1) to obtain a niobium-containing sediment crude product, wherein phosphorus pentoxide and potassium ions are basically removed, and added fluorine and nitrate are removed; the main reaction equation is: h 2 SiF 6 +6NH 4 OH=6NH 4 F+SiO 2 +4H 2 O；HNbF 6 +6NH 4 OH=Nb(OH) 5 +6NH 4 F+H 2 O；
Step 5, secondary purification
Adding the crude product containing niobium into oxalic acid for reaction, filtering to remove insoluble matters (mainly silicon dioxide) in the crude product, collecting filtrate, heating, concentrating, crystallizing, and separating liquid from solid to crystallize (removing residual sodium, potassium, titanium, silicon and phosphorus) to obtain refined niobium oxalate; the reaction equation is: 2Nb (OH) 5 +5H 2 C 2 O 4 =Nb 2 (C 2 O 4 ) 5 +10H 2 O；
Step 6, three times of purification
Adding the refined niobium oxalate into hydrochloric acid for solution recrystallization, and performing liquid-solid separation crystallization (the liquid-solid separation can remove sodium chloride and lithium chloride generated by the reaction of the hydrochloric acid with residual lithium oxide and sodium oxide), thereby obtaining the crystal which is the pure niobium oxalate.
Based on the technical scheme, the invention further optimizes and limits the following steps:
further, in the step 1, the niobium-containing glass is crushed into 80 mesh or more niobium-containing glass powder; the fineness firstly ensures the reaction speed, and secondly prevents the glass slag with too coarse granularity from scratching the wall of the reactor after the reaction; the specific crushing method is as follows: firstly, crushing niobium-containing glass into small glass blocks with the size of soybeans; and then crushing the small glass blocks into glass powder by a pair of rollers, sieving the glass powder with the size of more than or equal to 80 meshes, taking out the part below the sieve, and crushing the part above the sieve again to obtain the niobium-containing glass powder.
Further, the mass ratio of hydrofluoric acid to analytically pure nitric acid in step 2 is 9.8:1.
Further, in step 3.1: heating the mixed acid to 70-80 ℃, adding the niobium-containing glass powder into the mixed acid under the stirring state, heating to 90-100 ℃, and preserving heat for 2-3 hours to obtain a crude niobium-containing solution; wherein the mass ratio of the mixed acid to the niobium-containing glass powder is 1.8-2.3:1, and is preferably 1.82:1.
Further, the step 5 specifically comprises: adding the crude product of the niobium-containing precipitate into oxalic acid with the mass fraction of 20-30% and the preheating temperature of 90-100 ℃, carrying out heat preservation reaction for 2-3 hours to obtain the crude product of the niobium oxalate solution, filtering the crude product of the niobium oxalate solution, heating to 100-105 ℃ for concentrating and crystallizing, and separating and crystallizing while the solution is hot to obtain the refined product of the niobium oxalate.
Further, the step 6 specifically includes: adding the refined niobium oxalate into hydrochloric acid with the mass fraction of 5-8% (preferably 6.5 percent), the optimal impurity removal effect at the moment and the preheating temperature of 70-80 ℃, carrying out heat preservation reaction for 1-2 hours, removing residual sodium and lithium, ensuring the content of elements such as iron, cobalt, nickel, copper, cadmium, vanadium, titanium and the like to be qualified, obtaining a pure niobium-containing solution after the reaction is finished, heating the pure niobium-containing solution to 100-105 ℃ for concentrating and crystallizing, and putting the pure niobium-containing solution into a centrifugal machine while the pure niobium-containing solution is hot for solid-liquid separation and crystallization, thus obtaining the pure niobium oxalate.
Further, in order to improve the purity of the product, filtering the crude niobium-containing solution in the step 3.2 by using filter cloth with at least 3000 meshes; in the step 4, the bottom sediment is wrapped by filter cloth with at least 2500 meshes and is put into a centrifugal machine for liquid-solid separation, and the centrifugal speed is 1000 revolutions per minute; filtering the crude oxalate niobium solution by using at least 3000-mesh filter cloth in the step 5, wrapping the fished crystal by using at least 1000-mesh filter cloth, and putting the wrapped crystal into a centrifuge for liquid-solid separation, wherein the centrifugal speed is 1000 rpm; and step 6, wrapping the fished crystals with filter cloth of at least 1000 meshes, and putting the wrapped crystals into a centrifugal machine for liquid-solid separation, wherein the centrifugal speed is 1000 rpm.
The invention also provides niobium oxalate, which is characterized in that: the method for extracting niobium oxalate from the waste niobium-containing glass is prepared by adopting any one of the above methods.
The invention further provides a method for extracting niobium pentoxide from waste niobium-containing glass, which is characterized by comprising the following steps of:
step 1, preparing a pure niobium oxalate product by adopting any one of the methods for extracting niobium oxalate from waste niobium-containing glass;
and step 2, carrying out gradient heating and drying on the pure niobium oxalate product to obtain niobium pentoxide.
Further, the gradient heating and drying specifically comprises the following steps:
a first gradient: drying at 200-300 ℃ for 4-5 hours, removing redundant water and hydrochloric acid at low temperature, and protecting the crucible and the hearth;
a second gradient: drying at 800-900 ℃ for 4-6 hours to decompose niobium oxalate into niobium pentoxide while avoiding the generation of byproducts (including niobium trioxide and niobium hydroxide) to obtain high-purity niobium pentoxide; the reaction equation is: nb (Nb) 2 (C 2 O 4 ) 5 =Nb 2 O 5 +5CO+5CO 2 ；
And detecting a target product obtained after the second gradient drying, wherein the detection data are qualitatively that niobium pentoxide, sodium is less than 50ppm, potassium is less than 200ppm, iron, cobalt, nickel, copper, cadmium and vanadium are less than 1ppm, phosphorus is less than 0.13ppm, and chlorine is less than 50ppm.
The invention also provides a high-purity niobium pentoxide, which is characterized in that: the method for extracting niobium pentoxide from the waste niobium-containing glass is prepared by adopting any one of the above methods.
The beneficial effects of the invention are as follows:
1. the invention has the main raw materials of waste niobium-containing optical glass, the components are more complex, the niobium in the niobium-containing glass is extracted through a unique multi-stage impurity removal process, and the inorganic chemical reagent (oxalic acid is decomposed into carbon dioxide at high temperature and is harmless to the environment) is used in the niobium purification process.
2. The niobium pentoxide obtained by multistage purification has high purity and low impurity content, and can be directly used as a special optical glass additive.
3. The method can be applied to extracting niobium pentoxide from most other niobium-containing glass.
4. In the process of researching how to extract the niobium pentoxide from the waste niobium-containing glass, the invention also realizes the extraction of the high-purity niobium oxalate, and the extracted high-purity niobium oxalate not only can be used as a precursor for preparing the high-purity niobium pentoxide, but also can be used as a catalyst, and is widely used as a dielectric material additive, ferrite and the like.
Drawings
Fig. 1 is an XRD pattern of niobium pentoxide prepared in example 1.
Detailed Description
The invention is characterized in that:
according to the invention, after digestion and filtration of the niobium-containing waste glass, the waste glass is detected by Agilent 5110 ICP-OES, and the converted detection data are as follows:
the composition of the niobium-containing waste glass was analyzed based on the detection data, taking into consideration the properties of each component to be separated stepwise. Niobium-containing waste glass:
niobium pentoxide and silicon dioxide as main components, both dissolved in hot hydrofluoric acid; titanium dioxide is very insoluble in acid-base solution; firstly, dissolving the raw materials by mixed acid (the mass ratio of hydrofluoric acid to analytically pure nitric acid is=9-10:1) to remove titanium dioxide and most of lithium fluoride and sodium fluoride in the raw materials;
further, precipitating niobium (silicon is precipitated together in a silicon dioxide form) by ammonia water, and removing phosphorus, potassium, a small part of sodium and lithium and added fluorine and nitrate by water washing to obtain a crude product containing niobium precipitate;
further, oxalic acid is adopted to dissolve the crude product of niobium-containing precipitate, silicon dioxide is removed after filtration, and then sodium, potassium, titanium, silicon and phosphorus with little residue can be removed through recrystallization, so that refined niobium oxalate solution is obtained;
and finally, adding the refined niobium oxalate solution into hydrochloric acid for dissolution and recrystallization, effectively removing metal impurities such as iron and the like in the product to obtain high-purity niobium oxalate, and then carrying out gradient firing on the high-purity niobium oxalate to obtain the high-purity niobium pentoxide.
The main reaction equation is:
SiO 2 +6HF =H 2 SiF 6 +2H 2 O；
Nb 2 O 5 +12HF=2HNbF 6 +5H 2 O；
Na 2 O+2HF→2NaF+H 2 O；
Li 2 O+2HF→2LiF+H 2 O；
H 2 SiF 6 +6NH 4 OH=6NH 4 F+SiO 2 +4H 2 O；
HNbF 6 +6NH 4 OH=Nb(OH) 5 +6NH 4 F+H 2 O；
2Nb(OH) 5 +5H 2 C 2 O 4 =Nb 2 (C 2 O 4 ) 5 +10H 2 O；
Nb 2 (C 2 O 4 ) 5 =Nb 2 O 5 +5CO+5CO 2 。
the invention is further described below with reference to examples.
Example 1
In this example, high purity niobium pentoxide was extracted by the following steps:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into small glass blocks with the size of soybean, crushing the small glass blocks into glass powder by a pair of rollers, sieving with 80 meshes, taking the undersize part, and crushing the oversize part again to obtain niobium-containing glass powder;
step 2, preparing mixed acid
165 kg of hydrofluoric acid with the mass fraction of 50% is added into a polytetrafluoroethylene kettle, 16.5 kg of analytically pure nitric acid is added, the mass ratio of the hydrofluoric acid to the analytically pure nitric acid is 10:1, and the mixed acid is obtained after uniform stirring;
step 3, preparing niobium-containing solution
Step 3.1, heating the mixed acid obtained in the step 2 to 70-75 ℃, adding 98 kg of the niobium-containing glass powder obtained in the step 1 into the mixed acid under the stirring state, and preserving the temperature for 3 hours at 90-95 ℃ to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, filtering out insoluble substances (mainly titanium dioxide, lithium fluoride and sodium fluoride) in the crude niobium-containing solution, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-step purification of niobium element
Adding 20% ammonia water into the niobium-containing solution obtained in the step 3.2 under stirring, adjusting the pH value to 8.5 (the adding amount is based on the pH value because the volatilization amount of the ammonia water is large), depositing a large amount of the solution in a PP vat for 6-8 hours, removing the supernatant, taking out the bottom precipitate, performing centrifugal liquid-solid separation on the bottom precipitate to obtain a filter cake, and washing the filter cake obtained by liquid-solid separation to pH6.7 to obtain a crude niobium-containing precipitate;
step 5, niobium element secondary purification
Preparing an oxalic acid solution with the mass fraction of 20% in a reaction kettle, heating to 90-95 ℃, adding the crude product containing niobium obtained in the step 4 into the oxalic acid solution, preserving the temperature for 3 hours at 90-95 ℃ to obtain the crude product containing niobium oxalate, filtering the crude product containing niobium oxalate, removing insoluble substances to obtain refined product containing niobium oxalate, heating the refined product containing niobium oxalate to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and putting the obtained refined product containing niobium oxalate into a centrifuge while the crystals are hot for liquid-solid separation to obtain refined product containing niobium oxalate;
step 6, purifying the niobium element for three times
Adding 500kg of hydrochloric acid with the mass fraction of 5% into a polytetrafluoroethylene reaction kettle, heating to 70-75 ℃, adding the refined niobium oxalate obtained in the step 5, preserving heat and dissolving for 2 hours to obtain a pure niobium-containing solution, heating the pure niobium-containing solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and centrifuging while the crystals are hot to obtain the pure niobium oxalate;
step 7, niobium pentoxide preparation
Placing the pure niobium oxalate obtained in the step 6.2 into a ceramic crucible for gradient drying:
drying at 200 ℃ for 5 hours in a first gradient;
and (5) drying at 800 ℃ for 6 hours in a second gradient to obtain the high-purity niobium pentoxide.
The XRD pattern of the target product obtained in the embodiment is shown in figure 1, and the product is niobium pentoxide without other impurity peaks. The detection by Agilent 5110-ICP-OES shows that iron, cobalt, nickel, copper, chromium, cadmium, vanadium and manganese in niobium pentoxide are less than 1ppm, sodium is less than 50ppm, potassium is less than 200ppm, chlorine is less than 50ppm, and phosphorus is less than 0.13ppm. The test result of the aluminum fluoride prepared at this time meets the standard. The details are shown in table 1 below:
TABLE 1
Example 2:
in this example, high purity niobium pentoxide was extracted by the following steps:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into small glass blocks with the size of soybean, crushing the small glass blocks into glass powder by a pair of rollers, sieving with 80 meshes, taking the undersize part, and crushing the oversize part again to obtain niobium-containing glass powder;
step 2, preparing mixed acid
173 kg of hydrofluoric acid with the mass fraction of 50% is added into a polytetrafluoroethylene kettle, 17.6 kg of analytically pure nitric acid is added, the mass ratio of the hydrofluoric acid to the analytically pure nitric acid is 9.8:1, and the mixed acid is obtained by stirring uniformly;
step 3, preparing niobium-containing solution
Step 3.1, heating the mixed acid obtained in the step 2 to 75-80 ℃, adding 104.7 kg of the niobium-containing glass powder obtained in the step 1 into the mixed acid under the stirring state, and preserving the temperature for 3 hours at 95-100 ℃ to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, filtering out insoluble substances (mainly titanium dioxide, lithium fluoride and sodium fluoride) in the crude niobium-containing solution, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-step purification of niobium element
Adding 20% ammonia water into the niobium-containing solution obtained in the step 3.2 under stirring, adjusting the pH value to 8.8 (the adding amount is based on the pH value because the volatilization amount of the ammonia water is large), depositing a large amount of the ammonia water in a PP vat for 6-8 hours, removing the supernatant, taking out the bottom sediment, performing centrifugal liquid-solid separation on the bottom sediment to obtain a filter cake, and washing the filter cake obtained by liquid-solid separation to pH7.1 to obtain a crude niobium-containing sediment;
step 5, niobium element secondary purification
Preparing oxalic acid solution with mass fraction of 22% in a reaction kettle, heating to 95-100 ℃, adding the crude product containing niobium obtained in the step 4 into the oxalic acid solution, preserving heat for 3 hours at 95-100 ℃ to obtain crude product of the oxalic acid niobium solution, filtering the crude product of the oxalic acid niobium solution, removing insoluble matters to obtain refined product of the oxalic acid niobium solution, heating the refined product of the oxalic acid niobium solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and putting the obtained refined product of the oxalic acid niobium into a centrifuge while the crystals are hot for liquid-solid separation to obtain refined product of the oxalic acid niobium;
step 6, purifying the niobium element for three times
Adding 500kg of hydrochloric acid with the mass fraction of 6.5% into a polytetrafluoroethylene reaction kettle, heating to 70-75 ℃, adding the refined niobium oxalate obtained in the step 5, keeping the temperature and dissolving for 2 hours to obtain a pure niobium-containing solution, heating the pure niobium-containing solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and centrifuging while the crystals are hot to obtain the pure niobium oxalate;
step 7, niobium pentoxide preparation
Placing the pure niobium oxalate obtained in the step 6.2 into a ceramic crucible for gradient drying:
drying at 230 ℃ for 5 hours in a first gradient;
and (5) drying at 850 ℃ for 5 hours to obtain the high-purity niobium pentoxide.
The XRD pattern of the target product obtained in the embodiment is basically consistent with that of the attached figure 1, and the product is niobium pentoxide without other miscellaneous peaks. The detection by Agilent 5110-ICP-OES shows that iron, cobalt, nickel, copper, chromium, cadmium, vanadium and manganese in niobium pentoxide are less than 1ppm, sodium is less than 48ppm, potassium is less than 195ppm, chlorine is less than 50ppm, and phosphorus is less than 0.12ppm. The test result of the aluminum fluoride prepared at this time meets the standard. The details are shown in table 2 below:
TABLE 2
Example 3
In this example, high purity niobium pentoxide was extracted by the following steps:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into small glass blocks with the size of soybean, crushing the small glass blocks into glass powder by a pair of rollers, sieving with 80 meshes, taking the undersize part, and crushing the oversize part again to obtain niobium-containing glass powder;
step 2, preparing mixed acid
182 kg of hydrofluoric acid with the mass fraction of 53% is added into a polytetrafluoroethylene kettle, 19.2 kg of analytically pure nitric acid is added, the mass ratio of the hydrofluoric acid to the analytically pure nitric acid is 9.5:1, and the mixed acid is obtained after uniform stirring;
step 3, preparing niobium-containing solution
Step 3.1, heating the mixed acid obtained in the step 2 to 75-80 ℃, adding 100 kg of the niobium-containing glass powder obtained in the step 1 into the mixed acid under the stirring state, and preserving the temperature for 3 hours at 95-100 ℃ to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, filtering out insoluble substances (mainly titanium dioxide, lithium fluoride and sodium fluoride) in the crude niobium-containing solution, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-step purification of niobium element
Adding 20% ammonia water into the niobium-containing solution obtained in the step 3.2 under stirring, adjusting the pH value to 9 (the adding amount is based on the pH value because the volatilization amount of the ammonia water is large), depositing a large amount of the ammonia water in a PP vat for 6-8 hours, removing the supernatant, taking out the bottom sediment, performing centrifugal liquid-solid separation on the bottom sediment to obtain a filter cake, and washing the filter cake obtained by liquid-solid separation to pH7 to obtain a crude niobium-containing sediment;
step 5, niobium element secondary purification
Preparing an oxalic acid solution with the mass fraction of 30% in a reaction kettle, heating to 95-100 ℃, adding the crude product containing niobium obtained in the step 4 into the oxalic acid solution, preserving the temperature at 95-100 ℃ for 3 hours to obtain the crude product of the oxalic acid niobium solution, filtering the obtained crude product of the oxalic acid niobium solution, removing insoluble matters to obtain a refined product of the oxalic acid niobium solution, heating the refined product of the oxalic acid niobium solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and putting the obtained refined product of the oxalic acid niobium into a centrifuge while the crystals are hot for liquid-solid separation to obtain the refined product of the oxalic acid niobium;
step 6, purifying the niobium element for three times
Adding 500kg of hydrochloric acid with the mass fraction of 8% into a polytetrafluoroethylene reaction kettle, heating to 70-75 ℃, adding the refined niobium oxalate obtained in the step 5, keeping the temperature and dissolving for 2 hours to obtain a pure niobium-containing solution, heating the pure niobium-containing solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and centrifuging while the crystals are hot to obtain the pure niobium oxalate;
step 7, niobium pentoxide preparation
Placing the pure niobium oxalate obtained in the step 6.2 into a ceramic crucible for gradient drying:
drying at 300 ℃ for 4 hours in a first gradient;
and (5) drying at 900 ℃ for 4 hours to obtain the high-purity niobium pentoxide.
The XRD pattern of the target product obtained in the embodiment is basically consistent with that of the attached figure 1, and the product is niobium pentoxide without other miscellaneous peaks. The detection by Agilent 5110-ICP-OES shows that iron, cobalt, nickel, copper, chromium, cadmium, vanadium and manganese in niobium pentoxide are less than 1ppm, sodium is less than 50ppm, potassium is less than 200ppm, chlorine is less than 50ppm, and phosphorus is less than 0.14ppm. The test result of the aluminum fluoride prepared at this time meets the standard. The details are shown in table 3 below:
TABLE 3 Table 3
Example 4
In this example, high purity niobium pentoxide was extracted by the following steps:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into small glass blocks with the size of soybean, crushing the small glass blocks into glass powder by a pair of rollers, sieving with 80 meshes, taking the undersize part, and crushing the oversize part again to obtain niobium-containing glass powder;
step 2, preparing mixed acid
180 kg of hydrofluoric acid with the mass fraction of 55% is added into a polytetrafluoroethylene kettle, 20 kg of analytically pure nitric acid is added, the mass ratio of the hydrofluoric acid to the analytically pure nitric acid is 9:1, and the mixed acid is obtained after uniform stirring;
step 3, preparing niobium-containing solution
Step 3.1, heating the mixed acid obtained in the step 2 to 70-75 ℃, adding 91 kg of the niobium-containing glass powder obtained in the step 1 into the mixed acid under the stirring state, and preserving the heat for 2 hours at 100 ℃ to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, filtering out insoluble substances (mainly titanium dioxide, lithium fluoride and sodium fluoride) in the crude niobium-containing solution, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-step purification of niobium element
Adding 20% ammonia water into the niobium-containing solution obtained in the step 3.2 under stirring, adjusting the pH value to 8.6 (the adding amount is based on the pH value because the volatilization amount of the ammonia water is large), depositing a large amount of the ammonia water in a PP vat for 6-8 hours, removing the supernatant, taking out the bottom sediment, performing centrifugal liquid-solid separation on the bottom sediment to obtain a filter cake, and washing the filter cake obtained by liquid-solid separation to pH7.2 to obtain a crude niobium-containing sediment;
step 5, niobium element secondary purification
Preparing an oxalic acid solution with the mass fraction of 25% in a reaction kettle, heating to 100 ℃, adding the crude niobium-containing precipitate obtained in the step 4 into the oxalic acid solution, preserving the temperature of 100 ℃ for 2 hours to obtain the crude niobium oxalate solution, filtering the crude niobium oxalate solution to remove insoluble matters to obtain a refined niobium oxalate solution, heating the refined niobium oxalate solution to 100-105 ℃ for concentration, taking out the crystals after a large amount of crystallization occurs, and putting the crystals into a centrifuge while the crystals are hot for liquid-solid separation to obtain the refined niobium oxalate solution;
step 6, purifying the niobium element for three times
Adding 500kg of hydrochloric acid with the mass fraction of 7% into a polytetrafluoroethylene reaction kettle, heating to 75-80 ℃, adding the refined niobium oxalate obtained in the step 5, keeping the temperature and dissolving for 2 hours to obtain a pure niobium-containing solution, heating the pure niobium-containing solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and centrifuging while the crystals are hot to obtain the pure niobium oxalate;
step 7, niobium pentoxide preparation
Placing the pure niobium oxalate obtained in the step 6.2 into a ceramic crucible for gradient drying:
drying at 265 ℃ for 4.5 hours in a first gradient;
and (5) drying at 830 ℃ for 5 hours to obtain the high-purity niobium pentoxide.
The XRD pattern of the target product obtained in the embodiment is basically consistent with that of the attached figure 1, and the product is niobium pentoxide without other miscellaneous peaks. The detection by Agilent 5110-ICP-OES shows that iron, cobalt, nickel, copper, chromium, cadmium, vanadium and manganese in niobium pentoxide are less than 1ppm, sodium is less than 50ppm, potassium is less than 200ppm, chlorine is less than 50ppm, and phosphorus is less than 0.13ppm. The test result of the aluminum fluoride prepared at this time meets the standard. The details are shown in table 4 below:
TABLE 4 Table 4
Example 5
In this example, high purity niobium pentoxide was extracted by the following steps:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into small glass blocks with the size of soybean, crushing the small glass blocks into glass powder by a pair of rollers, sieving with 80 meshes, taking the undersize part, and crushing the oversize part again to obtain niobium-containing glass powder;
step 2, preparing mixed acid
180 kg of hydrofluoric acid with the mass fraction of 50% is added into a polytetrafluoroethylene kettle, 19.5 kg of analytically pure nitric acid is added, the mass ratio of the hydrofluoric acid to the analytically pure nitric acid is 9.2:1, and the mixed acid is obtained by stirring uniformly;
step 3, preparing niobium-containing solution
Step 3.1, heating the mixed acid obtained in the step 2 to 75-80 ℃, adding 87 kg of the niobium-containing glass powder obtained in the step 1 into the mixed acid under the stirring state, and preserving the temperature at 95 ℃ for 3 hours to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, filtering out insoluble substances (mainly titanium dioxide, lithium fluoride and sodium fluoride) in the crude niobium-containing solution, and collecting filtrate to obtain the niobium-containing solution;
step 4, one-step purification of niobium element
Adding 20% ammonia water into the niobium-containing solution obtained in the step 3.2 under stirring, adjusting the pH value to 8.7 (the adding amount is based on the pH value because the volatilization amount of the ammonia water is large), depositing a large amount of the ammonia water in a PP vat for 6-8 hours, removing the supernatant, taking out the bottom sediment, performing centrifugal liquid-solid separation on the bottom sediment to obtain a filter cake, and washing the filter cake obtained by liquid-solid separation to pH6.9 to obtain a niobium-containing sediment crude product;
step 5, niobium element secondary purification
Preparing an oxalic acid solution with the mass fraction of 20% in a reaction kettle, heating to 90 ℃, adding the crude niobium-containing precipitate obtained in the step 4 into the oxalic acid solution, preserving the temperature at 90 ℃ for 3 hours to obtain the crude niobium oxalate solution, filtering the crude niobium oxalate solution to remove insoluble matters to obtain a refined niobium oxalate solution, heating the refined niobium oxalate solution to 100-105 ℃ for concentration, taking out the crystals after a large amount of crystallization occurs, and putting the crystals into a centrifuge while the crystals are hot for liquid-solid separation to obtain the refined niobium oxalate solution;
step 6, purifying the niobium element for three times
Adding 500kg of hydrochloric acid with the mass fraction of 5% into a polytetrafluoroethylene reaction kettle, heating to 75-80 ℃, adding the refined niobium oxalate obtained in the step 5, preserving heat and dissolving for 1 hour to obtain a pure niobium-containing solution, heating the pure niobium-containing solution to 100-105 ℃ for concentration, fishing out the crystals after a large amount of crystallization occurs, and centrifuging while the crystals are hot to obtain the pure niobium oxalate;
step 7, niobium pentoxide preparation
Placing the pure niobium oxalate obtained in the step 6.2 into a ceramic crucible for gradient drying:
drying at 280 ℃ for 4.5 hours in a first gradient;
and (3) drying at 880 ℃ for 6 hours to obtain the high-purity niobium pentoxide.
The XRD pattern of the target product obtained in the embodiment is basically consistent with that of the attached figure 1, and the product is niobium pentoxide without other miscellaneous peaks. The detection by Agilent 5110-ICP-OES shows that iron, cobalt, nickel, copper, chromium, cadmium, vanadium and manganese in niobium pentoxide are less than 1ppm, sodium is less than 50ppm, potassium is less than 200ppm, chlorine is less than 50ppm, and phosphorus is less than 0.13ppm. The test result of the aluminum fluoride prepared at this time meets the standard. The details are shown in table 5 below:
TABLE 5
From the above 5 examples, it can be seen that the preparation process is very stable as long as the feeding proportion and the drying temperature are within the given ranges, and the niobium pentoxide obtained by purifying the niobium-containing glass slag meets the use standard of the special optical glass additive.
Claims (8)
1. The method for extracting niobium pentoxide from the waste niobium-containing glass is characterized by comprising the following steps of:
step 1, crushing niobium-containing glass
Crushing niobium-containing glass into niobium-containing glass powder;
step 2, preparing mixed acid
Mixing hydrofluoric acid with the mass fraction of 50-55% and analytically pure nitric acid in the mass ratio of 9-10:1, and uniformly stirring to obtain mixed acid;
step 3, preparing niobium-containing solution
Step 3.1, preheating the mixed acid, and adding the niobium-containing glass powder into the preheated mixed acid for reaction to obtain a crude niobium-containing solution;
step 3.2, filtering the crude niobium-containing solution, and collecting filtrate to obtain a niobium-containing solution;
step 4, one-time purification
Adding ammonia water into the niobium-containing solution, adjusting the pH to 8.5-9, settling, removing supernatant, centrifuging the bottom precipitate, performing liquid-solid separation to obtain a filter cake, and washing the filter cake with water until the pH value is 6.7-7.2 to obtain a crude niobium-containing precipitate;
step 5, secondary purification
Adding the crude product containing niobium into oxalic acid for reaction, and after the reaction is finished, sequentially filtering, collecting filtrate, heating, concentrating, crystallizing, and performing liquid-solid separation and crystallization to obtain refined niobium oxalate;
step 6, three times of purification
Adding the refined niobium oxalate into hydrochloric acid for dissolution and recrystallization, and performing liquid-solid separation and crystallization to obtain crystals, namely a pure niobium oxalate product;
step 7, preparing niobium pentoxide
And (3) carrying out gradient heating and drying on the pure niobium oxalate product to obtain niobium pentoxide.
2. The method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 1, wherein: in step 1, the niobium-containing glass is crushed into 80 mesh or more niobium-containing glass powder.
3. The method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 1, wherein: the mass ratio of hydrofluoric acid to analytically pure nitric acid in step 2 was 9.8:1.
4. A method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 1, 2 or 3, wherein: in step 3.1: heating the mixed acid to 70-80 ℃, adding the niobium-containing glass powder into the mixed acid under the stirring state, heating to 90-100 ℃, and preserving heat for 2-3 hours to obtain a crude niobium-containing solution; wherein the mass ratio of the mixed acid to the niobium-containing glass powder is 1.8-2.3:1.
5. The method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 4, wherein: the mass ratio of the mixed acid to the niobium-containing glass powder in the step 3.1 is 1.82:1.
6. The method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 4, wherein: the step 5 is specifically as follows: adding the crude product of the niobium-containing precipitate into oxalic acid with the mass fraction of 20-30% and the preheating temperature of 90-100 ℃, carrying out heat preservation reaction for 2-3 hours to obtain the crude product of the niobium oxalate solution, filtering the crude product of the niobium oxalate solution, heating to 100-105 ℃ for concentrating and crystallizing, and separating and crystallizing while the solution is hot to obtain the refined product of the niobium oxalate.
7. The method for extracting niobium pentoxide from waste niobium-containing glass as claimed in claim 6, wherein: the step 6 is specifically as follows: adding the refined niobium oxalate into hydrochloric acid with the mass fraction of 5-8% and the preheating temperature of 70-80 ℃, carrying out heat preservation reaction for 1-2 hours, obtaining a pure niobium-containing solution after the reaction is finished, heating the pure niobium-containing solution to 100-105 ℃ for concentrating and crystallizing, and separating and crystallizing while the solution is hot, thus obtaining the pure niobium oxalate.
8. The method for extracting niobium pentoxide from waste niobium-containing glass according to claim 1, wherein the gradient heating and drying is specifically as follows:
a first gradient: drying at 200-300 deg.c for 4-5 hr;
a second gradient: drying at 800-900 deg.c for 4-6 hr to obtain high purity niobium pentoxide.
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