CN115505734A - Method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag - Google Patents
Method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 58
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002893 slag Substances 0.000 title claims abstract description 21
- 239000000284 extract Substances 0.000 title claims abstract description 20
- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 18
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229940117975 chromium trioxide Drugs 0.000 title claims abstract description 6
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000011651 chromium Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 23
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 120
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 76
- 239000004530 micro-emulsion Substances 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 50
- 239000011780 sodium chloride Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 3
- 150000004706 metal oxides Chemical class 0.000 claims 3
- 239000012074 organic phase Substances 0.000 abstract description 20
- 238000000926 separation method Methods 0.000 abstract description 6
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 229910052804 chromium Inorganic materials 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- -1 vanadium anions Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag, and relates to the technical field of separation and extraction of vanadium by wet metallurgy. Adding a desiliconization agent to remove silicon in the leachate, then adding a reducing agent to selectively reduce Cr (VI) in the leachate to Cr (III), and selecting a proper extraction system to selectively extract vanadium, thereby realizing vanadium-chromium separation. The vanadium-loaded organic phase can be subjected to back extraction, precipitation and calcination to obtain high-purity vanadium pentoxide, and the raffinate is subjected to precipitation and calcination to obtain chromium sesquioxide. The method for preparing the vanadium pentoxide has the advantages of short flow, low cost and high efficiency, and can obtain the chromium sesquioxide while obtaining the high-purity vanadium pentoxide.
Description
Technical Field
The invention relates to the technical field of vanadium separation and extraction in hydrometallurgy, in particular to a method for preparing high-purity vanadium pentoxide and chromium sesquioxide by sodium roasting water extract of industrial vanadium slag.
Background
Vanadium is an important industrial raw material and has wide application, and comprises the following components: vanadium, as an alloying element or alloying additive, accounts for about 90% for the steel industry; as the main active ingredient of sulfuric acid industry and industrial denitration catalysts; the vanadium-containing alloy is applied to nuclear industry and aerospace; the colorful pigment can be used as pigment for ceramic coloring and production of colored glass and ink; the electrolyte is used as an electrode material or an electrolyte in the energy industry; can be used as effective trace component of medicine in medical field. In particular, the industrial application of high-purity vanadium pentoxide is increasing. High-purity vanadium pentoxide is used as a raw material for preparing high-end products, and can be applied to a plurality of high-precision industries: energy fields such as lithium vanadium oxide batteries, all vanadium flow batteries; the vanadium-aluminum alloy is applied to aerospace, military and civil use; preparing an industrial catalyst; and (3) preparing the luminescent material.
The vanadium has such wide application, so how to efficiently extract vanadium to prepare high-purity vanadium products is an important topic. At present, vanadium slag is mainly used as a raw material, vanadium is leached into a leaching solution through sodium salt roasting water leaching, and then vanadium pentoxide is prepared through a chemical precipitation method. If high-purity vanadium pentoxide needs to be prepared, multiple precipitation-redissolution processes are needed, which brings the problems of long process flow, high production cost, low production efficiency, low recovery rate, large wastewater amount and serious environmental pollution. Therefore, a short-flow and low-cost method needs to be developed to produce high-purity vanadium pentoxide.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag, which specifically comprises the steps of adding a desiliconization agent to remove silicon in the extract, then adding a reducing agent to selectively reduce Cr (VI) in the extract to Cr (III), and selecting a proper extraction system to selectively extract vanadium so as to realize vanadium-chromium separation. The vanadium-loaded organic phase can be subjected to back extraction, precipitation and calcination to obtain high-purity vanadium pentoxide, and the raffinate is subjected to precipitation and calcination to obtain chromium sesquioxide.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag, which comprises the following steps:
(1) Adding a desiliconization agent into the industrial vanadium slag sodium salt roasting water leaching solution, removing silicon in the industrial vanadium slag sodium salt roasting water leaching solution, and filtering to obtain a leaching solution;
(2) Adding a reducing agent into the leachate obtained in the step (1), selectively reducing Cr (VI) in the leachate to Cr (III), and obtaining a solution containing Cr (III);
(3) Preparing microemulsion by using quaternary ammonium salt, medium carbon chain alcohol, oil phase and mixed aqueous solution of NaOH and NaCl;
(4) Mixing the microemulsion obtained in the step (3) and the solution containing Cr (III) obtained in the step (2) according to a certain volume ratio, oscillating for a certain time for extraction, standing for layering, wherein the upper phase is a microemulsion phase, the lower phase is a water phase, and separating the microemulsion phase from the water phase;
(5) Washing, back extraction, precipitation, filtration, washing and calcination are carried out on the vanadium-loaded organic phase (upper micro-emulsion phase) obtained in the step (4), so as to prepare high-purity vanadium pentoxide with the purity of more than 99.99wt% and the direct yield of more than 88%;
(6) Adjusting the pH value of the lower-layer water phase obtained in the step (4) to perform alkaline precipitation, and preparing chromium sesquioxide through filtering, washing and calcining, wherein the purity of the chromium sesquioxide is more than 98.80%, and the direct yield of the chromium is more than 96%;
(7) And (3) recovering the organic phase (microemulsion phase) obtained after the back extraction in the step (5) by using a mixed aqueous solution of NaOH and NaCl, and replacing the microemulsion in the step (4) of the next reaction for recycling and extracting.
Based on the technical scheme, preferably, in the step (1), the concentration of vanadium in the sodium salt roasting water extract of the industrial vanadium slag is 20-40 g.L -1 。
Based on the technical scheme, preferably, in the step (1), after the pH = 8-11 of the sodium salt roasting water leaching solution of the industrial vanadium slag is adjusted, a desiliconization agent is added, wherein the desiliconization agent is aluminum sulfate, al is Si = 0.8-2:1 (according to the molar ratio of Si in the desiliconization agent to Al in the sodium salt roasting water leaching solution of the industrial vanadium slag), the desiliconization temperature is 60-90 ℃, and the stirring time is 1-2 h.
Based on the technical scheme, in the step (2), preferably, the pH of the leachate is adjusted to 3-6, and then a reducing agent is added, wherein the reducing agent is at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite and sulfurous acid, S: cr = 1.5-3:1 (calculated according to the molar ratio of S in the reducing agent to Cr in the solution), the reducing temperature is 45-70 ℃, and the stirring time is 20-60 min.
Based on the technical scheme, preferably, in the step (3), the quaternary ammonium salt, the medium carbon chain alcohol, the oil phase and the mixed aqueous solution of NaOH and NaCl are mixed and vibrated for 5-10 min, and the mixture is kept stand for layering, wherein the upper phase is the microemulsion.
Based on the above technical scheme, preferably, in the step (3), the quaternary ammonium salt is one of trioctylmethylammonium chloride, trinonylmethylammonium chloride and tridodecylmethylammonium chloride, and the mass concentration (mass fraction) of the quaternary ammonium salt in the microemulsion is 1-35%; the medium carbon chain alcohol is one of n-butyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptyl alcohol and n-octyl alcohol, and the mass concentration (mass fraction) of the medium carbon chain alcohol in the microemulsion is 5-35%; the oil phase is one of kerosene and n-heptane, and the mass concentration (mass fraction) of the oil phase in the microemulsion is 20-93%; the concentration of NaOH and NaCl in the mixed water solution of NaOH and NaCl is 0.1-2.0M, and the mass concentration (mass fraction) of the NaOH and NaCl in the microemulsion is 1-10%.
Based on the above technical scheme, preferably, in the step (4), the volume ratio O/A of the microemulsion to the solution containing Cr (III) is 1:1-10, and the oscillation time is 1-10 min.
Based on the above technical scheme, preferably, in the step (5), in the washing process, the washing solution is deionized water, the washing ratio of the vanadium-loaded organic phase (upper micro-emulsion phase) to the washing solution is O/A = 1:1-2, and the washing time is 1-2 min; in the back extraction process, the back extraction agent is a mixed aqueous solution of 1-2M NaOH and 1-4M NaCl, the washed vanadium-loaded organic phase (upper micro-emulsion phase) has O/A = 1-2:1 compared with the back extraction of the back extraction agent, and the back extraction time is 1-2 min; in the precipitation process, the precipitator is ammonium sulfate or ammonium chloride, the ammonium addition coefficient is 0.6-4.5, and the stirring time is 1-2 hours; washing the filtered precipitate according to the mass ratio of the precipitate to the deionized water of 1-2:1; in the calcining process, the calcining temperature is 450-600 ℃, and the calcining time is 1-2 h.
Based on the above technical scheme, preferably, in the step (6), the solution for adjusting the pH value is a 1-6M NaOH solution, and the pH of the solution is adjusted to 8-9; in the washing process, the washing liquid is deionized water, and washing is carried out according to the mass ratio of the precipitate to the deionized water of 1-2:1; in the calcining process, the calcining temperature is 800-1100 ℃, and the calcining time is 2-3 h.
Based on the above technical scheme, preferably, in the step (1), the step (2) and the step (6), the reagent used for adjusting the pH value is a sulfuric acid solution, and the concentration of the sulfuric acid solution is 4 to 16M.
Based on the above technical scheme, preferably, in the step (7), the concentrations of NaOH and NaCl in the mixed aqueous solution of NaOH and NaCl are both 0.1 to 2.0M, and the recovery time of the organic phase (microemulsion phase) is 5 to 10min compared with the recovery of the mixed aqueous solution of NaOH and NaCl with O/a =1:1 to 2.
Compared with the prior art, the invention has the following advantages:
1. compared with the extraction of vanadium by primary amine extraction and separation, the method has better effect. The primary amine extraction leach solution, even under optimum conditions, will have about 10% of the chromium entering the organic phase. Since V (V) and Cr (VI) exist in the leachate in the form of anions, the chromium inevitably enters the organic phase while vanadium is extracted, which results in an excessively high impurity content of vanadium pentoxide in the final product. In the invention, the reducing agent is added to selectively reduce Cr (VI) into Cr (III) to cause the charge difference of vanadium and chromium ions, the cationic extractant extraction system is used for selectively extracting vanadium anions, and chromium cations are remained in raffinate, thereby realizing the high-efficiency separation of vanadium and chromium and laying a foundation for preparing high-purity vanadium pentoxide.
2. The microemulsion belongs to a stable thermodynamic system, and a third phase and an emulsification phenomenon are not easy to generate in the extraction process, so that the loss of an organic phase is reduced; after extraction, the two phases are easy and quick to phase, which is beneficial to improving the actual production efficiency.
3. Compared with the traditional solvent extraction, the microemulsion extraction has the advantages that as countless nano-scale water spheres are dispersed in the microemulsion, the specific surface area is obviously increased, the reaction speed is higher, and the production efficiency is improved for the actual industrial production; meanwhile, the dispersed nano water spheres also increase the extraction saturation capacity of the microemulsion, and compared with the traditional solvent extraction microemulsion, the organic phase with the same quality can extract more vanadium elements.
4. The existing vanadium enterprise has the disadvantages of long technological process for preparing high-purity vanadium pentoxide, high production cost, low production efficiency and low yield, and simultaneously, chromium enters waste water to cause resource waste. The method for preparing vanadium pentoxide has the advantages of short flow, low cost and high efficiency, and can obtain high-purity vanadium pentoxide and chromium sesquioxide.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
1. Sodium salt roasting water extract of vanadium slag in Panpan steel vanadium plant is used as raw material, wherein the concentration of vanadium is 35 g.L -1 The pH was adjusted to 9 with 16M sulfuric acid solution, aluminum sulfate was added to it in a molar ratio of Al: si =1:1, desiliconization temperature 75 ℃, stirring time 1h, standing, cooling and filtering.
2. The filtrate obtained in step 1 was adjusted to pH 5 with 16M sulfuric acid solution, to which sodium sulfite was added at a reduction temperature of 60 ℃ and a stirring time of 25min in a ratio of S: cr = 1.6.
3. Mixing and oscillating trioctylmethylammonium chloride, isoamylol, kerosene and a mixed aqueous solution of NaOH and NaCl for 5min, standing and layering, wherein the upper phase is the microemulsion. Wherein the concentration of each component in the microemulsion is as follows:
the concentration of the trioctylmethylammonium chloride was: 35% (w/w)
The concentration of isoamyl alcohol is: 25% (w/w)
The concentration of kerosene was: 30% (w/w)
Mixed aqueous solution of NaOH and NaCl: 10% (w/w)
Wherein the concentration of NaOH in the mixed aqueous solution of NaOH and NaCl is as follows: 0.1M, the concentration of NaCl: 0.1M.
4. Mixing the microemulsion in the step 3 with the solution obtained in the step 2 according to the volume ratio of O/A =1:1, oscillating for 5min for extraction, standing for layering, wherein the upper phase is a loaded microemulsion phase, the lower phase is an aqueous phase, and separating the microemulsion phase from the aqueous phase.
5. Washing the vanadium-loaded organic phase (loaded microemulsion phase) in the step 4 with deionized water according to a washing phase ratio of O/A =1:1 for 2min; carrying out back extraction on the washed organic phase and a mixed solution of 1M NaOH and 2M NaCl according to the ratio of O/A =1:1 for 2min; adding ammonium sulfate into the lower layer stripping solution, wherein the ammonium adding coefficient is 2.4, and stirring for 1h; washing the filtered precipitate according to the mass of the precipitate and deionized water 1:1; the washed precipitate was dried and calcined at 500 ℃ for 2h. High-purity vanadium pentoxide with the purity of 99.99wt% can be obtained, and the direct yield of the vanadium is 89.20%.
6. And (3) adjusting the pH value of the lower layer of the water phase in the step (4) to 8.5 by using a 4M sulfuric acid solution, washing the filtered precipitate according to the mass ratio of the precipitate to the deionized water of 1:1, drying, and calcining for 2 hours at 800 ℃. The chromium sesquioxide with the purity of 98.83wt percent can be obtained, and the direct yield of the chromium is 96.04 percent.
7. And (3) recovering the organic phase (microemulsion phase) after the back extraction in the step (5), and selecting a mixed aqueous solution of 0.1M NaOH and 0.1M NaCl as a recovery solution, wherein the recovery time is 5min compared with O/A = 1:1. The recovered microemulsion is reused for extraction, the extraction rate is 99.12%, and the effect of the recovered microemulsion is not obviously different from that of a new microemulsion.
Example 2
1. Sodium salt roasting water extract of vanadium slag in Panpan steel vanadium plant is used as raw material, wherein the concentration of vanadium is 40 g.L -1 The pH thereof was adjusted to 8.5 with a 16M sulfuric acid solution, aluminum sulfate was added thereto at an Al: si =0.9 (molar ratio) desilication temperature of 75 ℃, stirred for 1h, left to stand, cooled and filtered.
2. The pH of the filtrate obtained in step 1 was adjusted to 3 with 16M sulfuric acid solution, to which sodium sulfite was added at a reduction temperature of 60 ℃ for a stirring time of 25min in accordance with S: cr = 1.6.
3. Mixing and shaking trioctylmethylammonium chloride, isoamylol, kerosene and a mixed aqueous solution of NaOH and NaCl for 5min, standing and layering, wherein the upper phase is the microemulsion. Wherein the concentration of each component in the microemulsion is as follows:
the concentration of the trioctylmethylammonium chloride was: 30% (w/w)
The concentration of isoamyl alcohol is: 20% (w/w)
The concentration of kerosene was: 42% (w/w)
Mixed aqueous solution of NaOH and NaCl: 8% (w/w)
Wherein the concentration of NaOH in the mixed aqueous solution of NaOH and NaCl is as follows: the concentration of 0.4M NaCl was: 0.4M.
4. Mixing the microemulsion in the step 3 with the solution obtained in the step 2 according to the volume ratio of O/A1:1, oscillating for 5min for extraction, standing for layering, wherein the upper phase is a loaded microemulsion phase, the lower phase is an aqueous phase, and separating the microemulsion phase from the aqueous phase.
5. Washing the vanadium-loaded organic phase (loaded microemulsion phase) in the step 4 with deionized water according to a washing phase ratio O/A =1:1 for 2min; carrying out back extraction on the washed organic phase and a mixed solution of 1M NaOH and 3M NaCl according to the ratio of O/A =1:1 for 2min; adding ammonium sulfate into the lower layer stripping solution, wherein the ammonium adding coefficient is 2.4, and stirring for 1h; washing the filtered precipitate according to the mass of the precipitate and deionized water 1:2; the washed precipitate was dried and calcined at 500 ℃ for 2h. High-purity vanadium pentoxide with the purity of 99.99wt% can be obtained, and the direct yield of the vanadium is 89.28%.
6. And (3) adjusting the pH of the lower layer of the water phase in the step (4) to 8.5 by using a 4M sulfuric acid solution, washing the filtered precipitate according to the mass ratio of the precipitate to the deionized water of 1:2, drying, and calcining for 2 hours at 850 ℃. The chromium sesquioxide with the purity of 98.85wt percent can be obtained, and the direct yield of the chromium is 96.15 percent.
7. And (3) recovering the organic phase (microemulsion phase) after the back extraction in the step (5), and selecting a mixed aqueous solution of 0.4M NaOH and 0.4M NaCl as a recovery solution, wherein the recovery time is 5min compared with O/A = 1:1. The recovered microemulsion is reused for extraction, the extraction rate is 99.11 percent, and the effect is not obviously different from that of the new microemulsion.
Example 3
1. Sodium salt roasting water extract of vanadium slag in Panpan steel vanadium plant is used as raw material, wherein the concentration of vanadium is 25 g.L -1 The pH was adjusted to 9.5 with a 16M sulfuric acid solution, to which was added aluminum sulfate at an Al: si =0.9 (molar ratio) desiliconization temperature of 75 ℃, stirred for 1h, left to stand, cooled and filtered.
2. The filtrate obtained in step 1 was adjusted to pH 3 with 16M sulfuric acid solution, to which sodium sulfite was added at a reduction temperature of 50 ℃ and a stirring time of 25min in a ratio of S: cr = 1.6.
3. Mixing and shaking trioctylmethylammonium chloride, isoamylol, kerosene and a mixed aqueous solution of NaOH and NaCl for 5min, standing and layering, wherein the upper phase is the microemulsion. Wherein the concentration of each component in the microemulsion is as follows:
the concentration of the trioctylmethylammonium chloride was: 35% (w/w)
The concentration of isoamyl alcohol is: 25% (w/w)
The concentration of kerosene was: 30% (w/w)
Mixed aqueous solution of NaOH and NaCl: 10% (w/w)
Wherein the concentration of NaOH in the mixed aqueous solution of NaOH and NaCl is as follows: the concentration of 0.6M NaCl was: 0.6M.
4. Mixing the microemulsion in the step 3 with the solution obtained in the step 2 according to the volume ratio of O/A1:1, oscillating for 5min for extraction, standing for layering, wherein the upper phase is a loaded microemulsion phase, the lower phase is a water phase, and separating the microemulsion phase from the water phase.
5. Washing the vanadium-loaded organic phase (loaded microemulsion phase) in the step 4 with deionized water according to a washing phase ratio of O/A =1:1 for 2min; carrying out back extraction on the washed organic phase and a mixed solution of 1M NaOH and 4M NaCl according to the ratio of O/A =1:1 for 2min; adding ammonium sulfate into the lower layer stripping solution, wherein the ammonium adding coefficient is 2.5, and stirring for 1h; washing the filtered precipitate according to the mass of the precipitate and deionized water 1:2; the washed precipitate was calcined at 500 ℃ for 2h after drying. High-purity vanadium pentoxide with the purity of 99.99wt% can be obtained, and the direct yield of the vanadium is 89.31%.
6. And (3) adjusting the pH value of the lower layer of the water phase in the step (4) to 8.0 by using a 4M sulfuric acid solution, washing the filtered precipitate according to the mass ratio of the precipitate to the deionized water of 1:2, drying, and calcining for 2 hours at 900 ℃. The chromium sesquioxide with the purity of 98.82wt percent can be obtained, and the direct yield of the chromium is 96.17 percent.
7. And (3) recovering the organic phase (microemulsion phase) after the back extraction in the step (5), and selecting a mixed aqueous solution of 0.6M NaOH and 0.6M NaCl as a recovery solution, wherein the recovery time is 5min compared with O/A = 1:1. The recovered microemulsion is reused for extraction, the extraction rate is 99.14 percent, and the effect is not obviously different from that of the new microemulsion.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. A method for preparing high-purity vanadium pentoxide and chromium trioxide from sodium salt roasting water extract of industrial vanadium slag is characterized by comprising the following steps:
(1) Adding a desiliconization agent into the industrial vanadium slag sodium salt roasting water leaching solution, removing silicon in the industrial vanadium slag sodium salt roasting water leaching solution, and filtering to obtain a leaching solution;
(2) Adding a reducing agent into the leachate obtained in the step (1), and reducing Cr (VI) in the leachate to Cr (III) to obtain a solution containing Cr (III);
(3) Preparing microemulsion by using quaternary ammonium salt, medium carbon chain alcohol, oil phase and mixed aqueous solution of NaOH and NaCl;
(4) Mixing the microemulsion obtained in the step (3) with the solution containing Cr (III) obtained in the step (2), oscillating for extraction, standing for layering, wherein the upper phase is a microemulsion phase, the lower phase is a water phase, and separating the microemulsion phase from the water phase;
(5) Washing, back extraction, precipitation, filtration, washing and calcination are carried out on the upper layer micro-emulsion phase obtained in the step (4) to prepare high-purity vanadium pentoxide;
(6) Adjusting the pH value of the lower-layer water phase obtained in the step (4) to perform alkaline precipitation, and preparing chromium sesquioxide through filtering, washing and calcining;
(7) And (4) recovering the microemulsion phase obtained after the back extraction in the step (5) by using a mixed aqueous solution of NaOH and NaCl, and replacing the microemulsion phase in the step (4) of the next reaction for recycling.
2. The method as claimed in claim 1, wherein in the step (1), the pH value of the industrial vanadium slag sodium roasting water extract is adjusted to 8-11, and then the desiliconization agent is added, wherein the desiliconization agent is aluminum sulfate, the molar ratio of Si in the desiliconization agent to Al in the industrial vanadium slag sodium roasting water extract is 0.8-2:1, the desiliconization temperature is 60-90 ℃, and the desiliconization time is 1-2 h.
3. The method according to claim 1 or 3, wherein in the step (2), the pH of the leachate is adjusted to 3-6, and then a reducing agent is added, wherein the reducing agent is at least one of sodium sulfite, sodium bisulfite, sodium metabisulfite and sulfurous acid, the molar ratio of S in the reducing agent to Cr in the leachate is 1.5-3:1, the reduction temperature is 45-70 ℃, and the reduction time is 20-60 min.
4. The method according to claim 1, wherein in the step (3), the quaternary ammonium salt, the medium carbon chain alcohol, the oil phase and the mixed aqueous solution of NaOH and NaCl are mixed and vibrated, and the mixture is kept standing for layering, and the upper phase is microemulsion.
5. The method according to claim 1 or 4, wherein in the step (3), the quaternary ammonium salt is one of trioctylmethylammonium chloride, trinonylmethylammonium chloride and tridodecylmethylammonium chloride, and the mass concentration of the quaternary ammonium salt in the microemulsion is 1-35%; the medium carbon chain alcohol is one of n-butyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptyl alcohol and n-octyl alcohol, and the mass concentration of the medium carbon chain alcohol in the microemulsion is 5-35%; the oil phase is one of kerosene and n-heptane, and the mass concentration of the oil phase in the microemulsion is 20% -93%; the concentration of NaOH and NaCl in the mixed aqueous solution of NaOH and NaCl is 0.1-2.0M, and the mass concentration of the NaOH and NaCl in the microemulsion is 1-10%.
6. The method according to claim 1, wherein in the step (4), the volume ratio O/A of the microemulsion to the solution containing Cr (III) is 1:1-10, and the oscillation time is 1-10 min.
7. The method as claimed in claim 1, wherein in the step (5), the washing process, the washing solution is deionized water, the microemulsion phase and the washing phase of the washing solution are O/A = 1:1-2, and the washing time is 1-2 min; in the back extraction process, the back extractant is a mixed aqueous solution of 1-2M NaOH and 1-4M NaCl, the back extraction ratio of the washed microemulsion phase to the back extractant O/A = 1-2:1, and the back extraction time is 1-2 min; in the precipitation process, the precipitator is ammonium sulfate or ammonium chloride, the ammonium addition coefficient is 0.6-4.5, and the stirring time is 1-2 h; washing the filtered precipitate according to the mass ratio of the precipitate to the deionized water of 1-2:1; in the calcining process, the calcining temperature is 450-600 ℃, and the calcining time is 1-2 h.
8. The method according to claim 1, wherein in the step (6), the pH value adjusting solution is a 1-6M NaOH solution, and the pH value of the solution is adjusted to 8-9; in the washing process, the washing liquid is deionized water, and the washing is carried out according to the mass ratio of the precipitate to the deionized water of 1-2:1; in the calcining process, the calcining temperature is 800-1100 ℃, and the calcining time is 2-3 h.
9. The method according to claim 1, wherein in the step (7), the concentrations of NaOH and NaCl in the mixed aqueous solution of NaOH and NaCl are both 0.1-2.0M, and the recovery time of the microemulsion phase and the mixed aqueous solution of NaOH and NaCl is 5-10 min compared with O/A = 1:1-2.
10. The method of claim 1, wherein the step of removing the metal oxide layer comprises removing the metal oxide layer from the metal oxide layerIn the step (1), the concentration of vanadium in the sodium salt roasting water extract of the industrial vanadium slag is 20-40 g.L -1 。
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