WO2010057410A1 - Clean production method of vanadium oxide - Google Patents
Clean production method of vanadium oxide Download PDFInfo
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- WO2010057410A1 WO2010057410A1 PCT/CN2009/074687 CN2009074687W WO2010057410A1 WO 2010057410 A1 WO2010057410 A1 WO 2010057410A1 CN 2009074687 W CN2009074687 W CN 2009074687W WO 2010057410 A1 WO2010057410 A1 WO 2010057410A1
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- WIPO (PCT)
- Prior art keywords
- vanadium
- water
- washing
- give
- vanadium oxide
- Prior art date
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 128
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 238000002386 leaching Methods 0.000 claims abstract description 53
- 239000002351 wastewater Substances 0.000 claims abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 19
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 45
- 239000002002 slurry Substances 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 58
- 238000000605 extraction Methods 0.000 abstract description 27
- 238000011084 recovery Methods 0.000 abstract description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 13
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 13
- 239000004571 lime Substances 0.000 abstract description 13
- 238000006386 neutralization reaction Methods 0.000 abstract description 7
- 239000008267 milk Substances 0.000 abstract description 6
- 210000004080 milk Anatomy 0.000 abstract description 6
- 235000013336 milk Nutrition 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 32
- 239000002893 slag Substances 0.000 description 27
- 159000000000 sodium salts Chemical class 0.000 description 23
- 239000000203 mixture Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 11
- 238000004065 wastewater treatment Methods 0.000 description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 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 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- -1 for example Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a clean production method of vanadium oxide, and belongs to the technical field of vanadium oxide extraction.
- Conventional vanadium extraction process using sodium salt comprises: adopting common sodium salts, such as Na 2 CO 3 , Na 2 SO 4 , or NaCl, as additives, and roasting the sodium salt with vanadium-containing raw material at high temperature, wherein vanadium in the raw material is oxidized to V + by oxygen in air, and then V + bonds with sodium salt to generate sodium vanadate easily dissolvable in water; leaching the roasted product with water to dissolve sodium vanadate into solution, carrying out solid-liquid separation, removing major impurities such as P, Si and so on from the solution by using CaCl 2 , adding ammonium salts such as (NH 4 ) 2 SO 4 , NH 4 Cl, (NH 4 ) 2 CO 3 , or NH 4 NO 3 etc.
- common sodium salts such as Na 2 CO 3 , Na 2 SO 4 , or NaCl
- ammonium salt has to be used in an amount much higher than theoretical amount during vanadium precipitation to give high quality vanadium product, such that wastewater after vanadium precipitation has high concentration of ammonia nitrogen and sodium salt and is most difficult to be treated, e.g., NH 4 + concentration usually is as high as 2,000-8,000 mg/L or even higher, and Na + concentration can be above 20g/L. Therefore, wastewater treatment is the most difficult problem to be handled in the vanadium extraction process using sodium salt.
- One scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and then discharge
- the ammonia removal technique mainly comprises air stripping method, membrane separation method, magnesium ammonium phosphate precipitation method, chemical oxidation method, zeolite adsorption method, and biological nitrogen removal method
- the sodium removal method mainly adopts concentration crystallization method.
- the disadvantages of this scheme comprise that cost of ammonia removal treatment and sodium removal treatment is too high to be accepted by manufacturing plants, new pollution is likely to occur during the treatment, and the recovered sodium salt is sodium sulfate containing many impurities, which will release SO 2 to pollute environment upon roasting and thus is not suitable as roasting additive.
- the other scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and return condensation water for circulation.
- the difference from the first scheme is that the water of the first scheme does not circulate, but has to meet national industrial wastewater discharge standard ( ⁇ 15mg/L for ammonia nitrogen wastewater), so it is very difficult to meet the standard, and high cost is required; although the second scheme does not discharge wastewater, a large amount of energy has to be consumed to evaporate wastewater, which also has the disadvantage of high cost, and evaporated gaseous ammonia is usually not recovered.
- vanadium extraction process using lime or limestone as roasting additive has been studied, which targets at some inherit shortcomings of vanadium extraction process using sodium salt, including (1) strict restriction on CaO content (less than 1.5%) in vanadium slag, because vanadium recovery yield drops 4.7-9% as CaO content in the slag increases 1%; (2) high cost due to large consumption amount of sodium salt and ammonium salt; and (3) environment pollution caused by large amount of sodium salt and ammonium salt in wastewater.
- the roasted material of vanadium extraction process using calcium salt can be leached with sulfuric aid, or with carbonate or bicarbonate. Germany Patent Application No. 2324737 and British Patent Application No.
- Tula Vanadium Plant of former Soviet Union constructed the world first (also the only one) vanadium manufacture plant adopting calcifying roasting-sulfuric acid leaching- vanadium hydrolysis precipitation process, which can give V 2 O 5 product with purity of 88-94% (92% on average) and containing main impurities of Mn, Mg, and Ca, and then V 2 O 5 product is smelted into vanadium iron also containing many impurities; therefore the manufacturer is non-competitive on international market, and mainly supplies product to domestic market, that is the main reason that other vanadium plants do not adopt this process.
- Russian patent application Nos To improve product competivity on market, Russian patent application Nos.
- 2001127026/02 and 96106854/02 disclosed method for producing high quality vanadium oxide from hydrolysis precipitate containing Mn, Ca, and Mg impurities.
- the method comprises adopting NaOH to dissolve hydrolysis precipitate, then adding ammonium salt like ammonium sulfate while heating, precipitating ammonium polyvanadate, and calcining to give high quality vanadium oxide with V 2 O 5 content higher than 98%.
- the method reduces total amount of ammonia-containing wastewater, but still requires wastewater treatment including ammonia removal and sodium removal; therefore the technical and economic difficulties of high cost and difficult ammonia nitrogen wastewater treatment still exist, additionally, vanadium recovery rate is lowered to some extent due to long treatment process and complicated procedures.
- the object of the present invention is to provide a clean vanadium oxide production method which can not only obtain high quality vanadium product but also circulate and reuse vanadium extraction wastewater.
- the vanadium oxide production method in the present invention comprises following steps including: a. mixing vanadium-containing material with additive to give mixed material, wherein the additive is CaO or limestone, and the amount of the additive makes the CaCVV 2 O 5 weight ratio in the mixed material be 0.5-1.4 : 1; b. roasting the mixed material at 860°C-950°C in oxidizing atmosphere for 60-240min to give roasted material; c. adding water into the roasted material to give slurry, stirring, and slowly adding sulfuric acid solution to leach the slurry while controlling pH at 2.5-3.5; d.
- step e removing P, Mn, and Mg impurities in the wastewater generated in step e to make Mn 2+ and Mg 2+ concentrations lower than 5g/L respectively, and P concentration lower than 0.005g/L to give circulation water, and returning the circulation water to step c for preparing slurry and to step d for washing the residue, wherein the solid raw material used in the above steps has total alkali metal amount not more than 0.3wt%, and total amount of Cl and NO 3 not more than 0.1wt%; and the liquid raw material used in the above steps has total alkali metal amount not more than O.lg/L, and total amount of Cl and NO 3 not more than O.lg/L.
- wastewater can be circulated and reused; and in addition, as the inventive method adopts calcifying roasting and sulfuric acid leaching to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, balance of the easily soluble ions can be maintained during circulation process, wastewater can be circulated and reused after treatment, and thus problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided.
- the vanadium -containing material can be various vanadium-containing raw materials useful for preparing vanadium oxide, such as vanadium slag or other vanadium-containing raw materials (such as vanadium-containing magnetite, and vanadium lead zinc ore, etc.), preferably vanadium slag.
- vanadium slag or other vanadium-containing raw materials (such as vanadium-containing magnetite, and vanadium lead zinc ore, etc.), preferably vanadium slag.
- the mixed material is pulverized to particle size of 0.1mm or less, to make vanadium be easily oxidized into V 5+ to generate vanadate.
- the oxidizing atmosphere can be pure oxygen, air, or mixture of oxygen and inert gas.
- the inert gas is preferably nitrogen gas.
- the roasted material is cooled and pulverized to 0.18mm or less to facilitate leaching before being prepared into slurry.
- the slurry is prepared by stirring the roasted material with water 1.5-4 times by weight.
- the adopted water is the washing water resulted from the residue washing, and if the washing water is insufficient, circulation water is adopted for supplement.
- the sulfuric acid solution for leaching has concentration of 10-75%, the leaching temperature is between room temperature and 58 0 C, and the leaching time is 30-90min. More preferably, pH of the slurry is regulated to 2.8-3.3 with 32-65wt% sulfuric acid solution.
- the washing times are preferably 5-7, the amount of water used for each washing is preferably 20-35wt% of the residue on dry basis, to maintain water balance in circulation process.
- the ammonium salt is preferably ammonium sulfate, ammonium bisulfate, ammonium carbonate, or ammonium bicarbonate.
- the circulation water obtained from treated wastewater after vanadium precipitation contains ammonium salt, when circulation water containing sulfate salt such as (NH 4 )2S ⁇ 4 is adopted for leaching within the leaching condition range in the present invention, NH 4+ has no adverse influence, and SO 4 2" is beneficial for improving leaching rate of calcified roasted material.
- Cl- and NO 3 - usually are easily soluble substances which are difficult to discharge and will affect product quality, and Cl- and NO 3 - in the circulation water have to be removed before using the circulation water, but Cl — and NO3 — removal is difficult and involves high cost, ammonium chloride and ammonium nitrate can not be used.
- step e when weight ratio of NH 3 /Mn is low, the precipitation time will be prolonged, but high quality vanadium product can be obtained; and when weight ratio of NH 3 ZMn is high, precipitation will be finished quickly, energy consumption can be significantly reduced, and product yield will be increased; therefore for overall effect, the amount of the added ammonium salt makes weight ratio of NH 3 /Mn in the leachate preferably within 0.7-1.0:1.
- the returned circulation water contains a certain amount of NH 4+ , if the weight ratio of NH 3 /Mn in the P-removed leachate already satisfies above requirement, ammonium salt is not added, and vanadium precipitation is directly carried out.
- the water washing of the precipitate is carried out for 2-4 times, and the amount of water used for each washing is 25-40wt% of the precipitate on dry basis.
- the wastewater can be treated according to various routine methods to remove P, Mn, and Mg, for example, lime milk is adopted to neutralize wastewater to pH 9-11, the wastewater is filtered to remove main impurities such as Mn, P, and Mg while obtaining wastewater neutralization residue useful as raw material for Mn recovery; or Mn can be individually recovered with other reagents, and then impurities like P and Mg are removed.
- the present invention has following beneficial effects: 1.
- the inventive method adopts calcifying roasting and sulfuric acid leaching technique to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, so that balance of the easily soluble ions can be maintained during circulation, and problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided.
- Ammonium salt is adopted to prepare high quality vanadium oxide product, so that technical problem that conventional calcifying roasting- sulfuric acid leaching process can not produce high quality vanadium product is solved.
- Weight ratio of NH 3 ZMn is controlled to control product quality and ammonium concentration in the solution, when the ratio in the leachate is lower than the value specified in the present invention, ammonium salt is added to regulate the ratio to the specified value, and then the vanadium precipitation is carried out; when the ratio in the leachate has already reached the specified value in the present invention, ammonium salt is not added, and vanadium precipitation is directly carried out, and part of NH 4 + is discharged along with ammonium polyvanadate precipitate, so that NH 4 + concentration in the system will not continuously increase to enable circulation and reuse.
- the circulation water containing sulfate salt such as (NH 4 ) 2 SO 4 is adopted for leaching; within the leaching condition range in the present invention, NH 4 + will not cause adverse influence, and SO 4 " is beneficial for increasing leaching rate of calcified roasted material, so that water circulation and reuse can be finally realized.
- the inventive method can greatly increase total recovery rate (up to 85-88%) of vanadium oxide from vanadium slag, while the recovery rate of the conventional vanadium extraction process using sodium salt is about 80%; therefore the inventive method has increased the recovery rate by 5-8% on average compared with conventional vanadium extraction process using sodium salt, and the obtained vanadium product has good quality, and meets Chinese National Standard No. GB3283-87.
- the inexpensive lime material is adopted to replace expensive sodium carbonate, the consumption amount of sulfuric acid is similar to that in the vanadium extraction process using sodium salt, and NH 4 + is almost completely consumed to precipitate vanadium while most ammonia in wastewater of conventional vanadium extraction process using sodium salt is lost in wastewater treatment; therefore, consumption and cost of various auxiliary and raw materials are significantly decreased.
- Fig. 1 shows flow chart of one preferred embodiment of the method in the present invention.
- step a vanadium slag and lime is mixed to give mixed material (equivalent to step a);
- the mixed material is calcified and roasted (equivalent to step b);
- Sulfuric acid solution is adopted to leach the roasted material at constant pH (equivalent to step c);
- Ammonium salt and sulfuric acid are added into the leachate to precipitate vanadium
- Ammonium polyvanadate obtained from vanadium precipitation is calcined or reduced to give high quality vanadium oxide (equivalent to step f);
- the wastewater obtained from vanadium precipitation is added with lime milk for neutralization, the obtained circulation water is returned to prepare slurry or wash residue, and
- Mn is recovered from the neutralization residue (equivalent to step g).
- Example 1 Roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(5).
- Common vanadium slag with composition shown in Table 1 is ground to less than 0.098mm, 28kg of ground vanadium slag powder is mixed with 1.96kg of lime (ground to below 0.1mm) containing CaO>98%, and then the mixture is roasted at 860 ° C in air for 240min, cooled, and ground to less than 0.18mm.
- 2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 50Og of the ground roasted material to prepare slurry, 10-32wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58 ° C, the reaction is carried out for 60min.
- the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6-7 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
- the leachate is subjected to P-removal treatment to make P satisfy TV/P>1000, and the vanadium precipitation procedure is carried out.
- Ammonium sulfate is added into the P-removed leachate to make NIHb/Mn weight ratio of the solution within 0.3-0.9, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 90 ° C, held for 60-120min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
- Ammonium polyvanadate precipitate is dried, calcined and melted at 500 ° C-800 ° C to give V2O5, and the composition of the obtained V2O5 is analyzed. (5) Wastewater treatment
- Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-10.0, and filtered.
- the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
- the neutralization residue obtained from the filtration is used as raw material for Mn recovery.
- steps (2)-(5) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 4:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
- the maximum value, the minimum value, and the average value of the recovery rate of the rest cycles are shown in Table 2; the maximum value, the minimum value, and the average value of the chemical compositions of the V2O5 product of the rest cycles are shown in Table 3, and the Table 3 also shows compositions of the metallurgical No. 98 and No. 99 of Chinese National Standard No. GB3283-87; and the maximum value, the minimum value, and the average value of the composition of the circulation water after circulation treatment for the rest cycles are shown in Table 4.
- the procedure of raw material pretreatment includes pulverization of bulk coarse vanadium slag, grinding, and iron removal, and a small amount of vanadium is lost in this process.
- the table 3 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
- roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(5).
- the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
- the leachate is subjected to P-removal treatment to make P satisfy TV/P ⁇ IOOO, and the vanadium precipitation procedure is carried out.
- Vanadium precipitation Ammonium sulfate is added into the P-removed leachate to make NIHb/Mn weight ratio of the solution within 0.6-3.0, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 90 0 C, held for 60-90min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
- Ammonium polyvanadate precipitate is dried, calcined and melted at 500 ° C-800 ° C to give
- V2O5, and V2O5 composition is analyzed.
- Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-9.5, and filtered.
- the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
- the neutralization residue obtained from the filtration is used as raw material for Mn recovery.
- steps (2)-(5) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 4:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
- the table 7 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
- roasted material prepared according to step (1) is adopted, 100 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(5).
- 2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 1,00Og of ground roasted material to prepare slurry, 50-75wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58°C, the reaction is carried out for 60min.
- the resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 5-6 times, water used for each time is 250ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate.
- the leachate is subjected to P-removal treatment to make P satisfy TV/P>1000, and the vanadium precipitation procedure is carried out.
- Vanadium precipitation Ammonium sulfate is added into the P-removed leachate to make NH 3 ZMn weight ratio of the solution within 0.7-0.9, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 90 0 C, held for 30-60min, and filtered, the precipitate is washed with tap water containing [Na+K] ⁇ 0.1g/L for 3 times and water used for each time is 60ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
- Ammonium polyvanadate precipitate is dried, calcined and melted at 500°C-800°C to give V 2 O 5 , and V 2 O 5 composition is analyzed.
- Wastewater treatment Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-10.0, and filtered.
- the filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle.
- the neutralization residue obtained from the filtration is used as raw material for Mn recovery.
- steps (2)-(5) are repeated, lOOOg of roasted material is used for each cycle, liquid solid ratio for each cycle is 2:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 100 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
- the table 11 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
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Abstract
Provided is a clean production method of vanadium oxide, which belongs to the technical field of vanadium oxide extraction, and can not only obtain high quality vanadium product but also circulate and reuse vanadium extraction wastewater. The method comprises preparing raw material to be roasted, calcifying roasting, leaching, solid-liquid separating, vanadium precipitating with ammonium salt, and removing ammonia by calcination or reducing to prepare vanadium oxide; where vanadium extraction wastewater is returned to the system for circulation and reuse after neutralization treatment with lime milk, and no wastewater discharge is realized. Vanadium recovery rate is improved, and production cost is reduced. By combining with other techniques, the method can also convert waste resulted from extraction into secondary resource for reuse, so as to realize clean production.
Description
A clean production method of vanadium oxide
Technical field
The present invention relates to a clean production method of vanadium oxide, and belongs to the technical field of vanadium oxide extraction.
Technical background
Conventional vanadium extraction process using sodium salt comprises: adopting common sodium salts, such as Na2CO3, Na2SO4, or NaCl, as additives, and roasting the sodium salt with vanadium-containing raw material at high temperature, wherein vanadium in the raw material is oxidized to V + by oxygen in air, and then V + bonds with sodium salt to generate sodium vanadate easily dissolvable in water; leaching the roasted product with water to dissolve sodium vanadate into solution, carrying out solid-liquid separation, removing major impurities such as P, Si and so on from the solution by using CaCl2, adding ammonium salts such as (NH4)2SO4, NH4Cl, (NH4)2CO3, or NH4NO3 etc. thereto, regulating pH of the solution to 1.5-2.5, heating the solution to above 900C, and holding at the temperature for 40-90min to separate out ammonium polyvanadate precipitate from the solution; removing impurities such as sodium salts carried in the ammonium polyvanadate precipitate by washing with water after filtering, drying, and calcining the precipitate to remove ammonia to give V2Os, or reducing the precipitate at high temperature with reducing gas such as coal gas or natural gas to give V2O3. Presently, most manufacturers in the world adopt this process to produce vanadium products.
This process has the advantages of high product quality, stable process, and easy control. However, ammonium salt has to be used in an amount much higher than theoretical amount during vanadium precipitation to give high quality vanadium product, such that wastewater after vanadium precipitation has high concentration of ammonia nitrogen and sodium salt and is most difficult to be treated, e.g., NH4 + concentration usually is as high as 2,000-8,000 mg/L or even higher, and Na+ concentration can be above 20g/L. Therefore, wastewater treatment is the most difficult problem to be handled in the vanadium extraction process using sodium salt. If the wastewater is directly returned to leaching step for circulation, as sodium vanadate in roasted material (also referred to as "roasted product") is continuously dissolved in water while sodium salt can not be discharged from the solution, sodium salt concentration in the solution becomes increasingly high, the ammonium salt amount required by vanadium
precipitation becomes increasingly large, the solution quickly becomes viscous, it is difficult to carry out filtration or vanadium precipitation, and actually the circulation can not be continued after 1-2 cycles; therefore the wastewater can not be directly circulated and reused. Presently, there are mainly two schemes for solving pollution problems of wastewater from vanadium extraction process using sodium salt. One scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and then discharge wherein the ammonia removal technique mainly comprises air stripping method, membrane separation method, magnesium ammonium phosphate precipitation method, chemical oxidation method, zeolite adsorption method, and biological nitrogen removal method, and the sodium removal method mainly adopts concentration crystallization method. The disadvantages of this scheme comprise that cost of ammonia removal treatment and sodium removal treatment is too high to be accepted by manufacturing plants, new pollution is likely to occur during the treatment, and the recovered sodium salt is sodium sulfate containing many impurities, which will release SO2 to pollute environment upon roasting and thus is not suitable as roasting additive. The other scheme is to remove heavy metals, carry out ammonia removal and sodium removal treatments, and return condensation water for circulation. The difference from the first scheme is that the water of the first scheme does not circulate, but has to meet national industrial wastewater discharge standard ( ≤Ξ 15mg/L for ammonia nitrogen wastewater), so it is very difficult to meet the standard, and high cost is required; although the second scheme does not discharge wastewater, a large amount of energy has to be consumed to evaporate wastewater, which also has the disadvantage of high cost, and evaporated gaseous ammonia is usually not recovered.
Therefore, treatment and utilization of wastewater having high ammonia nitrogen and high sodium salt resulted from vanadium extraction process using sodium salt is urgently to be solved in the field.
Since 1960s and 1970s, vanadium extraction process using lime or limestone as roasting additive, usually called vanadium extraction process using calcium salt or calcifying roasting vanadium extraction process, has been studied, which targets at some inherit shortcomings of vanadium extraction process using sodium salt, including (1) strict restriction on CaO content (less than 1.5%) in vanadium slag, because vanadium recovery yield drops 4.7-9% as CaO content in the slag increases 1%; (2) high cost due to large consumption amount of sodium salt and ammonium salt; and (3) environment pollution caused by large amount of sodium salt and ammonium salt in wastewater. The roasted material of vanadium extraction process using calcium salt can be leached with sulfuric aid, or with carbonate or bicarbonate.
Germany Patent Application No. 2324737 and British Patent Application No. 1394024 reported a method for leaching calcified roasted material with sodium carbonate solution. US Patent No. 3853985 reported a method for leaching calcified roasted material with ammonium carbonate or ammonium bicarbonate. 'Thermodynamics and kinetics of vanadium slag calcium salt roasting- carbonate leaching" (Vanadium titanium, 1997, No. 6: 1-6) reported thermodynamics and kinetics of leaching the calcified roasted material using carbonate and bicarbonate. Due to use of sodium salt and ammonium slat, the above methods in the literatures also have the problem of ammonia nitrogen wastewater treatment. British Patent Application No. 1394024 also reported a method including leaching roasted material with sulfuric acid or hydrochloric acid, regulating pH of the acidic leachate to 1.6-1.9, heating to hydrolyze and precipitate vanadium, and drying and calcining the precipitate to give vanadium oxide product containing about 93.5% of V2O5 and considerable amount of impurities. "Study of V2O5 extraction process by vanadium slag lime roasting method" (Iron Steel Vanadium Titanium, 1992, 13(6): 1-9) reported the study on V2O5 production by subjecting atomized vanadium slag to calcifying roasting and sulfuric acid leaching, in which the obtained acidic leachate is added with sulfuric acid to regulate pH to 2, and then heated to hydrolyze and precipitate vanadium to give product with purity of 93.6-93.92%. "Study of V2O5 extraction by vanadium slag calcium salt roasting- sulfuric acid leaching" reported study of calcifying roasting and sulfuric acid leaching of vanadium slag . Tula Vanadium Plant of former Soviet Union constructed the world first (also the only one) vanadium manufacture plant adopting calcifying roasting-sulfuric acid leaching- vanadium hydrolysis precipitation process, which can give V2O5 product with purity of 88-94% (92% on average) and containing main impurities of Mn, Mg, and Ca, and then V2O5 product is smelted into vanadium iron also containing many impurities; therefore the manufacturer is non-competitive on international market, and mainly supplies product to domestic market, that is the main reason that other vanadium plants do not adopt this process. To improve product competivity on market, Russian patent application Nos. 2001127026/02 and 96106854/02 disclosed method for producing high quality vanadium oxide from hydrolysis precipitate containing Mn, Ca, and Mg impurities. The method comprises adopting NaOH to dissolve hydrolysis precipitate, then adding ammonium salt like ammonium sulfate while heating, precipitating ammonium polyvanadate, and calcining to give high quality vanadium oxide with V2O5 content higher than 98%. The method reduces total amount of ammonia-containing wastewater, but still requires wastewater treatment including ammonia removal and sodium removal; therefore the technical and economic difficulties of high cost
and difficult ammonia nitrogen wastewater treatment still exist, additionally, vanadium recovery rate is lowered to some extent due to long treatment process and complicated procedures.
Until now, there's no relevant report regarding process which can not only give high quality vanadium product, but also completely solve the problem of vanadium extraction wastewater treatment and reuse. Summary of the invention
The object of the present invention is to provide a clean vanadium oxide production method which can not only obtain high quality vanadium product but also circulate and reuse vanadium extraction wastewater.
The vanadium oxide production method in the present invention comprises following steps including: a. mixing vanadium-containing material with additive to give mixed material, wherein the additive is CaO or limestone, and the amount of the additive makes the CaCVV2O5 weight ratio in the mixed material be 0.5-1.4 : 1; b. roasting the mixed material at 860°C-950°C in oxidizing atmosphere for 60-240min to give roasted material; c. adding water into the roasted material to give slurry, stirring, and slowly adding sulfuric acid solution to leach the slurry while controlling pH at 2.5-3.5; d. removing residue after leaching to give leachate, subjecting the leachate to P-removal treatment to make weight ratio of total V to P (hereinafter referred to as TV/P) in the leachate >1000, washing the residue with circulation water to give washing water useful for preparing slurry in next leaching; e. adding ammonium salt in the P-removed leachate to make weight ratio of NH3/Mn in the leachate be 0.3-3.0 : 1 (the vanadium -containing material usually contains an amount of
Mn), regulating pH of the solution with sulfuric acid to 1.5-2.5, heating to a temperature between 90 °C and boiling temperature, holding at the temperature for 30-120min, filtering, and washing and drying the precipitate to give ammonium polyvanadate; f. subjecting the ammonium polyvanadate to calcination to remove ammonia to give V2O5, or reducing the ammonium polyvanadate to give V2O3; and g. removing P, Mn, and Mg impurities in the wastewater generated in step e to make Mn2+ and Mg2+concentrations lower than 5g/L respectively, and P concentration lower than
0.005g/L to give circulation water, and returning the circulation water to step c for preparing slurry and to step d for washing the residue, wherein the solid raw material used in the above steps has total alkali metal amount not more than 0.3wt%, and total amount of Cl and NO3 not more than 0.1wt%; and the liquid raw material used in the above steps has total alkali metal amount not more than O.lg/L, and total amount of Cl and NO3 not more than O.lg/L.
According to the present invention, wastewater can be circulated and reused; and in addition, as the inventive method adopts calcifying roasting and sulfuric acid leaching to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, balance of the easily soluble ions can be maintained during circulation process, wastewater can be circulated and reused after treatment, and thus problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided. In step a, the vanadium -containing material can be various vanadium-containing raw materials useful for preparing vanadium oxide, such as vanadium slag or other vanadium-containing raw materials (such as vanadium-containing magnetite, and vanadium lead zinc ore, etc.), preferably vanadium slag.
Preferably, in step a, the mixed material is pulverized to particle size of 0.1mm or less, to make vanadium be easily oxidized into V5+ to generate vanadate. In step b, the oxidizing atmosphere can be pure oxygen, air, or mixture of oxygen and inert gas. The inert gas is preferably nitrogen gas. During roasting, appropriate roasting temperature and time can be selected within the range in the present invention, for example when the roasting temperature is high (such as 9500C), the roasting time can be shortened (such as 60min), and when the roasting temperature is low (such as 8600C), the roasting time can be prolonged (about 240min).
Preferably, in step c, the roasted material is cooled and pulverized to 0.18mm or less to facilitate leaching before being prepared into slurry.
Preferably, in step c, the slurry is prepared by stirring the roasted material with water 1.5-4 times by weight. The adopted water is the washing water resulted from the residue washing, and if the washing water is insufficient, circulation water is adopted for supplement. The
sulfuric acid solution for leaching has concentration of 10-75%, the leaching temperature is between room temperature and 580C, and the leaching time is 30-90min. More preferably, pH of the slurry is regulated to 2.8-3.3 with 32-65wt% sulfuric acid solution. During washing the residue, the washing times are preferably 5-7, the amount of water used for each washing is preferably 20-35wt% of the residue on dry basis, to maintain water balance in circulation process.
P-removal reagent can be adopted for P-removal treatment, as long as TWP ^ 1000 is satisfied. In step e, the ammonium salt is preferably ammonium sulfate, ammonium bisulfate, ammonium carbonate, or ammonium bicarbonate. The circulation water obtained from treated wastewater after vanadium precipitation contains ammonium salt, when circulation water containing sulfate salt such as (NH4)2Sθ4 is adopted for leaching within the leaching condition range in the present invention, NH4+ has no adverse influence, and SO4 2" is beneficial for improving leaching rate of calcified roasted material. As Cl- and NO3- usually are easily soluble substances which are difficult to discharge and will affect product quality, and Cl- and NO3- in the circulation water have to be removed before using the circulation water, but Cl — and NO3 — removal is difficult and involves high cost, ammonium chloride and ammonium nitrate can not be used. In step e, when weight ratio of NH3/Mn is low, the precipitation time will be prolonged, but high quality vanadium product can be obtained; and when weight ratio of NH3ZMn is high, precipitation will be finished quickly, energy consumption can be significantly reduced, and product yield will be increased; therefore for overall effect, the amount of the added ammonium salt makes weight ratio of NH3/Mn in the leachate preferably within 0.7-1.0:1. As the returned circulation water contains a certain amount of NH4+, if the weight ratio of NH3/Mn in the P-removed leachate already satisfies above requirement, ammonium salt is not added, and vanadium precipitation is directly carried out.
Preferably, in step e, the water washing of the precipitate is carried out for 2-4 times, and the amount of water used for each washing is 25-40wt% of the precipitate on dry basis. In step g, the wastewater can be treated according to various routine methods to remove P, Mn, and Mg, for example, lime milk is adopted to neutralize wastewater to pH 9-11, the
wastewater is filtered to remove main impurities such as Mn, P, and Mg while obtaining wastewater neutralization residue useful as raw material for Mn recovery; or Mn can be individually recovered with other reagents, and then impurities like P and Mg are removed. The present invention has following beneficial effects: 1. The inventive method adopts calcifying roasting and sulfuric acid leaching technique to give vanadium solution substantially free of alkali metal ions, and various raw materials (including supplement water) are substantially free of easily soluble ions of alkali metal, halogen, and nitrate, so that balance of the easily soluble ions can be maintained during circulation, and problems of wastewater treatment of conventional vanadium extraction process using sodium salt are avoided.
2. Ammonium salt is adopted to prepare high quality vanadium oxide product, so that technical problem that conventional calcifying roasting- sulfuric acid leaching process can not produce high quality vanadium product is solved.
3. Weight ratio of NH3ZMn is controlled to control product quality and ammonium concentration in the solution, when the ratio in the leachate is lower than the value specified in the present invention, ammonium salt is added to regulate the ratio to the specified value, and then the vanadium precipitation is carried out; when the ratio in the leachate has already reached the specified value in the present invention, ammonium salt is not added, and vanadium precipitation is directly carried out, and part of NH4 + is discharged along with ammonium polyvanadate precipitate, so that NH4 + concentration in the system will not continuously increase to enable circulation and reuse.
4. The circulation water containing sulfate salt such as (NH4)2SO4 is adopted for leaching; within the leaching condition range in the present invention, NH4 + will not cause adverse influence, and SO4 " is beneficial for increasing leaching rate of calcified roasted material, so that water circulation and reuse can be finally realized.
5. The inventive method can greatly increase total recovery rate (up to 85-88%) of vanadium oxide from vanadium slag, while the recovery rate of the conventional vanadium extraction process using sodium salt is about 80%; therefore the inventive method has increased the recovery rate by 5-8% on average compared with conventional vanadium extraction process using sodium salt, and the obtained vanadium product has good quality, and meets Chinese National Standard No. GB3283-87.
6. The inexpensive lime material is adopted to replace expensive sodium carbonate, the
consumption amount of sulfuric acid is similar to that in the vanadium extraction process using sodium salt, and NH4 + is almost completely consumed to precipitate vanadium while most ammonia in wastewater of conventional vanadium extraction process using sodium salt is lost in wastewater treatment; therefore, consumption and cost of various auxiliary and raw materials are significantly decreased.
Brief Description of Drawings
Fig. 1 shows flow chart of one preferred embodiment of the method in the present invention.
Preferred Embodiments
The present invention will be further described through following examples.
The following examples all adopt the flow as shown in the Fig. 1. The preferred examples are briefly described in combination with Fig. 1.
Firstly, vanadium slag and lime is mixed to give mixed material (equivalent to step a); The mixed material is calcified and roasted (equivalent to step b);
Sulfuric acid solution is adopted to leach the roasted material at constant pH (equivalent to step c);
After leaching, residue and leachate are separated out, the residue is washed with diluted suUimc acid solution of pH 3 -6, and the washing water is collected for preparing slurry (equivalent to step d);
Ammonium salt and sulfuric acid are added into the leachate to precipitate vanadium
(equivalent to step e);
Ammonium polyvanadate obtained from vanadium precipitation is calcined or reduced to give high quality vanadium oxide (equivalent to step f); The wastewater obtained from vanadium precipitation is added with lime milk for neutralization, the obtained circulation water is returned to prepare slurry or wash residue, and
Mn is recovered from the neutralization residue (equivalent to step g).
Example 1 Roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes
steps (2)-(5).
(1) Preparation of roasted material:
Common vanadium slag with composition shown in Table 1 is ground to less than 0.098mm, 28kg of ground vanadium slag powder is mixed with 1.96kg of lime (ground to below 0.1mm) containing CaO>98%, and then the mixture is roasted at 860 °C in air for 240min, cooled, and ground to less than 0.18mm.
Table 1 Main components of vanadium slag (%)
(2) Leaching of roasted material
2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 50Og of the ground roasted material to prepare slurry, 10-32wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58°C, the reaction is carried out for 60min. The resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6-7 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate. The leachate is subjected to P-removal treatment to make P satisfy TV/P>1000, and the vanadium precipitation procedure is carried out. (3) Vanadium precipitation
Ammonium sulfate is added into the P-removed leachate to make NIHb/Mn weight ratio of the solution within 0.3-0.9, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 90 °C, held for 60-120min, and filtered, the precipitate is washed with tap water containing [Na+K]<0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation. (4) V2O5 production by calcination
Ammonium polyvanadate precipitate is dried, calcined and melted at 500°C-800°C to give V2O5, and the composition of the obtained V2O5 is analyzed. (5) Wastewater treatment
Lime milk with low water content is prepared, added into the wastewater of vanadium
precipitation to regulate pH of the solution to 9.0-10.0, and filtered. The filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle. The neutralization residue obtained from the filtration is used as raw material for Mn recovery. The above steps (2)-(5) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 4:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
Except the first cycle without vanadium precipitation, the maximum value, the minimum value, and the average value of the recovery rate of the rest cycles are shown in Table 2; the maximum value, the minimum value, and the average value of the chemical compositions of the V2O5 product of the rest cycles are shown in Table 3, and the Table 3 also shows compositions of the metallurgical No. 98 and No. 99 of Chinese National Standard No. GB3283-87; and the maximum value, the minimum value, and the average value of the composition of the circulation water after circulation treatment for the rest cycles are shown in Table 4.
Table 2 Vanadium recovery rate in circulation process (%)
The recovery rates of the raw material pretreatment and ammonia removal by calcination in the above Table 2 are obtained from long term industrial production data.
Note: The procedure of raw material pretreatment includes pulverization of bulk coarse vanadium slag, grinding, and iron removal, and a small amount of vanadium is lost in this process.
It can be observed from Table 2 that the total average recovery rate of V2O5 from vanadium slag reaches 88.40% by the inventive method.
Table 3 Main components OfV2Os product obtained by the circulation process(%)
The table 3 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
Table 4 Main components of circulation water (g/L)
It can be observed from Table 4 that, after 51 cycles of wastewater circulation, various impurity ions have no enrichment tendency, and circulation and reuse of vanadium extraction wastewater in low cost is realized, wherein K and Na are mainly from vanadium slag raw material, and sum of K+Na in the circulation water is stabilized within 0.2-0.4g/L and does not increase after 51 cycles.
Example 2
Roasted material prepared according to step (1) is adopted, 51 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(5).
(1) Preparation of roasted material: The vanadium slag shown in Table 5 is ground to less than 0.098mm.
Table 5 Main components of vanadium slag (%)
28kg of ground vanadium slag powder is mixed with 1.82kg of lime (ground to below 0.1mm) containing 98% CaO, and then the mixture is roasted at 950 °C in air for 60min, cooled, and ground to less than 0.18mm.
(2) Leaching of roasted material
1250ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 50Og of the ground roasted material to prepare slurry, 32-65wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room
temperature-58°C, the reaction is carried out for 60min. The resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 6 times, water used for each time is 120ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate. The leachate is subjected to P-removal treatment to make P satisfy TV/P≥IOOO, and the vanadium precipitation procedure is carried out.
(3) Vanadium precipitation Ammonium sulfate is added into the P-removed leachate to make NIHb/Mn weight ratio of the solution within 0.6-3.0, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 900C, held for 60-90min, and filtered, the precipitate is washed with tap water containing [Na+K]<0.1g/L for 3 times and water used for each time is 30ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation. (4) V2Os production by calcination
Ammonium polyvanadate precipitate is dried, calcined and melted at 500°C-800°C to give
V2O5, and V2O5 composition is analyzed.
(5) Wastewater treatment
Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-9.5, and filtered. The filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for leaching in the next cycle. The neutralization residue obtained from the filtration is used as raw material for Mn recovery. The above steps (2)-(5) are repeated, 50Og of roasted material is used for each cycle, liquid solid ratio for each cycle is 4:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 51 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
Except the first cycle without vanadium precipitation, the maximum value, the minimum value, and the average value of the recovery rate of the rest cycles are shown in Table 6; the
maximum value, the minimum value, and the average value of the chemical compositions of the V2Os product of the rest cycles are shown in Table 7; and the maximum value, the minimum value, and the average value of the composition of the circulation water after circulation treatment for the rest cycles are shown in Table 8.
Table 6 Vanadium recovery rate in circulation process (%)
The recovery rates of the raw material pretreatment and ammonia removal by calcination in the above Table 6 are obtained from long term industrial production data. It can be observed from Table 6 that the total average recovery rate of V2O5 from vanadium slag reaches 87.21% by the inventive method.
Table 7 Main components of V2Os product obtained by the circulation process (%)
The table 7 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
Table 8 Main components of circulation water (g/L)
It can be observed from Table 8 that, after 51 cycles of wastewater circulation, various impurity ions have no enrichment tendency, and circulation and reuse of vanadium extraction wastewater in low cost is realized, wherein K and Na are mainly from vanadium slag raw material, and sum of K+Na in the circulation water is stabilized within 0.2-0.4g/L and does not increase after 51 cycles.
Example 3
Roasted material prepared according to step (1) is adopted, 100 cycles of wastewater circulation test are carried out according to the inventive method, and each cycle includes steps (2)-(5).
(1) Preparation of roasted material:
110kg of vanadium slag with composition shown in Table 9 is ground to less than 0.098mm, the ground vanadium slag powder is mixed with 7.7kg of lime (ground to below 0.1mm) containing 98% CaO, and then the mixture is roasted at 920 °C in air for 150min, cooled, and ground to less than 0.18mm.
Table 9 Main components of vanadium slag (%)
(2) Leaching of roasted material
2,000ml of water resulted from residue washing of last cycle (clear water is used for the first cycle) is added to 1,00Og of ground roasted material to prepare slurry, 50-75wt% sulfuric acid solution is slowly added continuously while stirring, pH is controlled at 2.8-3.3 during leaching process while the slurry temperature is held at a temperature between room temperature and 58°C, the reaction is carried out for 60min. The resultant is filtered to give leachate, the residue is washed with circulation water (clear water is used for the first cycle) for 5-6 times, water used for each time is 250ml, the washing water is combined for preparing slurry for leaching of next cycle, and the residue is dried and weighed to determine TV (total vanadium) content and calculate vanadium leaching rate. The leachate is subjected to P-removal treatment to make P satisfy TV/P>1000, and the vanadium precipitation procedure is carried out.
(3) Vanadium precipitation Ammonium sulfate is added into the P-removed leachate to make NH3ZMn weight ratio of the solution within 0.7-0.9, a small amount of sulfuric acid is used to regulate pH to 1.5-2.5, then the resultant is heated to above 900C, held for 30-60min, and filtered, the precipitate is washed with tap water containing [Na+K]<0.1g/L for 3 times and water used for each time is 60ml, and the washing wastewater is combined with supernatant of vanadium precipitation to give wastewater of vanadium precipitation.
(4) V2O5 production by calcination
Ammonium polyvanadate precipitate is dried, calcined and melted at 500°C-800°C to give V2O5, and V2O5 composition is analyzed.
(5) Wastewater treatment Lime milk with low water content is prepared, added into the wastewater of vanadium precipitation to regulate pH of the solution to 9.0-10.0, and filtered. The filtrate is regulated to pH of 5-7 with diluted sulfuric acid to give circulation water as residue washing water for
leaching in the next cycle. The neutralization residue obtained from the filtration is used as raw material for Mn recovery.
The above steps (2)-(5) are repeated, lOOOg of roasted material is used for each cycle, liquid solid ratio for each cycle is 2:1, vanadium precipitation is not carried out after leaching in the first cycle, the leachate is used for slurry preparation of the second cycle to increase vanadium concentration of the leachate; then during leaching in each of the rest cycles, residue washing water of last cycle is used in step (2), and the insufficient part is supplemented by circulation water; circulation water is used for washing the residue, and the insufficient part is supplemented by clear water. 100 cycles are carried out, and no wastewater containing ammonia nitrogen is discharged from the system.
Except the first cycle without vanadium precipitation, the maximum value, the minimum value, and the average value of the recovery rate of the rest cycles are shown in Table 10; the maximum value, the minimum value, and the average value of the chemical compositions of the V2O5 product of the rest cycles are shown in Table 11; and the maximum value, the minimum value, and the average value of the composition of the circulation water after circulation treatment for the rest cycles are shown in Table 12.
Table 10 Vanadium recovery rate in circulation process (%)
The recovery rates of the raw material pretreatment and ammonia removal by calcination in the above Table are obtained from long term industrial production data. It can be observed from Table 10 that the total average recovery rate of V2Os from vanadium slag reaches 86.39% by the inventive method.
Table 11 Main components of V2O5 product obtained by the circulation process(%)
The table 11 shows that the vanadium product obtained by the process has good product quality, and meets Chinese National Standard No. GB3283-87.
Table 12 Main components of circulation water (g/L)
It can be observed from Table 12 that, after 100 cycles of wastewater circulation, various impurity ions have no enrichment tendency, and circulation and reuse of vanadium extraction wastewater in low cost is realized, wherein K and Na are mainly from vanadium slag raw material, and sum of K+Na in the circulation water is stabilized within 0.2-0.4g/L and does not increase after 100 cycles.
Claims
1. A production method of vanadium oxide, comprising the following steps: a. mixing vanadium-containing material with additive to give mixed material, wherein the additive is CaO or limestone, and the amount of the additive makes the CaCVV2Os weight ratio in the mixed material be 0.5-1.4 : 1; b. roasting the mixed material at 860°C-950°C in oxidizing atmosphere for 60-240min to give roasted material; c. adding water into the roasted material to give slurry, stirring, and slowly adding sulfuric acid solution to leach the slurry while controlling pH at 2.5-3.5; d. removing residue after leaching to give leachate, subjecting the leachate to P-removal treatment to make weight ratio of total V to P in the leachate >1000, washing the residue with circulation water to give washing water useful for preparing slurry in next leaching; e. adding ammonium salt in the P-removed leachate to make weight ratio of NH3/Mn in the leachate be 0.3-3.0 : 1, regulating pH of the solution with sulfuric acid to 1.5-2.5, heating to a temperature between 90 °C and boiling temperature, holding at the temperature for 30-120min, filtering, and washing and drying the precipitate to give ammonium polyvanadate; f. subjecting the ammonium polyvanadate to calcination to remove ammonia to give V2O5, or reducing the ammonium polyvanadate to give V2O3; and g. removing P, Mn, and Mg impurities in the wastewater generated in step e to make Mn2+ and Mg2+concentrations lower than 5g/L respectively, and P concentration lower than 0.005g/L to give circulation water, and returning the circulation water to step c for preparing slurry and to step d for washing the residue, wherein the solid raw material used in the above steps has total alkali metal amount not more than 0.3wt%, and total amount of Cl and NO3 not more than 0.1wt%; and the liquid raw material used in the above steps has total alkali metal amount not more than 0.1 g/L, and total amount of Cl and NO3 not more than 0.1 g/L.
2. The production method of vanadium oxide according to claim 1, wherein the mixed material obtained in step a has particle size of 0.1mm or less.
3. The production method of vanadium oxide according to claim 1, wherein in step c, the roasted material is cooled and pulverized to 0.18mm or less before being prepared into slurry.
4. The production method of vanadium oxide according to claim 1, wherein in step c, the concentration of the sulfuric acid solution is 10-75wt%, the leaching temperature is 10-58 °C, and the leaching time is 30-90min.
5. The production method of vanadium oxide according to claim 1, wherein the circulation water obtained in step g is returned to step d to wash the residue to obtain washing water, the washing water is returned to step c for leaching and preparing slurry, if the washing water is not sufficient, the circulation water is adopted for supplement.
6. The production method of vanadium oxide according to claim 1 or 5, wherein in step c, the weight ratio of total amount of water for slurry preparation to the roasted material is 1.5-4 : 1.
7. The production method of vanadium oxide according to claim 1, wherein during washing of the residue, the washing times are 5-7, and the amount of water used for each washing is 20-35wt% of the residue on dry basis.
8. The production method of vanadium oxide according to claim 1, wherein in step e, the amount of the added ammonium salt makes weight ratio of NIHb/Mn in the leachate within 0.7-1.0 : 1.
9. The production method of vanadium oxide according to claim 1 or 8, wherein in step e, the ammonium salt is ammonium sulfate, ammonium bisulfate, ammonium carbonate, or ammonium bicarbonate.
10. The production method of vanadium oxide according to claim 1, wherein in step e, the water for washing the precipitate is tap water or production water, the washing times are 2-4, and the amount of water used for each washing is 25-40wt% of the precipitate on dry basis.
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| RU2175681C1 (en) * | 2000-08-30 | 2001-11-10 | ОАО "Чусовской металлургический завод" | Method for production of vanadium pentaoxide from man-made raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104843789A (en) * | 2015-04-30 | 2015-08-19 | 河北钢铁股份有限公司承德分公司 | Method for purifying vanadium pentoxide |
| CN105219974A (en) * | 2015-11-05 | 2016-01-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of raising vanadium slag V 2o 5the method of content |
| CN105969984A (en) * | 2016-05-16 | 2016-09-28 | 武汉理工大学 | Preparation method of vanadium trioxide |
| CN113737025A (en) * | 2021-07-23 | 2021-12-03 | 中南大学 | Efficient vanadium extraction method and efficient vanadium extraction device for high-silicon refractory stone coal vanadium ore |
| CN114350963A (en) * | 2021-11-29 | 2022-04-15 | 攀钢集团研究院有限公司 | Recycling method of calcified vanadium extraction tailings |
| CN114350963B (en) * | 2021-11-29 | 2024-02-23 | 攀钢集团研究院有限公司 | Recycling method of calcified vanadium extraction tailings |
| CN114644357A (en) * | 2022-03-11 | 2022-06-21 | 万循材料科技有限公司 | Method for preparing ammonium metavanadate by sodium modification vanadium extraction combined alkali preparation and low-cost vanadium slag utilization |
| CN116005028A (en) * | 2022-12-30 | 2023-04-25 | 四川省银河化学股份有限公司 | Method for preparing vanadium alloy from calcium vanadate |
| CN116005028B (en) * | 2022-12-30 | 2023-11-03 | 四川省银河化学股份有限公司 | Method for preparing vanadium alloy from calcium vanadate |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201006530B (en) | 2011-10-26 |
| NZ587969A (en) | 2012-12-21 |
| RU2010143127A (en) | 2012-04-27 |
| CN101412539B (en) | 2010-12-08 |
| RU2454369C1 (en) | 2012-06-27 |
| CN101412539A (en) | 2009-04-22 |
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