CN116837230A - Method for cleaning vanadium slag and extracting vanadium and application thereof - Google Patents
Method for cleaning vanadium slag and extracting vanadium and application thereof Download PDFInfo
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- CN116837230A CN116837230A CN202310446044.6A CN202310446044A CN116837230A CN 116837230 A CN116837230 A CN 116837230A CN 202310446044 A CN202310446044 A CN 202310446044A CN 116837230 A CN116837230 A CN 116837230A
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- vanadium
- sodium
- mother liquor
- chromium
- leaching
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 113
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000002893 slag Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004140 cleaning Methods 0.000 title abstract description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 88
- 239000012452 mother liquor Substances 0.000 claims abstract description 85
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 45
- 239000011734 sodium Substances 0.000 claims abstract description 45
- 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 abstract description 44
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 44
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 44
- 238000002386 leaching Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001556 precipitation Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims abstract description 19
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 15
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 55
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052804 chromium Inorganic materials 0.000 claims description 24
- 239000011651 chromium Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000292 calcium oxide Substances 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 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 abstract description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 10
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910001199 N alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for cleaning vanadium slag and extracting vanadium and application thereof. The method comprises the following steps: mixing vanadium slag and sodium salt, sintering, adding roasting clinker, water, chromium-removing mother liquor and impurity-removing slag, leaching to obtain tailings and leaching liquor, removing impurities from the leaching liquor to obtain purifying liquid, and carrying out precipitation treatment on the purifying liquid to obtain vanadium-precipitating mother liquor and calcium vanadate; adding a first reducing agent into the vanadium precipitation mother liquor to obtain chromium hydroxide, and calcining to obtain chromium oxide; leaching vanadium from the calcium vanadate, carbon dioxide, crystallization mother liquor and calcined tail gas to obtain a calcium salt and sodium vanadate solution, evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, reducing the sodium metavanadate, an auxiliary agent and a second reducing agent at high temperature to obtain a reduction clinker, and removing sodium from the reduction clinker, sodium bicarbonate mother liquor and water to obtain vanadium trioxide. The invention successfully prepares the chromium oxide and vanadium oxide products, and realizes the high-value utilization of the high-chromium vanadium slag.
Description
Technical Field
The invention belongs to the technical field of metallurgical chemical industry, and particularly relates to a method for cleaning vanadium slag and extracting vanadium and application thereof.
Background
Vanadium is an important rare metal element, and main products thereof comprise vanadium pentoxide, vanadium trioxide, vanadium-nitrogen alloy, ferrovanadium alloy, vanadium-aluminum alloy and the like. Vanadium is widely used in aviation, chemical industry, metallurgy, steel and other industries because of its advantages such as anti-fatigue effect, excellent hardness and strength. The current vanadium slag vanadium extraction occupies 80% of the total industry, wherein 90% is the sodium-modified vanadium extraction technical route. The key point of preparing vanadium oxide by using vanadium slag as raw material is separation of vanadium and sodium. The traditional method realizes the separation of vanadium and sodium based on the combination difference of sodium and ammonium and vanadate, so as to prepare vanadium oxide, but the method is also a root causing serious three wastes pollution in the current vanadium industry.
CN109930008A discloses a method for extracting vanadium from vanadium slag. Mixing and roasting vanadium slag and a magnesium compound, carrying out acid leaching on roasting clinker by sulfuric acid, carrying out vanadium precipitation on ammonium salt, and roasting to obtain vanadium pentoxide; and (3) respectively precipitating manganese hydroxide and magnesium hydroxide by introducing ammonia water into the vanadium precipitation liquid, calcining the magnesium hydroxide into magnesium oxide, and returning vanadium slag for roasting. The method uses magnesium salt to replace sodium salt, avoids the generation of sodium sulfate wastewater, but generates more ammonia nitrogen-containing wastewater and ammonia tail gas.
CN106544515a discloses a method for extracting vanadium from vanadium slag, which comprises the following specific steps: spraying an aqueous solution of an alkali metal-containing alkaline substance into vanadium slag under the condition of first heating and stirring to obtain a mixture, and sequentially carrying out second heating and stirring and water leaching on the mixture to extract vanadium; wherein the temperature of the first heating and stirring is 80-120 ℃; the temperature of the second heating and stirring is 500-750 ℃. However, the method only obtains vanadium leaching solution, the subsequent vanadium product obtaining still needs to pass through the traditional process, and the mixing process of vanadium slag and alkali liquor has very high requirements on equipment.
CN112080651a discloses a method for extracting vanadium by high-calcium low-sodium ammonium composite roasting, which comprises the steps of uniformly mixing vanadium slag with limestone, sodium-containing compounds and ammonium salt in proportion, roasting, leaching, washing and filtering to obtain vanadium leaching solution and residues, and then precipitating vanadium with ammonium salt and calcining to obtain vanadium pentoxide. Although the method improves the recovery rate of vanadium, ammonium salt can be decomposed to generate ammonia gas during roasting, a new pollution source is added, and vanadium precipitation wastewater contains a large amount of ammonia nitrogen and sulfur, so that the environmental pollution is serious.
CN114854988A discloses a method for utilizing CO 2 The method for selectively separating vanadium and chromium in the vanadium-chromium material utilizes carbon dioxide to selectively oxidize vanadium in the vanadium-chromium-containing raw material to realize vanadium-chromium separation, and comprises the following specific steps: mixing the vanadium-chromium material and carbonate uniformly, briquetting, putting into a shaft furnace, introducing carbon dioxide for roasting, cooling, crushing, dissolving to obtain vanadium-containing solution and chromium-containing residues, recovering vanadium from the vanadium-containing solution by a precipitation method, and preparing the chromium alloy from the chromium-containing residues. The vanadium is oxidized and partial chromium is oxidized at the same time, and the oxidized chromium can enter products and wastewater, so that the quality of the products is reduced, and the difficulty of wastewater treatment is increased. The method also has high ammonia nitrogen and high sulfur waste water and ammonia-containing tail gas.
Therefore, most technicians input a great deal of research on the vanadium extraction technology of vanadium slag at present, but the discharge problem of high-salt high-ammonia nitrogen wastewater and ammonia-containing waste gas is not solved. Therefore, a novel method for extracting vanadium from sulfur-free and ammonium-free vanadium slag is developed, and the reduction of three-waste emission is a problem which needs to be solved by the person skilled in the art at present.
Disclosure of Invention
The invention aims to provide a method for cleaning vanadium slag and extracting vanadium and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention aims to provide a method for cleanly extracting vanadium from vanadium slag, which comprises the following steps of:
(1) Mixing vanadium slag and sodium salt, sintering, adding roasting clinker, water, chromium-removing mother liquor and impurity-removing slag, leaching to obtain tailings and leaching liquor, removing impurities from the leaching liquor to obtain purifying liquid, and carrying out precipitation treatment on the purifying liquid to obtain vanadium-precipitating mother liquor and calcium vanadate;
(2) Adding a first reducing agent into the vanadium precipitation mother liquor in the step (1) to obtain chromium hydroxide, and calcining to obtain chromium sesquioxide;
(3) Leaching vanadium from the calcium vanadate, carbon dioxide, crystallization mother liquor and calcined tail gas in the step (1) to obtain a calcium salt and sodium vanadate solution, evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, reducing the sodium metavanadate, an auxiliary agent and a second reducing agent at high temperature to obtain a reduction clinker, and removing sodium from the reduction clinker, sodium bicarbonate mother liquor and water to obtain vanadium trioxide.
According to the method provided by the invention, the separation of vanadium and sodium is completed according to the solubility difference between vanadium and chromium and sodium salt and calcium salt, and the chromium trioxide and vanadium trioxide products are successfully prepared by introducing a reducing agent and an auxiliary agent, so that the high-value utilization of high-chromium vanadium slag is realized. Compared with the traditional method, the method eliminates the introduction of sulfur and ammonium, avoids the generation of high-salt and high-ammonia nitrogen wastewater from the source, and realizes zero discharge of wastewater and solid waste through closed circulation of sodium salt and a transforming agent. In addition, the whole system does not produce ammonia-containing waste gas. The whole process has the advantages of simple operation, high conversion rate and low cost, the required equipment is conventional equipment in the chemical industry field, the industrial process is easy to realize, and the economic and environmental benefits are obvious.
As a preferable technical scheme of the invention, the sodium salt in the step (1) is sodium carbonate and/or sodium bicarbonate.
Preferably, the sintering temperature in step (1) is 700 to 1100 ℃, wherein the temperature may be 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the molar ratio of total sodium to total vanadium in the reaction system in the sintering in the step (1) is controlled to be (1-1.4): 1, wherein the molar ratio can be 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1, and the like, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, the mass ratio of the water and the baked clinker in the step (1) is (1-3): 1, wherein the mass ratio can be 1:1, 2:1 or 3:1, etc., but is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
As a preferred technical scheme of the present invention, the removing impurities in the step (1) includes: adding calcium oxide into the leaching solution to remove impurities, thereby obtaining impurity-removed slag and purifying liquid.
Preferably, in the impurity removal, calcium oxide (p+si) = (2 to 4): 1, wherein the calcium oxide (p+si) may be 2:1, 3:1 or 4:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the impurity removing slag is returned to the step (1) for recycling.
As a preferred embodiment of the present invention, the precipitation treatment in step (1) includes: and adding calcium oxide to the purifying liquid to precipitate vanadium, so as to obtain vanadium precipitation mother liquor and calcium vanadate.
Preferably, the molar ratio of total calcium to total vanadate in the reaction system in the precipitation treatment in the step (1) is controlled to be (1-1.4): 1, wherein the molar ratio can be 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
According to the preferred technical scheme, carbon dioxide is introduced into the vanadium precipitation mother liquor in the step (2) to recover sodium bicarbonate, so as to obtain sodium bicarbonate mother liquor, and a reducing agent is added into the sodium bicarbonate mother liquor, so as to obtain chromium oxide and chromium removal mother liquor.
Preferably, the pH of the solution at the time of recovering the sodium bicarbonate is 7.0 to 9.0, wherein the pH may be 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8 or 9.0, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the first reducing agent comprises any one or a combination of at least two of formic acid, oxalic acid, formaldehyde, hydrazine hydrate, methanol or ethanol, wherein typical but non-limiting examples of the combination are: a combination of formic acid and oxalic acid, a combination of oxalic acid and formaldehyde, a combination of formaldehyde and hydrazine hydrate, a combination of hydrazine hydrate and methanol or a combination of methanol and ethanol, and the like.
Preferably, the chromium-removing mother liquor is returned to the step (1) for recycling.
Preferably, the temperature of the calcination in the step (2) is 900 to 1600 ℃, wherein the temperature may be 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
In the preferred embodiment of the present invention, the pH of the solution is controlled to 9.0 to 10.0 in the leaching in the step (3), wherein the pH may be 9.0, 9.2, 9.4, 9.6, 9.8 or 10.0, etc., but the present invention is not limited to the listed values, and other non-listed values within the range are equally applicable.
Preferably, the calcium salt in the step (3) returns to the step (1) as a impurity removing agent after being calcined.
As a preferable technical scheme of the invention, the sodium vanadate solution in the step (3) is evaporated and crystallized to obtain sodium metavanadate, condensed water and crystallization mother liquor.
Preferably, the promoter of step (3) comprises any one or a combination of at least two of alumina, aluminium hydroxide or aluminium phosphate, wherein typical but non-limiting examples of such combinations are: a combination of aluminum oxide and aluminum hydroxide, a combination of aluminum hydroxide and aluminum phosphate, or a combination of aluminum oxide and aluminum phosphate, etc.
Preferably, the second reductant of step (3) comprises any one or a combination of at least two of hydrogen, CO, gas or natural gas, wherein typical but non-limiting examples of the combination are: a combination of hydrogen and CO, a combination of CO and gas, a combination of gas and natural gas, or a combination of hydrogen and natural gas, etc.
Preferably, the temperature of the high-temperature reduction in the step (3) is 600 to 900 ℃, wherein the temperature may be 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the molar ratio of total aluminum to total sodium in the high temperature reduction in step (3) is controlled to be (1-1.4): 1, wherein the molar ratio can be 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
According to the preferred technical scheme, the reduced clinker, the sodium bicarbonate mother solution and the water in the step (3) are subjected to sodium removal to obtain vanadium trioxide and sodium removal solution.
Preferably, in the sodium removal process, the mass ratio of the control water to the reduced clinker is (2-5): 1, wherein the mass ratio can be 2:1, 3:1, 4:1 or 5:1, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, carbon dioxide is introduced into the sodium removal solution to control the pH to 10.0-12.0, wherein the pH can be 10.0, 10.2, 10.4, 10.6, 10.8, 11.0, 11.2, 11.4, 11.6, 11.8 or 12.0, but not limited to the recited values, and other non-recited values in the range are equally applicable to obtain the auxiliary agent and the auxiliary agent mother liquor.
Preferably, carbon dioxide is continuously introduced into the auxiliary agent, and the pH is controlled to be 7.0-9.0, wherein the pH can be 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8 or 9.0, and the like, but the auxiliary agent is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, so that sodium bicarbonate and sodium bicarbonate mother solution are obtained.
Preferably, the sodium bicarbonate is returned to step (1) as a impurity removing agent.
Preferably, the sodium bicarbonate mother liquor is returned to the step (3) to participate in sodium removal.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Mixing vanadium slag and sodium salt, sintering at 700-1100 ℃, adding roasting clinker, water, chromium-removing mother liquor and impurity-removing slag, leaching, controlling the mole ratio of total sodium and total vanadium in a reaction system to be (1-1.4): 1, obtaining tailings and leaching liquid, removing impurities from the leaching liquid to obtain purifying liquid, and performing precipitation treatment on the purifying liquid to obtain vanadium-precipitating mother liquor and calcium vanadate, wherein the mole ratio of total calcium and total vanadate in the reaction system is controlled to be (1-1.4): 1 in the precipitation treatment;
(2) Adding a first reducing agent into the vanadium precipitation mother liquor in the step (1) to obtain chromium hydroxide, and calcining to obtain chromium sesquioxide;
(3) Leaching vanadium from the calcium vanadate, carbon dioxide, crystallization mother liquor and calcined tail gas in the step (1) to obtain a calcium salt and sodium vanadate solution, evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, reducing the sodium metavanadate, the auxiliary agent and the second reducing agent at a high temperature of 600-900 ℃ to obtain reduced clinker, and removing sodium from the reduced clinker, sodium bicarbonate mother liquor and water to obtain vanadium trioxide.
The second purpose of the invention is to provide an application of the method for cleanly extracting vanadium from vanadium slag, which is applied to the technical field of metallurgical chemical engineering.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method provided by the invention directly converts the high-chromium vanadium slag into high-valued chromium trioxide and vanadium trioxide products. The invention does not need the introduction of sulfur and ammonium, avoids the generation of high-salt and high-ammonia nitrogen wastewater from the source, and realizes the zero discharge of wastewater and solid waste through the closed circulation of sodium salt and a transforming agent. In addition, the whole system does not produce ammonia-containing waste gas. The whole process has the advantages of simple operation, high conversion rate and low cost, the required equipment is conventional equipment in the chemical industry field, the industrial process is easy to realize, and the economic and environmental benefits are obvious.
(2) The product obtained by the method has high purity, the purity of the chromium oxide product meets the requirements of class I qualified products in HG/T2775-2010, and the purity of the vanadium oxide product meets the brand V in GB/T40301-2021 2 O 3 66.
Drawings
FIG. 1 is a flow chart of a method for cleaning and extracting vanadium from vanadium slag in examples 1-10 of the invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for cleaning vanadium slag and extracting vanadium, which is shown in a flow chart of fig. 1, and comprises the following steps:
(1) Roasting vanadium slag and sodium salt at 1000 ℃, controlling the molar ratio of total sodium to total vanadium in a reaction system to be 1.1:1, mixing roasting clinker, water, chromium removal mother liquor, vanadium precipitation mother liquor and impurity removal slag, and carrying out vanadium-chromium leaching, wherein the mass ratio of water to roasting clinker is 2:1, obtaining tailings and leaching liquid; adding calcium oxide into the leaching solution to remove impurities, wherein the mass ratio of the calcium oxide is as follows: (p+si) =3: 1, obtaining impurity-removed slag and purifying liquid, returning the impurity-removed slag to the step (1), adding calcium oxide into the purifying liquid to precipitate vanadium, and controlling the molar ratio of total calcium to total vanadate in a reaction system to be 1.2:1 to obtain vanadium-precipitated mother liquor and calcium vanadate;
(2) Introducing carbon dioxide into the vanadium precipitation mother liquor, controlling the pH of the solution to be 8, recovering sodium bicarbonate and returning to the step (1), adding formic acid into the sodium bicarbonate mother liquor to reduce the high-valence chromium in the solution to trivalent chromium to obtain chromium hydroxide and chromium removal mother liquor, returning the chromium removal mother liquor to the step (1), and calcining the chromium hydroxide to obtain chromium sesquioxide;
(3) Mixing calcium vanadate, carbon dioxide, crystallization mother liquor and calcination tail gas to leach vanadium, controlling the PH of the solution to be 9-10 (or separating out calcium in a precipitation form) to obtain calcium salt and sodium vanadate solution, and returning the calcium salt to the step (1) after calcination; evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, condensed water and crystallization mother liquor, mixing sodium metavanadate, aluminum oxide and hydrogen, and reducing at 750 ℃ to obtain reduction clinker, wherein the molar ratio of total aluminum to total sodium in a reaction system is controlled to be 1.1:1; mixing the reduced clinker, sodium bicarbonate mother liquor and water for sodium removal, and controlling the mass ratio of water to the reduced clinker to be 3:1, obtaining vanadium trioxide and sodium removal solution; introducing carbon dioxide into the sodium removal solution, controlling the PH of the solution to be 11, obtaining an auxiliary agent and auxiliary agent mother liquor, continuously introducing carbon dioxide into the auxiliary agent mother liquor, controlling the PH of the solution to be 8, obtaining sodium bicarbonate and sodium bicarbonate mother liquor, returning the sodium bicarbonate to the step (1), and returning the sodium bicarbonate mother liquor for recycling.
Example 2
The embodiment provides a method for cleaning vanadium slag and extracting vanadium, which is shown in a flow chart of fig. 1, and comprises the following steps:
(1) Roasting vanadium slag and sodium salt at 1100 ℃, controlling the molar ratio of total sodium to total vanadium in a reaction system to be 1.2:1, mixing roasting clinker, water, chromium removal mother liquor, vanadium precipitation mother liquor and impurity removal slag, and carrying out vanadium-chromium leaching, wherein the mass ratio of water to roasting clinker is 3:1, obtaining tailings and leaching liquid; adding calcium oxide into the leaching solution to remove impurities, wherein the mass ratio of the calcium oxide is as follows: (p+si) =4: 1, obtaining impurity-removed slag and purifying liquid, returning the impurity-removed slag to the step (1), adding calcium oxide into the purifying liquid to precipitate vanadium, and controlling the molar ratio of total calcium to total vanadate in a reaction system to be 1.1:1 to obtain vanadium-precipitated mother liquor and calcium vanadate;
(2) Introducing carbon dioxide into the vanadium precipitation mother liquor, controlling the pH of the solution to 7.5, recovering sodium bicarbonate and returning to the step (1), adding oxalic acid into the sodium bicarbonate mother liquor to reduce the high-valence chromium in the solution to trivalent chromium to obtain chromium hydroxide and chromium removal mother liquor, returning the chromium removal mother liquor to the step (1), and calcining the chromium hydroxide to obtain chromium sesquioxide;
(3) Mixing calcium vanadate, carbon dioxide, crystallization mother liquor and calcination tail gas to leach vanadium, controlling the PH of the solution to be 9-10 (or separating out calcium in a precipitation form) to obtain calcium salt and sodium vanadate solution, and returning the calcium salt to the step (1) after calcination; evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, condensed water and crystallization mother liquor, mixing sodium metavanadate, aluminum hydroxide and CO, and reducing at 900 ℃ to obtain reduction clinker, wherein the molar ratio of total aluminum to total sodium in a reaction system is controlled to be 1.2:1; mixing the reduced clinker, sodium bicarbonate mother liquor and water for sodium removal, and controlling the mass ratio of water to the reduced clinker to be 2:1, obtaining vanadium trioxide and sodium removal solution; introducing carbon dioxide into the sodium removal solution, controlling the PH of the solution to be 10, obtaining an auxiliary agent and auxiliary agent mother liquor, continuously introducing carbon dioxide into the auxiliary agent mother liquor, controlling the PH of the solution to be 7, obtaining sodium bicarbonate and sodium bicarbonate mother liquor, returning the sodium bicarbonate to the step (1), and returning the sodium bicarbonate mother liquor for recycling.
Example 3
The embodiment provides a method for cleaning vanadium slag and extracting vanadium, which is shown in a flow chart of fig. 1, and comprises the following steps:
(1) Roasting vanadium slag and sodium salt at 800 ℃, controlling the molar ratio of total sodium to total vanadium in a reaction system to be 1:1, mixing roasting clinker, water, chromium removal mother liquor, vanadium precipitation mother liquor and impurity removal slag to carry out vanadium-chromium leaching, wherein the mass ratio of water to roasting clinker is 2:1, obtaining tailings and leaching liquid; adding calcium oxide into the leaching solution to remove impurities, wherein the mass ratio of the calcium oxide is as follows: (p+si) =2: 1, obtaining impurity-removed slag and purifying liquid, returning the impurity-removed slag to the step 1, adding calcium oxide into the purifying liquid to precipitate vanadium, and controlling the molar ratio of total calcium to total vanadate in a reaction system to be 1:1 to obtain vanadium precipitation mother liquor and calcium vanadate;
(2) Introducing carbon dioxide into the vanadium precipitation mother liquor, controlling the pH of the solution to be 8.5, recovering sodium bicarbonate and returning to the step (1), adding formaldehyde into the sodium bicarbonate mother liquor to reduce the high-valence chromium in the solution to trivalent chromium to obtain chromium hydroxide and chromium removal mother liquor, returning the chromium removal mother liquor to the step (1), and calcining the chromium hydroxide to obtain chromium sesquioxide;
(3) Mixing calcium vanadate, carbon dioxide, crystallization mother liquor and calcination tail gas to leach vanadium, controlling the PH of the solution to be 9-10 (or separating out calcium in a precipitation form) to obtain calcium salt and sodium vanadate solution, and returning the calcium salt to the step (1) after calcination; evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, condensed water and crystallization mother liquor, mixing sodium metavanadate, aluminum phosphate and coal gas, and then reducing at 600 ℃ to obtain reduction clinker, wherein the molar ratio of total aluminum to total sodium in a reaction system is controlled to be 1:1; mixing the reduced clinker, sodium bicarbonate mother liquor and water for sodium removal, and controlling the mass ratio of water to the reduced clinker to be 4:1, obtaining vanadium trioxide and sodium removal solution; introducing carbon dioxide into the sodium removing solution, controlling the PH of the solution to be 12, obtaining an auxiliary agent and auxiliary agent mother liquor, continuously introducing carbon dioxide into the auxiliary agent mother liquor, controlling the PH of the solution to be 8.5, obtaining sodium bicarbonate and sodium bicarbonate mother liquor, returning the sodium bicarbonate to the step (1), and returning the sodium bicarbonate mother liquor for recycling.
Example 4
In this example, the procedure was the same as in example 1 except that the mass ratio of water to clinker in step (1) was replaced with 1:1.
Example 5
In this example, the procedure was the same as in example 1 except that the molar ratio of total calcium to total vanadate in the reaction system controlled in step (1) was replaced with 1.4:1.
Example 6
In this example, the conditions were the same as in example 1 except that the molar ratio of total aluminum to total sodium in the reaction system controlled in step (3) was replaced with 1.4:1.
Example 7
In this example, the conditions were the same as in example 1 except that the mass of the control water and the reduced clinker in step (3) was replaced with 5:1.
Example 8
This comparative example was conducted under the same conditions as in example 1 except that the molar ratio of total calcium to total vanadate in the reaction system in step (1) was replaced with 0.8:1.
Example 9
In this example, the conditions were the same as in example 1 except that the molar ratio of total aluminum to total sodium in the reaction system in step (3) was replaced with 0.7:1.
Example 10
In this example, the conditions were the same as in example 1 except that the mass ratio of water to reduced clinker in step (3) was replaced with 1:1.
The purities of the chromium and vanadium trioxide prepared in examples 1-10 were tested and the test results are shown in Table 1.
TABLE 1
The chromium oxide in examples 1-7 of the invention has a purity which meets the requirements of class I qualified products in HG/T2775-2010 and the vanadium oxide has a purity which meets the brand V in GB/T40301-2021 2 O 3 66. In example 5, compared with example 1, since the calcium oxide is too much in step (1), a large amount of calcium oxide remains and enters the calcium vanadate in a solid phase form, and the purity of the product is not affected although the calcium salt is discharged during the leaching of the vanadium, the energy consumption and the utilization rate of the calcium are affected, that is, the economy is adversely affected. In example 7, the amount of water added in step (3) was too high compared with example 1, and the purity of vanadium trioxide was not affected, but the recovery rate of sodium was affected, that is, the economical efficiency was adversely affected.
The chromium oxide content in example 8 was 90.4% and did not meet the requirements for class I quality in HG/T2775-2010; the vanadium content of the obtained vanadium trioxide product is 66.3 percent, and meets the brand V in GB/T40301-2021 2 O 3 66. The chromium oxide content in example 9 was 98.3% meeting the requirements of class I quality in HG/T2775-2010; the vanadium content of the obtained vanadium trioxide product is 62.1 percent, and does not meet the brand V in GB/T40301-2021 2 O 3 66. The chromium oxide content in example 10 was 98.7% meeting the requirements of class I quality in HG/T2775-2010; the vanadium content of the obtained vanadium trioxide product is 60.5 percent, and does not meet the brand V in GB/T40301-2021 2 O 3 66. Compared with example 1, due to the insufficient water addition in example 10, the impurities in the reduced clinker cannot be completely washed out and partially enter into the vanadium trioxide product, reducing the product quality.
It should be understood, however, that the present invention is not limited to the above embodiments, and that any changes or substitutions that may be easily contemplated by those skilled in the art within the scope of the present invention are within the scope of the present invention as disclosed herein.
Claims (10)
1. The method for cleanly extracting vanadium from vanadium slag is characterized by comprising the following steps of:
(1) Mixing vanadium slag and sodium salt, sintering, adding roasting clinker, water, chromium-removing mother liquor and impurity-removing slag, leaching to obtain tailings and leaching liquor, removing impurities from the leaching liquor to obtain purifying liquid, and carrying out precipitation treatment on the purifying liquid to obtain vanadium-precipitating mother liquor and calcium vanadate;
(2) Adding a first reducing agent into the vanadium precipitation mother liquor in the step (1) to obtain chromium hydroxide, and calcining to obtain chromium sesquioxide;
(3) Leaching vanadium from the calcium vanadate, carbon dioxide, crystallization mother liquor and calcined tail gas in the step (1) to obtain a calcium salt and sodium vanadate solution, evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, reducing the sodium metavanadate, an auxiliary agent and a second reducing agent at high temperature to obtain a reduction clinker, and removing sodium from the reduction clinker, sodium bicarbonate mother liquor and water to obtain vanadium trioxide.
2. The process according to claim 1, wherein the sodium salt of step (1) is sodium carbonate and/or sodium bicarbonate;
preferably, the sintering temperature in the step (1) is 700-1100 ℃;
preferably, in the step (1), the molar ratio of total sodium to total vanadium in the reaction system is controlled to be (1-1.4): 1;
preferably, the mass ratio of the water and the baked clinker in the step (1) is (1-3): 1.
3. The method according to claim 1 or 2, wherein the removing of impurities of step (1) comprises: adding calcium oxide into the leaching solution to remove impurities to obtain impurity-removed slag and purifying liquid;
preferably, in the impurity removal, calcium oxide (p+si) = (2 to 4): 1;
preferably, the impurity removing slag is returned to the step (1) for recycling.
4. A method according to any one of claims 1 to 3, wherein the precipitation treatment of step (1) comprises: adding calcium oxide into the purifying liquid to precipitate vanadium, so as to obtain vanadium precipitation mother liquor and calcium vanadate;
preferably, in the precipitation treatment in the step (1), the molar ratio of the total calcium to the total vanadate in the reaction system is controlled to be (1-1.4): 1.
5. The method according to any one of claims 1 to 4, wherein carbon dioxide is introduced into the vanadium precipitation mother liquor of step (2) to recover sodium bicarbonate, so as to obtain sodium bicarbonate mother liquor, and a reducing agent is added into the sodium bicarbonate mother liquor, so as to obtain chromium oxide and chromium removal mother liquor;
preferably, when the sodium bicarbonate is recovered, the pH of the solution is 7.0-9.0;
preferably, the first reducing agent comprises any one or a combination of at least two of formic acid, oxalic acid, formaldehyde, hydrazine hydrate, methanol or ethanol;
preferably, the chromium-removing mother liquor is returned to the step (1) for recycling;
preferably, the temperature of the calcination in the step (2) is 900-1600 ℃.
6. The method according to any one of claims 1 to 5, wherein the pH of the solution is controlled to be 9.0 to 10.0 during leaching in step (3);
preferably, the calcium salt in the step (3) returns to the step (1) as a impurity removing agent after being calcined.
7. The method according to any one of claims 1 to 6, wherein the sodium vanadate solution in step (3) is evaporated and crystallized to obtain sodium metavanadate, condensed water and a crystallization mother liquor;
preferably, the auxiliary agent in the step (3) comprises any one or a combination of at least two of alumina, aluminum hydroxide or aluminum phosphate;
preferably, the second reducing agent of step (3) comprises any one or a combination of at least two of hydrogen, CO, gas or natural gas;
preferably, the high-temperature reduction temperature in the step (3) is 600-900 ℃;
preferably, the molar ratio of total aluminum to total sodium in the high-temperature reduction in the step (3) is controlled to be (1-1.4): 1.
8. The method according to any one of claims 1 to 7, wherein the reduced clinker of step (3), sodium bicarbonate mother liquor and water are subjected to sodium removal to obtain vanadium trioxide and a sodium removal solution;
preferably, in the sodium removal process, the mass ratio of water to the reduced clinker is controlled to be (2-5): 1;
preferably, introducing carbon dioxide into the sodium removal solution, and controlling the pH value to be 10.0-12.0 to obtain an auxiliary agent and an auxiliary agent mother solution;
preferably, continuously introducing carbon dioxide into the auxiliary agent, and controlling the pH value to be 7.0-9.0 to obtain sodium bicarbonate and sodium bicarbonate mother solution;
preferably, the sodium bicarbonate is returned to step (1) as a impurity removing agent;
preferably, the sodium bicarbonate mother liquor is returned to the step (3) to participate in sodium removal.
9. The method according to any one of claims 1-8, characterized in that the method comprises the steps of:
(1) Mixing vanadium slag and sodium salt, sintering at 700-1100 ℃, adding roasting clinker, water, chromium-removing mother liquor and impurity-removing slag, leaching, controlling the mole ratio of total sodium and total vanadium in a reaction system to be (1-1.4): 1, obtaining tailings and leaching liquid, removing impurities from the leaching liquid to obtain purifying liquid, and performing precipitation treatment on the purifying liquid to obtain vanadium-precipitating mother liquor and calcium vanadate, wherein the mole ratio of total calcium and total vanadate in the reaction system is controlled to be (1-1.4): 1 in the precipitation treatment;
(2) Adding a first reducing agent into the vanadium precipitation mother liquor in the step (1) to obtain chromium hydroxide, and calcining to obtain chromium sesquioxide;
(3) Leaching vanadium from the calcium vanadate, carbon dioxide, crystallization mother liquor and calcined tail gas in the step (1) to obtain a calcium salt and sodium vanadate solution, evaporating and crystallizing the sodium vanadate solution to obtain sodium metavanadate, reducing the sodium metavanadate, the auxiliary agent and the second reducing agent at a high temperature of 600-900 ℃ to obtain reduced clinker, and removing sodium from the reduced clinker, sodium bicarbonate mother liquor and water to obtain vanadium trioxide.
10. Use of the method for clean vanadium extraction from vanadium slag according to any one of claims 1 to 9, characterized in that the method is applied in the technical field of metallurgical chemical industry.
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