CN113957272B - Vanadium slag vanadium extraction method using sintering process red mud as additive - Google Patents
Vanadium slag vanadium extraction method using sintering process red mud as additive Download PDFInfo
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- CN113957272B CN113957272B CN202111125806.XA CN202111125806A CN113957272B CN 113957272 B CN113957272 B CN 113957272B CN 202111125806 A CN202111125806 A CN 202111125806A CN 113957272 B CN113957272 B CN 113957272B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 138
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000005245 sintering Methods 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 title claims abstract description 58
- 238000000605 extraction Methods 0.000 title claims abstract description 38
- 239000000654 additive Substances 0.000 title claims abstract description 17
- 230000000996 additive effect Effects 0.000 title claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 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
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002308 calcification Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- UMRUNOIJZLCTGG-UHFFFAOYSA-N calcium;manganese Chemical compound [Ca+2].[Mn].[Mn].[Mn].[Mn] UMRUNOIJZLCTGG-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- -1 manganese vanadate compound Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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
- C22B7/001—Dry 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
- 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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/04—Working-up slag
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of comprehensive utilization of vanadium resources and red mud solid wastes, and discloses a vanadium slag vanadium extraction method using sintering process red mud as an additive. The method comprises the following steps: (1) Mixing the dried and crushed sintering red mud with the fine powder vanadium slag, and then roasting at high temperature to obtain clinker; (2) Crushing the clinker, mixing the crushed clinker with water, adjusting the pH value of the obtained mixed solution to acidic leaching, and filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings. The sintering method red mud is used as a roasting additive to extract vanadium from vanadium slag, so that the process is simple, the waste utilization can be realized, the cost is reduced, good social and economic benefits are achieved, and the leaching rate of vanadium is high. Vanadium can be further extracted from the vanadium-containing leaching solution to obtain a vanadium oxide product; the vanadium extraction tailings can be returned to the blast furnace for reuse after being subjected to desulfurization and dephosphorization.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of vanadium resources and red mud solid waste, in particular to a vanadium extraction method from vanadium slag by taking sintering red mud as an additive.
Background
The vanadium extraction process of vanadium slag mainly comprises a sodium roasting process and a calcification roasting process, namely, sodium salt or calcium salt is used as an additive, and the high-temperature roasting and the water leaching or acid leaching are carried out to obtain vanadium-containing leachate and vanadium extraction tailings. In the vanadium slag sodium salt roasting process, the liquid treatment process after vanadium precipitation is complex and the production cost is high, and the generated vanadium-chromium reduction slag and the mixture of sodium sulfate containing vanadium and chromium and ammonium sulfate belong to hazardous wastes. In the calcification roasting process, the tailings after acid leaching do not contain sodium salt, the liquid after vanadium precipitation is treated and then returns to a system for utilization, the comprehensive recovery of waste and the closed cycle of liquid materials can be realized, no waste gas is generated in the whole process, and the aim of clean vanadium extraction can be achieved. In recent years, techniques such as magnesium roasting, manganese roasting, and calcium-manganese composite roasting have been studied in the field of vanadium extraction from vanadium slag.
Chinese patent CN 101412539B provides a clean production method of vanadium oxide, which comprises the steps of preparing roasting raw materials, calcifying roasting, leaching, solid-liquid separation, ammonium salt vanadium precipitation, calcining deamination or reduction and the like to prepare vanadium oxide, vanadium extraction wastewater is neutralized by lime milk and then returns to a system for recycling, and zero discharge of wastewater is realized. The invention also improves the recovery rate of vanadium, which is higher than the prior art, and reduces the production cost. Through combination with other technologies, the method can also convert wastes such as residues after vanadium extraction into secondary resources, and reuse the secondary resources to realize clean production; chinese patent CN 109930008B selects a magnesium-containing compound as a roasting additive and recovers impurity metal ions in the leaching solution, thereby reducing the production cost, increasing the environmental friendliness and establishing a new method for extracting vanadium from vanadium slag with zero emission of three wastes; the Chinese patent CN 103898329B uses a manganese roasting method, and takes a tetravalent manganese material as an oxidant, so that vanadium and manganese are combined in the roasting process to form a manganese vanadate compound, thereby effectively avoiding the ring formation phenomenon of vanadium slag in the roasting process and reducing the roasting temperature of the vanadium slag; chinese patent CN 112111661A takes a compound containing calcium and manganese as an additive, and the compound is fully mixed with vanadium slag fine powder and then roasted to obtain clinker, and then vanadium is extracted by acid leaching twice, and the comprehensive leaching rate of vanadium by using the method reaches 94-97%.
The red mud is polluting waste residue discharged when extracting aluminum oxide in the aluminum industry, and generally 1.0-2.0 tons of red mud are additionally generated when 1 ton of aluminum oxide is produced on average. China, the fourth major alumina producing country in the world, discharges red mud as high as millions of tons every year. The resource utilization of red mud has become an urgent subject facing the alumina industry and even the whole aluminum industry. For bauxite with low aluminum content (A/S < 7), alumina is often extracted by a sintering process, thereby producing sintering red mud.
The Chinese patent CN 100339332C utilizes red mud, fly ash, lime and external additives of a sintering method as a pavement base material, can form higher integral strength and frost resistance, and is particularly suitable for popularization and application in the north of China; chinese CN 101480568B modifies red mud obtained by a sintering method, and then the modified red mud is used as a coal-fired sulfur-fixing agent, so that the red mud can be effectively utilized to reduce the problem caused by stacking, and the content of the red mud in coal-fired flue gas can be effectively reducedSO 2 (ii) a Chinese CN 109821412B modifies activated carbon with a mixture of red mud from a sintering process and coal gangue to prepare low-cost composite modified activated carbon for flue gas desulfurization and denitration, expands the high-added-value application of the red mud from the sintering process and the coal gangue, and realizes a new idea of treating wastes with processes of wastes against one another; chinese patent CN 102745733B adopts the steps of settling separation, slurry roasting, circulating water leaching, filter residue acid leaching, aging silicon extraction, circulating acid leaching and the like to the sintering process red mud to obtain products such as aluminum hydroxide, micro silicic acid, gypsum, iron powder and the like; chinese patent CN 104001885B utilizes red mud produced by a sintering method to produce square billet crystallizer casting powder; chinese patent CN 102336579B utilizes red mud to produce high-performance ceramsite; chinese patent CN 107586065B uses sintering red mud as adhesive to produce mineral wool board.
According to the review, the sintering process red mud in the prior art is applied in many aspects, but no relevant report of vanadium extraction roasting additive of vanadium slag by using sintering process red mud is found.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a vanadium slag vanadium extraction method taking sintering process red mud as an additive.
In order to achieve the aim, the invention provides a vanadium extraction method of vanadium slag by taking red mud of a sintering method as an additive, which comprises the following steps:
(1) Mixing the dried and crushed red mud obtained by the sintering method with the fine powder vanadium slag, and then roasting at high temperature to obtain clinker;
(2) Crushing the clinker, mixing the crushed clinker with water, adjusting the pH value of the obtained mixed solution to acidic leaching, and filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
Preferably, in the step (1), the sintering process red mud contains 40 to 49 wt% of CaO.
Preferably, in the step (1), the fine vanadium slag contains 17-18 wt% of V 2 O 5 And 1 to 2 weight percent CaO.
Preferably, in the dried and crushed sintering red mud in the step (1), more than 80% of the sintering red mud has a particle size of less than 95um.
Preferably, in the fine powder vanadium slag in the step (1), the particle size of more than 80% of the fine powder vanadium slag is less than 95um.
Preferably, in the step (1), caO in the red mud and the fine vanadium slag of the sintering method and V in the red mud and the fine vanadium slag of the sintering method 2 O 5 The molar ratio of (b) is 2.0 to 2.6.
Preferably, in the step (1), the high-temperature roasting temperature is 840-900 ℃, and the high-temperature roasting time is 100-180 min.
Preferably, in step (2), the particle size of the crushed clinker is less than 95um.
Preferably, in step (2), the pH of the resulting mixed solution is adjusted to acidity using sulfuric acid.
Preferably, in the step (2), the solid-to-liquid ratio of the leaching solution is 3-5 ml/g; the leaching pH value is 2.5-3.5; the leaching temperature is 40-60 ℃; the leaching time is 40-80 min.
The inventor finds that the red mud usually contains a large amount of CaO and SiO in vanadium slag vanadium extraction research 2 、Al 2 O 3 、Fe 2 O 3 And a certain content of silicate minerals, which have certain potential activity. Compared with Bayer process red mud and combination process red mud, the CaO content in the sintering process red mud is higher, and the red mud can be used as a roasting additive for extracting vanadium from vanadium slag. The invention uses the red mud of the sintering method as a calcium source, combines vanadium and calcium to generate calcium vanadate through calcification oxidation roasting, and then carries out acid leaching to obtain vanadium-containing leaching solution and vanadium extraction tailings. Further extracting vanadium from the vanadium-containing leaching solution to obtain a vanadium oxide product, and performing desulfurization and dephosphorization treatment on the vanadium-extracted tailings, so that the vanadium-extracted tailings can be returned to the blast furnace for recycling.
The invention has the following advantages: 1) The sintering method red mud is used as industrial solid waste and is used as a vanadium slag roasting additive, so that the roasting cost can be obviously reduced; 2) Vanadium is extracted from vanadium slag by using the red mud of the sintering method, so that the stockpiling of the red mud of the sintering method can be reduced, and the resource utilization of the red mud is realized; 3) The method has the advantages of convenient operation, wide application range, low cost and good social and economic benefits.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a vanadium slag vanadium extraction method using sintering process red mud as an additive, which comprises the following steps:
(1) Mixing the dried and crushed sintering red mud with the fine powder vanadium slag, and then roasting at high temperature to obtain clinker;
(2) Crushing the clinker, mixing the crushed clinker with water, adjusting the pH value of the obtained mixed solution to acidic leaching, and filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
In the method, the red mud obtained by the sintering method has high CaO content and contains a large amount of SiO 2 、Al 2 O 3 、Fe 2 O 3 And the like. The sintering red mud refers to sintering red mud generated by extracting alumina from bauxite with low aluminum content (A/S is less than 7) by adopting a sintering method.
In a specific embodiment, in the step (1), the sintering process red mud contains 40 to 49 wt% of CaO. In a more specific embodiment, the sintering red mud further contains 19 to 20 wt% of SiO 2 10 to 11% by weight of Al 2 O 3 5 to 6% by weight of TiO 2 。SiO 2 、Al 2 O 3 And TiO 2 2 The presence of (b) greatly affects the leaching of vanadium.
In the method, the fine powder vanadium slag can be vanadium slag commonly used in the field.
In a specific embodiment, in the step (1), the fine vanadium slag contains 17 to 18 weight percent of V 2 O 5 And 1 to 2% by weight of CaO. In a more specific embodiment, the fine vanadium slag further contains 10 to 11 wt% of SiO 2 4 to 5% by weight of Al 2 O 3 14 to 15% by weight of TiO 2 。SiO 2 、Al 2 O 3 And TiO 2 The presence of (b) greatly affects the leaching of vanadium.
In order to further improve the sintering efficiency, the vanadium slag and the red mud of the sintering method are fully combined to generate calcium vanadate, and the particle size of the vanadium slag and the red mud of the sintering method needs to be controlled.
In a specific embodiment, in the sintering process red mud dried and crushed in step (1), more than 80% of the sintering process red mud has a particle size of less than 95um, that is, after the sintering process red mud is dried and crushed, the ratio of the 160-mesh screen underflow is more than 80%, preferably more than 90%.
In a specific embodiment, in the refined powder vanadium slag in the step (1), the particle size of more than 80% of the refined powder vanadium slag is less than 95um, that is, the ratio of 160-mesh screen underflow in the refined powder vanadium slag is more than 80%, preferably more than 82%.
In a preferred embodiment, in the step (1), caO in the sintering process red mud and the fine powder vanadium slag and V in the sintering process red mud and the fine powder vanadium slag 2 O 5 The molar ratio of (1) to (2.0-2.6), namely the total molar weight of CaO in the sintering process red mud and the fine powder vanadium slag and V in the sintering process red mud and the fine powder vanadium slag 2 O 5 The ratio of the total molar amount of (B) is 2.0 to 2.6, and may be, for example, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 or 2.6.
In the method of the present invention, in the step (1), the high-temperature roasting temperature may be 840 to 900 ℃, for example, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃ or 900 ℃; the high-temperature roasting time can be 100-180 min, such as 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min.
In a specific embodiment, in the step (2), the particle size of the crushed clinker is less than 95um, that is, the whole crushed clinker is sieved by a 160-mesh sieve. In the step, the grain size of the clinker is controlled within the range, so that vanadium leaching is facilitated, and the leaching rate of vanadium can be further improved. There is a certain amount of vanadium loss during clinker crushing.
In particular embodiments, the leach pH may be adjusted using mineral acids conventionally used in the art.
In a preferred embodiment, in step (2), the pH of the resulting mixed solution may be adjusted to acidity using sulfuric acid. The sulfuric acid is adopted to adjust the pH value, so that the subsequent treatment of the waste liquid is facilitated.
In the method of the present invention, in order to improve the leaching rate of vanadium, the leaching process can be controlled within a preferable range.
In a preferred embodiment, in step (2), the leach solution solids ratio may be 3 to 5ml/g, for example 3ml/g, 3.2ml/g, 3.4ml/g, 3.6ml/g, 3.8ml/g, 4ml/g, 4.2ml/g, 4.4ml/g, 4.6ml/g, 4.8ml/g or 5ml/g.
In a preferred embodiment, in step (2), the leach pH may be 2.5 to 3.5, for example 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 or 3.5.
In a preferred embodiment, in step (2), the leaching temperature may be 40 to 60 ℃, for example 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃.
In a preferred embodiment, in step (2), the leaching time may be 40 to 80min, for example 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min or 80min.
The sintering method red mud is used as a roasting additive to extract vanadium from vanadium slag, so that the process is simple, the waste utilization can be realized, the cost is reduced, good social benefit and economic benefit are realized, and the leaching rate of vanadium is high. Vanadium can be further extracted from the vanadium-containing leaching solution to obtain a vanadium oxide product; the vanadium extraction tailings can be returned to the blast furnace for recycling after desulfurization and dephosphorization treatment.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The compositions of the red mud produced by sintering process and the vanadium slag produced from the refined powder used in examples 1 to 3 are shown in Table 1, wherein the V content in the material is V 2 O 5 And (6) counting. The proportion of the fine powder vanadium slag used in the examples 1 to 3 to the 160-mesh screen underflow is 90.12%; the proportion of 160-mesh screen underflow in the sintering process red mud is 83.28 percent.
TABLE 1 main Components/% of Red mud and Fine powder vanadium slag of sintering Process
| V 2 O 5 | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | TiO 2 | MnO | MgO | Na 2 O | K 2 O | Loss due to burn | |
| Sintering process red mud | / | 42.67 | 19.25 | 10.87 | 9.13 | 5.39 | / | 1.90 | 2.40 | 0.20 | 8.07 |
| Fine powder vanadium slag | 17.50 | 1.70 | 10.16 | 4.62 | 38.10 | 14.60 | 8.63 | 1.72 | / | / | / |
Example 1
100g of fine powder vanadium slag is taken and mixed with 21.25g of red mud by a sintering method, and n (CaO)/n (V) in the obtained mixed material 2 O 5 ) =2.0, then adding the mixed material into a muffle furnace for high-temperature roasting, controlling the high-temperature roasting temperature to be 840 ℃, and keeping the temperature for 180min; after the roasted clinker is cooled, the clinker is crushed to be totally filtered by a 160-mesh screen, the crushed clinker is 120.10g, then the crushed clinker is added into 480ml of water, sulfuric acid with the mass concentration of 30% is added, and the mixture is soakedMaintaining the pH value at 2.5, the solid-to-solid ratio of the leaching solution at 4ml/g, keeping the leaching temperature at 40 ℃, and controlling the leaching time at 80min; filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
Detecting V in vanadium extraction tailings 2 O 5 The content of the vanadium extraction tailings is 1.20 percent, the dry weight of the vanadium extraction tailings is 118.91g, and the leaching rate of the vanadium is 91.76 percent.
Example 2
200g of fine powder vanadium slag is evenly mixed with 50.08g of sintering method red mud, and n (CaO)/n (V) in the obtained mixed material 2 O 5 ) =2.3, then the mixed material is added into a muffle furnace for high-temperature roasting, the high-temperature roasting temperature is controlled at 900 ℃, and the heat preservation time is 100min; after the roasted clinker is cooled, crushing the clinker until the clinker passes through a 160-mesh screen, wherein the crushed clinker is 246.56g, then adding the crushed clinker into 740ml of water, adding 70% sulfuric acid to maintain the pH value during leaching at 2.8, keeping the leaching solution-solid ratio at 3ml/g, keeping the leaching temperature at 50 ℃, and controlling the leaching time to be 40min; filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
Detecting V in vanadium extraction tailings 2 O 5 The content of (2) is 1.32%, the dry weight of the vanadium extraction tailings is 245.33g, and the leaching rate of vanadium is 90.61%.
Example 3
300g of fine vanadium slag powder is evenly mixed with 86.48g of red mud by a sintering method to obtain a mixed material, wherein n (CaO)/n (V) is contained in the mixed material 2 O 5 ) =2.6, then the mixed material is added into a muffle furnace for high-temperature roasting, the high-temperature roasting temperature is controlled to 870 ℃, and the heat preservation time is 140min; after the roasted clinker is cooled, crushing the clinker until the clinker passes through a 160-mesh screen completely, wherein the crushed clinker is 380.25g, then adding the crushed clinker into 1900ml of water, adding 50% sulfuric acid to maintain the pH value in leaching at 3.5, keeping the solid-to-solid ratio of a leaching solution at 5ml/g, keeping the leaching temperature at 60 ℃, and controlling the leaching time to be 60min; filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
Detecting V in vanadium extraction tailings 2 O 5 The content of the vanadium extraction tailings is 1.16 percent, the dry weight of the vanadium extraction tailings is 380.33g, and the leaching rate of the vanadium is 91.46 percent.
Comparative example
200g of fine vanadium slag and 39.24g of limestone (54.45 percent of CaO content) are mixed uniformly, and n (CaO)/n (V) in the obtained mixed material 2 O 5 ) =2.3, then adding the mixed material into a muffle furnace for high-temperature roasting, controlling the high-temperature roasting temperature to be 870 ℃, and keeping the temperature for 140min; after the roasted clinker is cooled, crushing the clinker until the clinker passes through a 160-mesh screen, wherein the crushed clinker is 212.25g, then adding the crushed clinker into 640ml of water, adding 50% sulfuric acid to maintain the pH value during leaching at 3.5, keeping the leaching solution-solid ratio at 5ml/g, keeping the leaching temperature at 60 ℃, and controlling the leaching time to be 60min; filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings.
Detecting V in vanadium extraction tailings 2 O 5 The content of (2) is 1.35%, the dry weight of the vanadium extraction tailings is 213.8g, and the leaching rate of vanadium is 91.70%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (6)
1. A vanadium slag vanadium extraction method taking sintering process red mud as an additive is characterized by comprising the following steps:
(1) Mixing the dried and crushed sintering red mud with the fine powder vanadium slag, and then roasting at high temperature to obtain clinker;
(2) Crushing the clinker, mixing the crushed clinker with water, adjusting the pH value of the obtained mixed solution to acidic leaching, and filtering to obtain vanadium-containing leaching solution and vanadium extraction tailings;
in the dried and crushed sintering red mud in the step (1), more than 80 percent of the sintering red mud has the particle size of less than 95um; in the fine powder vanadium slag in the step (1), the particle size of more than 80% of the fine powder vanadium slag is less than 95um;
in the step (1), caO in the red mud and the fine powder vanadium slag of the sintering method and V in the red mud and the fine powder vanadium slag of the sintering method 2 O 5 The molar ratio of (A) to (B) is 2.0-2.6;
in the step (2), the solid-to-solid ratio of the leaching solution is 3-5 ml/g; the leaching pH value is 2.5-3.5; the leaching temperature is 40-60 ℃; the leaching time is 40-80 min.
2. The method according to claim 1, characterized in that in step (1), the sintering process red mud contains 40-49 wt.% CaO.
3. The method according to claim 1, wherein in the step (1), the fine powder vanadium slag contains 17-18 wt% of V 2 O 5 And 1 to 2% by weight of CaO.
4. The method as claimed in claim 1, wherein, in the step (1), the temperature of the high-temperature roasting is 840-900 ℃; the high-temperature roasting time is 100-180 min.
5. The method of claim 1, wherein in step (2), the crushed clinker has a particle size of less than 95um.
6. The method according to claim 1, wherein in the step (2), the pH of the resulting mixed solution is adjusted to acidity using sulfuric acid.
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