CN102851521A - Method for extracting vanadium through oxidation conversion of vanadium-containing ores - Google Patents
Method for extracting vanadium through oxidation conversion of vanadium-containing ores Download PDFInfo
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- CN102851521A CN102851521A CN2011103059094A CN201110305909A CN102851521A CN 102851521 A CN102851521 A CN 102851521A CN 2011103059094 A CN2011103059094 A CN 2011103059094A CN 201110305909 A CN201110305909 A CN 201110305909A CN 102851521 A CN102851521 A CN 102851521A
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- vanadium
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a method for extracting vanadium through oxidation conversion of vanadium-containing ores. The method comprises the following steps: fragmenting, ball-milling and sieving the vanadium-containing ores; adding a sulfur-containing oxidizing agent and sulfuric acid to carry out oxidation extraction; deeply oxidizing through sodium chlorate; carrying out ion exchange; carrying out vanadium precipitation; and calcining to produce V2O5 products. When the method is utilized to produce V2O5, the vanadium extraction rate reaches above 90%, the vanadium recovery rate is greater than 80%, and the vanadium extraction rate is substantially higher than that of present vanadium extraction technologies. The method disclosed in the invention has the advantages of ore roasting process omitting, elimination of the pollution of Cl2 and HCl gases to the environment, process flow simplification, production cost reduction, and substantial improvement of the vanadium extraction rate and the vanadium recovery rate.
Description
Technical field:
The present invention relates to a kind of method of oxidation conversion leaching vanadium extraction from contain navajoite stone, belong to technical field of wet metallurgy.
Background technology:
Vanadium mainly is present in stone coal mine, contains in vanadium clay pit and the vanadium titano-magnetite.Rock coal containing alum (also claiming to contain the vanadium black shale) and clay pit are the main navajoite resources of China, spread all over more than 20 provinces and regions such as China Hunan, Hubei, Jiangxi, Zhejiang, Shaanxi, Guangxi, total reserves is 7 times of vanadium total reserves in the vanadium titano-magnetite, surpasses the summation of other various countries' vanadium reserves of the world.The so abundant valuable navajoite stone resource that contains is developed and utilized, have huge economic potential and social benefit.
The traditional technology of bone coal and clay pit vanadium extraction is flat kiln sodium-salt calcination method.The advantage of this technique is that extractive technique is ripe, investment is little, shortcoming is to turn the rate of soaking and the rate of recovery is low, the roasting conversion rate of vanadium is usually 60%, total recovery is about 50%, and the ore consumption is large, serious waste of resources, particularly in roasting process, add Industrial Salt (sodium-chlor) and produce the toxic and harmfuls such as a large amount of containing hydrogen chlorides, chlorine, wherein chlorine is industrial hypertoxic gas, and serious environment pollution is so China has forbidden this method substantially.
At present, China has focused on that full wet method controls golden vanadium extraction research, because full wet method process for extracting vanadium does not need roasting, has fundamentally eliminated topsoil, is fit to scale operation, is the developing direction of from now on navajoite vanadium extraction therefore.Up to now, the complete topmost method of wet method vanadium extraction is direct pickling process, and directly at high temperature and long Leaching Vanadium under the leaching condition, leaching yield increases than roasting method with high-concentration sulfuric acid.But this method sulfuric acid consumption is large, and production cost is high, does not possess feasibility economically.
Therefore, how to improve V leaching rate, Reduction of acid consumption is an important problem of vanadium hydrometallurgy.
Summary of the invention:
The objective of the invention is the deficiency for direct acid-leaching vanadium-extracted technology, provide a kind of and leach extraction vanadium method by the oxidation conversion of selecting suitable oxygenant to significantly improve the leaching yield of vanadium, greatly reduce the consumption of sulfuric acid simultaneously.
Owing to the vanadium part in Rock coal containing alum or the clay pit is present in the mica lattice with the trivalent aluminium of six coordinations of trivalent vanadium isomorph form displacement in mica, if Leaching Vanadium must destroy the structure of mica from mica, and make it oxidation just may be by solvent extraction.Except adopting traditional sodium roasting to break the mica structure and change into the vanadium of solubility, also can directly destroy its mica structure with acid.Namely under certain temperature and acidity, hydrogen ion enters mica crystal lattice aluminium, and ionic radius is changed, and vanadium is discharged.The trivalent vanadium that discharges is dissolved by acid after being become tetravalence or pentavalent by institute's oxidizer oxidation.
Then utilize ion exchange technique to carry out the separation and purification enrichment, adopting ammonium salt precipitation technical change is ammonium meta-vanadate, and last thermal degradation is the Vanadium Pentoxide in FLAKES product.
Technical scheme of the present invention is as follows: add industrial sulphuric acid in leaching in the pond, will contain vanadium crushing raw ore, ball milling to crossing 80 mesh sieves, put into the leaching pond, add in the leaching pond by the weight ratio of 0.1-5% and contain thiooxidant K
2S
2O
7Or Na
2S
2O
7Or (NH
4)
2S
2O
7Or K
2S
2O
8Or Na
2S
2O
8Or (NH
4)
2S
2O
8, and stir, press solid-to-liquid ratio 1: 0.5-5, sour ore deposit than 1: the add-on of 2-9 control water, frequently stir, under 10-100 ℃ of temperature, leached 1-12 hour filtering separation.Add the sodium chlorate solution that vanadiumcontent 0.5-1 doubly measures in the vanadium solution behind oxidation acid leaching, the tetravalence vanadium is oxidized to the pentavalent vanadium, then solution containing vanadium is adsorbed with the strong basicity macroporous anion exchange resin, the rear solution of absorption carries out desorb with 10% NaOH and 5%NaCl mixing solutions.To contain vanadium elutriant NH behind the Pro-concentration with ion exchange process
4The Cl precipitation generates the ammonium meta-vanadate precipitation, filters, and after the oven dry of ammonium meta-vanadate filter cake, sends into calcining furnace, is decomposed into V 400-600 ℃ of calcination
2O
5Product.The tail gas HCl recovery, the NH of generation
4Cl returns the precipitation operation and uses.The product purity that this explained hereafter goes out reaches YB/T 5304-2006 standard, and the leaching yield of vanadium is greater than 90%, and the rate of recovery of vanadium is greater than 80%.
Because the present invention contains navajoite stone without the direct acidleach of roasting, work simplification has reduced energy consumption and production cost; Eliminated the Cl that sodium roasting produces
2, the HCl flue gas is to the pollution of environment and the corrosion of equipment, belongs to process for cleanly preparing; V leaching rate, the rate of recovery and resource utilization have greatly been improved.
Embodiment:
Embodiment one:
(1) pulverizing ball milling sieves: stone coal mine is extremely crossed 80 mesh sieves through broken, ball milling.(2) oxidation acid leaching: being to contain 30% of navajoite grain weight amount to add the vitriol oil in the leaching pond by the consumption of sulfuric acid, is that the 3% dosage ratio that contains navajoite grain weight amount adds K by the consumption of oxygenant
2S
2O
8And mix is even.Add-on by solid-to-liquid ratio control in 1: 1 water.Frequently stir, (95 ℃ of temperature) leached 10 hours under heating condition, filtering separation.(3) deep oxidation: add a certain amount of sodium chlorate solution in the vanadium solution of oxidation acid leaching, making tetravalence vanadium complete oxidation is the pentavalent vanadium.(4) ion-exchange: the solution containing vanadium behind the deep oxidation is adsorbed with the strong basicity macroporous anion exchange resin, and the rear solution of absorption carries out desorb with 10% NaOH and 5%NaCl mixed solution.(5) precipitation: the vanadium elutriant that contains behind the Pro-concentration with ion exchange process is generated the ammonium meta-vanadate precipitation with the ammonium chloride precipitation.The ammonium meta-vanadate that is settled out is embathed three times with the 1-2% aqueous ammonium chloride solution again remove impurity, liquid recycles after treatment.(6) calcining and decomposing: after the oven dry of ammonium meta-vanadate filter cake, sending into calcining furnace, is the Vanadium Pentoxide in FLAKES product 400-600 ℃ of calcining and decomposing.The tail gas HCl recovery generates ammonium chloride and returns the use of precipitation operation.Use K
2S
2O
8As oxygenant, the leaching yield of vanadium is 91.5% in the bone coal, and the rate of recovery of vanadium is 83.0%.
Embodiment two:
According to above-mentioned broken ball milling sieve, the step such as oxidation acid leaching, deep oxidation, ion-exchange, precipitation, calcining operates successively, wherein in burden process, the oxygenant that adds in the bone coal breeze is K
2S
2O
7, the leaching yield of bone coal is 90.6%,, the rate of recovery of vanadium is 81.5%.
Embodiment three:
According to above-mentioned broken ball milling sieve, the step such as oxidation acid leaching, deep oxidation, ion-exchange, precipitation, calcining operates successively, wherein in burden process, the oxygenant that adds in the bone coal breeze is (NH
4)
2S
2O
8, the leaching yield of bone coal is 91.8%, the rate of recovery of vanadium is 82.2%.
Claims (2)
- One kind from contain navajoite stone oxidation conversion leach the method for vanadium extraction, it is characterized in that in the leaching pond, adding industrial sulphuric acid, to contain vanadium crushing raw ore, ball milling to crossing 80 mesh sieves, put into the leaching pond, add in the leaching pond by the weight ratio of 0.1-5% and to contain thiooxidant and stir, by solid-to-liquid ratio 1: 0.5-5, sour ore deposit than 1: the add-on of 2-9 control water, frequently stirring, under 10-100 ℃ of temperature, leached 1-12 hour filtering separation.Add the sodium chlorate solution that vanadiumcontent 0.5-1 doubly measures in the vanadium solution behind oxidation acid leaching, the tetravalence vanadium is oxidized to the pentavalent vanadium, then solution containing vanadium is adsorbed with the strong basicity macroporous anion exchange resin, the rear solution of absorption carries out desorb with 10% NaOH and 5%NaCl mixing solutions.To contain vanadium elutriant NH behind the Pro-concentration with ion exchange process 4The Cl precipitation generates the ammonium meta-vanadate precipitation, filters, and after the oven dry of ammonium meta-vanadate filter cake, sends into calcining furnace, is decomposed into V 400-600 ℃ of calcination 2O 5Product.
- 2. saidly according to claim 1 contain the method that oxidation conversion in the navajoite stone leaches vanadium extraction, it is characterized in that the said thiooxidant that contains is K 2S 2O 7Or Na 2S 2O 7Or (NH 4) 2S 2O 7Or K 2S 2O 8Or Na 2S 2O 8Or (NH 4) 2S 2O 8
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103059094A CN102851521A (en) | 2011-09-27 | 2011-09-27 | Method for extracting vanadium through oxidation conversion of vanadium-containing ores |
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|---|---|---|---|
| CN2011103059094A CN102851521A (en) | 2011-09-27 | 2011-09-27 | Method for extracting vanadium through oxidation conversion of vanadium-containing ores |
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| CN102851521A true CN102851521A (en) | 2013-01-02 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841682A (en) * | 2015-04-03 | 2015-08-19 | 张伟峰 | Comprehensive utilization method of stone coal resources |
| CN105648210A (en) * | 2016-01-13 | 2016-06-08 | 晟通亿和（天津）企业管理咨询有限公司 | Comprehensive utilization method of vanadium, heat energy, vanadium recovery process neutral dregs and tailings in low heating value stone coal vanadium ores |
| CN106048260A (en) * | 2016-08-15 | 2016-10-26 | 陕西华源矿业有限责任公司 | Technology of extracting vanadium from stone coal by resin adsorption in strong acid system |
| CN108866354A (en) * | 2018-06-20 | 2018-11-23 | 吉首大学 | A method of from high efficiency extraction vanadium in stone containing navajoite |
| CN109852820A (en) * | 2019-02-22 | 2019-06-07 | 梁刘友 | A method of producing vanadic anhydride |
| CN113106270A (en) * | 2021-03-26 | 2021-07-13 | 西部矿业股份有限公司 | Method for efficiently recovering vanadium based on modified acid leaching of vanadium-containing metallurgical slag |
-
2011
- 2011-09-27 CN CN2011103059094A patent/CN102851521A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841682A (en) * | 2015-04-03 | 2015-08-19 | 张伟峰 | Comprehensive utilization method of stone coal resources |
| CN105648210A (en) * | 2016-01-13 | 2016-06-08 | 晟通亿和（天津）企业管理咨询有限公司 | Comprehensive utilization method of vanadium, heat energy, vanadium recovery process neutral dregs and tailings in low heating value stone coal vanadium ores |
| CN105648210B (en) * | 2016-01-13 | 2018-01-26 | 晟通亿和（天津）企业管理咨询有限公司 | In a kind of low heat value vanadium from stone coal vanadium, heat energy, process for extracting vanadium and the method for comprehensive utilization of slag and tailings |
| CN106048260A (en) * | 2016-08-15 | 2016-10-26 | 陕西华源矿业有限责任公司 | Technology of extracting vanadium from stone coal by resin adsorption in strong acid system |
| CN108866354A (en) * | 2018-06-20 | 2018-11-23 | 吉首大学 | A method of from high efficiency extraction vanadium in stone containing navajoite |
| CN108866354B (en) * | 2018-06-20 | 2020-12-04 | 吉首大学 | Method for efficiently extracting vanadium from vanadium-containing ore |
| CN109852820A (en) * | 2019-02-22 | 2019-06-07 | 梁刘友 | A method of producing vanadic anhydride |
| CN113106270A (en) * | 2021-03-26 | 2021-07-13 | 西部矿业股份有限公司 | Method for efficiently recovering vanadium based on modified acid leaching of vanadium-containing metallurgical slag |
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Application publication date: 20130102 |