CN101550492B - Method for extracting vanadium pentoxide from vanadium-containing ferro phosphorus - Google Patents

Method for extracting vanadium pentoxide from vanadium-containing ferro phosphorus Download PDF

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Publication number
CN101550492B
CN101550492B CN2008101433739A CN200810143373A CN101550492B CN 101550492 B CN101550492 B CN 101550492B CN 2008101433739 A CN2008101433739 A CN 2008101433739A CN 200810143373 A CN200810143373 A CN 200810143373A CN 101550492 B CN101550492 B CN 101550492B
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vanadium
roasting
vanadium pentoxide
extracting
soda ash
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CN101550492A (en
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阳云徕
王勇军
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HUNAN CHUANGDA METALLURGICAL GROUP CO Ltd
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HUNAN CHUANGDA METALLURGICAL GROUP CO Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for extracting vanadium pentoxide from vanadium-containing ferro phosphorus, the method adds lime and soda ash for oxidation roasting and carries out leaching by clean water and ion-exchanging, thereby extracting the vanadium pentoxide from the vanadium-containing ferro phosphorus. The 15-35 percent of lime is added into ferro phosphorus ore for carrying out ballmilling, 30-50 percent of soda ash (calculated by the weight of the crude ore) is added for granulation, granulation materials enter a rotary kiln for oxidation roasting, the stirring leaching is carried out in clean water solution, vanadium-containing solution uses ion exchange resin for absorbing vanadium; the elution, the vanadium sedimentation and the pyrolysis are further carried out, therebyobtaining a vanadium pentoxide product. The production process of the method completely eliminates the environmental pollution caused by waste gas, waste water and waste residue, the use of the limeand the soda ash as additives for roasting can not only fix more than 90 percent of phosphorus in the ferro phosphorus ore into the leached residue, but also fully oxidize the vanadium in the ferro phosphorus ore for generating sodium vanadate and avoid the problem of easy sintering caused by high iron content of raw materials, so that the impurities which enter the vanadium solution are fewer andthe yield rate of the vanadium is as high as 82-88 percent.

Description

From vanadophosphoric ferric, extract the method for Vanadium Pentoxide in FLAKES
Technical field
The present invention relates to the chemical industry metallurgical field, particularly a kind of method of from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES.
Background technology
Vanadium is the high-melting-point rare metal, has many good performances.In industries such as metallurgy, chemical industry purposes is widely arranged, along with the high speed development of China's modernization construction, the demand of vanadium and compound thereof is increasing.But navajoite resource scarcity and dispersion, current main source are to extract Vanadium Pentoxide in FLAKES from contain bone coal ore deposit and v-ti magnetite.In recent years, the process for extracting vanadium that contains the scherbinaite colliery has been done many researchs and production practice both at home and abroad, also obtained the effect of a lot of satisfactions, but that the bone coal ore deposit contains vanadium is low, generally contain V 2O 50.6~1.2%, and the present smelting technology ubiquity rate of recovery is low, facility investment is big, working cost is high, and waste water and waste residue shortcoming such as are difficult to eliminate fully to the pollution of environment.
For addressing the above problem, Chinese patent CN1970803A discloses " utilizing the technology of vanadophosphoric ferric extraction smelting of vanadium vanadium iron ", and this technology comprises the steps:
1, at first vanadophosphoric ferric (containing V5%) is dropped in the electric furnace in 1.5 times of amounts that contain the V ratio with NaCO3, be heated to 2000 ℃, melting was poured in the hot metal ladle after 2 hours, was blown into oxygen-rich air when temperature drops to 1400 ℃ in melt, skimmed the scum silica frost that contains vanadium phosphorus;
2, fused molten iron ingot casting in the hot metal ladle is cooled to the finished product ingot iron;
3, step 1 skim the scum silica frost that contains vanadium phosphorus through cooling, be milled to powder (fineness reaches 100 orders), make pelletizing, roasting 2 hours with addition of sodium salt powder (yellow soda ash); The roasting process temperature is controlled at 900 ℃;
4, by the water logging pelletizing solvend in the pelletizing is dissolved into acquisition vanadic acid sodium and sodium phosphate mixing solutions in the water, adds CaO in this solution, go through 24 hours precipitations, through press filtration, the phosphorus slag filter cake is mixed and made into phosphate fertilizer through chemical industry slaking and smelted furnace cinder proportioning again;
5, in the filtrate that step 4 produced, add sulfuric acid, obtain the Vanadium Pentoxide in FLAKES solid sediment; Through press filtration, be melt into the sheet vanadium, deliver to electrosmelting again and produce the vanadium iron finished product.
This technology combines electric furnace smelting method deironing and water immersing method smelting process for extracting vanadium, dephosphorization technique and technology in the vanadium have been innovated, and fully utilize, reach effect preferably, and solved the low problem of the rate of recovery to a certain extent, but because it adopts the electric furnace smelting method deironing, so there are production cost height, deficiency that facility investment is big; Simultaneously, because it adopts water immersing method to smelt process for extracting vanadium, the loss of the phosphorous height of product, vanadium is big, the not high deficiency of the rate of recovery of vanadium so exist.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, (contain V and provide a kind of raw material to contain the vanadium height 2O 5More than 9%), production cost is low, investment is little, the rate of recovery of vanadium is high extracts the method for Vanadium Pentoxide in FLAKES from vanadophosphoric ferric.
Technical scheme of the present invention is: a kind of method of extracting Vanadium Pentoxide in FLAKES from vanadophosphoric ferric, it is levigate with being mixed into ball mill after vanadophosphoric ferric and the lime fragmentation, the ball milling material adds the roasting again of granulating behind the soda ash, roasting material adds water and advances the wet-type ball mill wet ball mill, the ball milling ore pulp leaches with mechanical stirring, leaches slurry filtration, after containing vanadium solution and sending storage tank cooling clarification, send anionite-exchange resin absorption vanadium, the vanadium of absorption obtains high-grade Vanadium Pentoxide in FLAKES product through wash-out, precipitated crystal, pyrolysis.
Allocating amount of lime into is 15~35% of vanadium ferrophosphorus weight, and allocating soda ash weight into is 30~50% of vanadium ferrophosphorus weight.
Roasting material needs to granulate earlier, and the spherolite diameter is controlled in the scope of Φ 3~15mm, maturing temperature 〉=750 ℃,<900 ℃, roasting time is〉2 hours ,≤5 hours.
Roasting is discharged the direct slide of heat material and is gone into tank, is mixed into wet-type ball mill pulp ball milling (mechanical milling process reality also is leaching process), material: water=1:1.5~5, utilize heat to expect water temperature is raised to 50~95 ℃, heating outside not needing.
The hot ore pulp of ball milling send mechanical agitating tank, 35~95 ℃ of temperature, and extraction time 0.5~1.5 hour in the time of leaching process, can blast the partial roasting flue gas, the CO in the flue gas in groove 2More favourable with heat to the leaching of vanadium.
The present invention is owing to adopt as above design, compared with prior art, Automation of Manufacturing Process degree height, easy to operate, stable and reliable operation, the recovery rate of vanadium can reach 82-88%, the valuable metals such as iron in the also recyclable raw material, eliminated the influence of the three wastes fully, had that production cost is low, characteristics such as the rate of recovery height of little, the vanadium of investment, pollution-free, good product quality environment.
Below in conjunction with embodiment detailed content of the present invention is further described.
Embodiment
Embodiment one:
A kind of method of extracting Vanadium Pentoxide in FLAKES from vanadophosphoric ferric, it comprises the steps:
Ball milling: vanadophosphoric ferric and lime are mixed into dry method respectively after the fragmentation to drive the streaming ball mill levigate, the size range of ball milling material is that 80% breeze granularity is at the 100-200 order, lime adding amount is 15-35% (by a raw ore weight) of kakoxene weight, can adjust the add-on of lime according to the content of iron, phosphorus in the raw material.
Granulate, roasting: the ball milling material adds the roasting of granulating behind an amount of soda ash, and the add-on of soda ash is the 30-50% (by raw ore weight) of kakoxene weight, can adjust the add-on of soda ash according to the content of vanadium in the raw material; The spherolite diameter of granulating is Φ 3-15mm, and the too big burning of particle diameter is not saturating, and too little flue dust is many; Roasting adopt high-level efficiency, automatization, easy to operate, reliable, raw material is changed and output fluctuation has the rotary kiln of very strong adaptive faculty, also can adopt fluidizing furnace, 750 ℃~780 ℃ of maturing temperatures, roasting time is 2.1~2.5 hours, and the heat energy in the roasting process can adopt heavy oil, Sweet natural gas or coal gas.
Wet ball mill: roasting is discharged the direct slide of heat material and is gone into tank, is mixed into wet-type ball mill pulp ball milling (mechanical milling process reality also is leaching process), material: water=1:1.5~2.0, with the heat material water temperature is raised to 50~95 ℃, and do not heat outside not needing.Add the water wet ball mill while hot and can make full use of heat energy, leaching process does not need outer heating, can save extraction time again, is again the process that leaches in the time of ball milling.
Leach: the hot ore pulp behind the wet ball mill is sent into mechanical agitating tank, and 35~40 ℃ of temperature extraction time 0.5-1.5 hour, can blast the partial roasting flue gas simultaneously, and utilize the CO in the flue gas in groove 2And heat, more favourable to the leaching of vanadium.
Filter, clarification: the slag liquid that leaches ore pulp separates and adopts band filter to filter, countercurrent washing slag 2-5 time, the wash water total amount be the quantity of slag 2-3 doubly, filtered liquid and the 1st wash water are merged into ion exchange liquid and are clarified stand-byly, all the other washingss return use.
The absorption vanadium: the ion exchange liquid that filters after clarifying send anionite-exchange resin absorption vanadium, and the exchange tail washings mainly contains cation impurities such as a small amount of sodium, silicon, phosphorus, can all return use after treatment.
Wash-out, precipitated crystal: the anionite-exchange resin NaCL+NH that adsorbs saturated vanadium 4The mixing solutions wash-out of CL obtains the strong solution of ammonium vanadate and vanadic acid sodium, and ammonium vanadate and sodium vanadate solution send in the precipitation pond and add NH 4CL, precipitated crystal goes out ammonium meta-vanadate, and sedimentation time is more than 2 hours.
Pyrolysis: ammonium meta-vanadate is delivered in the calcining furnace after washing, dehydration, obtains the Vanadium Pentoxide in FLAKES product of purity more than 99% 400-550 ℃ of following pyrolysis.
Embodiment two:
A kind of method of from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES, 810~840 ℃ of its ball milling material maturing temperatures, roasting time is 3.0~3.5 hours; The material of wet ball mill: water=1:3.0~3.5; 70~75 ℃ of the extraction temperatures of the hot ore pulp behind the wet ball mill.All the other steps are identical with embodiment one.
Embodiment three:
A kind of method of from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES, 870~899 ℃ of its ball milling material maturing temperatures, roasting time is 4~5 hours; The material of wet ball mill: water=1:4~5; The extraction temperature 90-95 of the hot ore pulp behind the wet ball mill ℃.All the other steps are identical with embodiment one.
The present invention adopts lime and soda ash to make roasting additive, both the phosphorus more than 90% in the kakoxene can be fixed in the leached mud, can make the abundant oxidation of vanadium in the kakoxene again and generate water-soluble vanadic acid sodium, also can avoid because of the high agglomerating problem easily of raw material iron content, the impurity that enters vanadium solution is few, and service water after treatment can all return use, and leached mud iron content height can be made ferrophosphorus and sell, or direct marketing gives the cement mill, or smelts into the pig iron by magnetic method.

Claims (3)

1. method of from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES, it is characterized in that being mixed into ball mill after vanadophosphoric ferric and the lime fragmentation levigate, allocating amount of lime into is 15~35% of vanadium ferrophosphorus weight, the ball milling material adds the roasting again of granulating behind the soda ash, allocating soda ash weight into is 30~50% of vanadium ferrophosphorus weight, roasting material adds water and advances the wet-type ball mill wet ball mill, the ball milling ore pulp leaches with mechanical stirring, leach slurry filtration, after containing vanadium solution and sending storage tank cooling clarification, send anionite-exchange resin absorption vanadium, the vanadium of absorption is through wash-out, precipitated crystal, pyrolysis obtains high-grade Vanadium Pentoxide in FLAKES product.
2. the method for from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES according to claim 1, it is characterized in that roasting material needs to granulate earlier, the spherolite diameter is controlled in the scope of Φ 3~15mm, maturing temperature 〉=750 ℃,<900 ℃, roasting time be>2 hours ,≤5 hours; Roasting is discharged the direct slide of heat material and is gone into tank, is mixed into wet-type ball mill pulp ball milling, and mechanical milling process reality also is leaching process, material: water=1: 1.5~5, utilize heat to expect water temperature is raised to 50~95 ℃, heating outside not needing.
3. the method for from vanadophosphoric ferric, extracting Vanadium Pentoxide in FLAKES according to claim 1 and 2, it is characterized in that the hot ore pulp of ball milling send mechanical agitating tank, 35~95 ℃ of temperature, extraction time 0.5~1.5 hour, in the time of leaching process, in groove, blast the partial roasting flue gas.
CN2008101433739A 2008-10-16 2008-10-16 Method for extracting vanadium pentoxide from vanadium-containing ferro phosphorus Active CN101550492B (en)

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CN101898793B (en) * 2010-07-28 2011-08-31 攀钢集团冶金工程技术有限公司 Leaching method of vanadium-containing clinker
CN102430266B (en) * 2010-09-29 2014-12-10 攀钢集团钢铁钒钛股份有限公司 Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide

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