Patent Application
20150139873
The invention relates to a method for the extraction of vanadiumpentoxide, V2O5, from a source containing vanadium.
Vanadiumpentoxide, V2O5, is mainly used as a catalyst in the chemical industry and for the production of ferrovanadium.
In the past there has been a great interest to recover vanadium or vanadium oxide from different sources. In particular, different routes for selective pre-oxidation of vanadium from raw iron has received much attention and e.g. EP 235 291, EP 134 351, U.S. Pat. No. 4,071,355 and GB 1 281 203 discloses recovery of vanadium oxide from molten metal.
The general object of the present invention is to provide an alternative production route for the extraction of vanadium from various sources in the form of vanadium pentoxide. This and other objects are achieved by means of a method as defined in claim 1. Preferred embodiments of the invention are specified in the dependent claims.
The present inventors have found that it is possible to extract vanadium in the form of in the form of vanadium pentoxide, V2O5, by evaporation of this oxide. To be specific, the claimed method includes the steps of:
The invention is defined in the claims.
Basically any vanadium containing source can be used in the claimed method. However from a practical point of view the vanadium containing source is suitably selected from the group of: ore, slag, ash and V2O5 formed by roasting vanadium-sulphide from spent petroleum refining catalysts since these are the most important sources. If the vanadium in said source is not in the form of vanadium pentoxide, V2O5, then it is necessary to convert at least part of the vanadium to V2O5 In most cases all vanadium is converted to V2O5 This is done by roasting the sulphide or by oxidation of the lower oxides (V3+/V4+) to pentoxide (V5+).
Preferably the ore is selected from the iron sands, magnetite, hematite, titani-ferrous magnetite and vanadium-titanium magnetite; the slag is selected from converter slag, submerged arc furnace slag, ladle slag and slag obtained by selective oxidation of vanadium from raw iron; and the ash is selected from petroleum coke ash, in particular fly ash and boiler ash.
The evaporation is promoted by an oxidizing atmosphere and the evaporation increases with increasing partial pressure of oxygen such that oxygen-enriched air and pure oxygen results in higher evaporation ability than in air.
Evaporation can take place from a solid and/or a liquid V2O5—containing source. A major source of supply is slag from the steel industry. In this case the slag should be liquid and an oxidizing gas is preferably blown into or through the liquid slag bath held at 1200° C. to 1900° C., preferably 1450° C. to 1700° C. The slag normally comprises at least three of the following components CaO, MgO, MnO, SiO2, TiO2, FeOx and VOx, wherein x indicates that the oxides need not be stoichiometric and that more than one valence state may present. Vanadium can have three valence states: V3+, V4+ and V5+. High slag basicities stabilizes higher vanadium oxidation states such that one should expect V4+/V5+ to be the predominant redox-pair.
Ash, such as petroleum coke ash can optionally be mixed with one or more of components selected from CaO, MgO, MnO, SiO2, TiO2, Al2O3 and FeOx and subjected to at least partly melting wherein the ash/slag mixture is liquid or solid-liquid mixture and held at 1200° C. to 1900° C., preferably 1450° C. to 1700° C. and wherein oxygen or oxygen enriched air is blown through the slag bath for generation and evaporation of V2O5.
Evaporation of V2O5 from a solid vanadium-containing source is a feasible alternative, in particular when using ore. The Swedish magnetite ore for instance contains about 1.5% V. In one preferred embodiment magnetite ore is roasted to hematite at a temperature in the range of 1100-1300° C. by using oxygen as a carrier gas in a fluidized bed reactor. In this case, the temperature should be adjusted to lay just under the softening temperature of the vanadium containing iron ore in order to avoid problems with sticking. As an alternative to oxygen, air or oxygen enriched air containing 22-99% oxygen may be used.
As a precursor for the source of V2O5, it is possible use vanadium-sulphide, V3 S4, from spent catalysts. V354 is deposited in high amounts on petroleum refining catalysts for desulphurization. When these catalysts are spent said sulphide can be converted to oxide by a roasting treatment and thus provide a source of V2O5. The roasting can be performed by conventional methods known in the art. The roasting of V3 S4 and the evaporation of V2O5 may be performed in a single step by oxidizing the V3 S4 at temperatures of at least 1000° C., so that V2O5 is evaporated as it is formed.
The evaporated V2O5 is recovered by subjecting the V2O5 containing gas to condensation. Any type of condensation can be used. A conventional cold trap may be used.
Vanadium containing slag from the production of high alloyed tool steels was treated according to the invention. The slag had the following composition in weight percent; 5% V2O5, 37.5% CaO, 20% FeO, and 37.5% SiO2.
The slag was split in two samples. The samples were heated in air under laboratory conditions in a platinum crucible at 1853K respectively 1873K during 120 minutes. The exit gas from the furnace was cooled, filtered and formed oxide particles were collected. For the sample heated to 1823K 80% by weight of V2O5 was recovered. For the sample heated to 1873K 90% by weight of V2O5 was recovered. The purity of the vanadium pentoxide was over 95% by weight.
Pet coke slag was heated in an alumina crucible and melted in an electric arc furnace. The slag had the following composition expressed in weight percent; 42.8% V2O3, 12.5% CaO, 10.7% FeO, 7.4% Al2O3 and 26.6% SiO2.
The slag was heated in the furnace from room temperature to a temperature of 1480° C. Air was blown into the liquid slag. This resulted in an oxidation of FeO to Fe2O3 and of V2O3 to V2O5. The slag was kept liquid under oxidizing conditions for 400 minutes. The reaction was found to be faster with oxygen blowing. The exit gas was condensed in a cold trap.
The amount of V2O5 found in the cold trap was equivalent to 92% by weight of the original amount in the pet coke slag. The purity of the vanadium pentoxide was over 98% by weight.
A Swedish magnetite ore containing 95% Fe3O4, 1.5% V2O5 and the residual mainly SiO2 was heated in an alumina crucible for two hours at 1623K under a flow of oxygen enriched air containing 50% oxygen. The content of V2O5 in the magnetite ore decreased after 2 hours processing from 1.5% to 0.3%. The purity of the vanadium pentoxide was 95% by weight.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1250767-9 | Jul 2012 | SE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SE2013/050852 | 7/3/2013 | WO | 00 |
