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Dokumentenidentifikation EP1511691 15.02.2007
EP-Veröffentlichungsnummer 0001511691
Titel VERFAHREN ZUR HERSTELLUNG VON VANADYLSULFATLÖSUNG
Anmelder Highveld Steel & Vanadium Corp. Ltd., Witbank, ZA
Erfinder DORMEHL, Gerhardus, Andries, 1055 Middleburg, ZA;
MONAGHAN, Albert, Patrick, 1034 Witbank, ZA
Vertreter Patentanwälte Gesthuysen, von Rohr & Eggert, 45128 Essen
DE-Aktenzeichen 60310927
Vertragsstaaten AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IT, LI, LU, MC, NL, PT, RO, SE, SI, SK, TR
Sprache des Dokument EN
EP-Anmeldetag 26.05.2003
EP-Aktenzeichen 037560745
WO-Anmeldetag 26.05.2003
PCT-Aktenzeichen PCT/IB03/02002
WO-Veröffentlichungsnummer 2003101893
WO-Veröffentlichungsdatum 11.12.2003
EP-Offenlegungsdatum 09.03.2005
EP date of grant 03.01.2007
Veröffentlichungstag im Patentblatt 15.02.2007
IPC-Hauptklasse C01G 31/02(2006.01)A, F, I, 20051017, B, H, EP

Beschreibung[en]
BACKGROUND TO THE INVENTION

THIS invention relates to a process for the preparation of a vanadyl sulphate solution.

It is known to produce vanadyl sulphate by dissolving vanadium pentoxide in hot dilute sulphuric acid under vigorous agitation and continued heating with the aid of sulphur dioxide as a reducing agent.

WO 02/04353 disclose a process for the preparation of a vanadyl sulphate solution by mixing vanadium pentoxide and vanadium trioxide and adding sulphuric acid solution.

The limited solubility of sulphur dioxide in acidic and aqueous solutions results in the emission of sulphur dioxide from the solution and this presents an environmental hazard. Overdosing of the solution with SO2 gas results in the unwanted formation of the lower valent vanadium sulphate, namely V2SO4 and not vanadyl sulphate (VOSO4).

Since the dissolution of vanadium pentoxide in sulphuric acid is endothermic heat has to be provided to drive the formation of vanadyl sulphate.

There is thus always a need for a new method for the production of vanadyl sulphate.

SUMMARY OF THE INVENTION

According to the invention a process for producing a vanadyl sulphate solution includes the steps of:

  1. (1) providing a starting material comprising vanadium trioxide (V2O3);
  2. (2) contacting the vanadium trioxide with an appropriate volume and concentration of a sulphuric acid solution to produce a vanadium trioxide suspension; and
  3. (3) contacting the vanadium trioxide suspension with a strong oxidising agent that is capable of raising the valency or oxidation state of the vanadium, thereby to dissolve the vanadium trioxide in the sulphuric acid to produce the vanadyl sulphate solution (VOSO4).

Various strong oxidising agents including peroxides and permanganate such as hydrogen peroxide, sodium peroxide and potassium permanganate, for example, can be used. Hydrogen peroxide is particularly preferred as it does not introduce any impurities into the final product.

The hydrogen peroxide is typically added slowly to the vanadium trioxide suspension due to the violent nature of the reaction.

BRIEF DESCRIPTION OF THE DRAWING

The invention will now be described in more detail, by way of example only, with reference to the accompanying drawings in which:

Figure 1
is a graph indicating the mass relationship between varying quality V2O3 expressed as V2O5 against constant 4.5g V2O5 portions in a 4.0 molar sulphuric acid solution; and
Figure 2
indicates the reduction potential in mVolt against the mass of the V2O3 used.

DESCRIPTION OF A PREFERRED EMBODIMENT

The crux of the invention is to use a strong oxidising agent to dissolve vanadium trioxide (V2O3), commonly referred to as Hivox, in a sulphuric acid solution to produce vanadyl sulphate (VOSO4).

In carrying out the process, a strong oxidising agent such as a peroxide or permanganate, for example, is used to dissolve the V2O3 in a warm sulphuric acid solution with constant stirring. Although various strong oxidising agents such as hydrogen peroxide, sodium peroxide, potassium permanganate, iodine, potassium iodate, potassium bromate, bromine, ammonium persulfate, persulfates of sodium and potassium, cerium (IV) sulphate, and potassium dichromate, for example, can be used, hydrogen peroxide is preferred as it does not introduce any impurities into the final product.

As the quality of industrial grade Hivox ranges typically from 115 to 122 percent equivalent V2O5, figure 1 can be used in order to determine an appropriate quantity of V2O3 for use in the process, depending on the quality of the starting material used. The required solution can be obtained by monitoring the reduction potential thereof in mVolt, as shown in figure 2, during the dissolution process. The start of production of vanadyl sulphate is illustrated at the point where the graph dips sharply.

The invention will now be illustrated by way of the following non-limiting example.

Example

Hydrogen peroxide was used to dissolve 3.0 grams Hivox (V2O3) in a warm (50°C) 4.0 molar sulphuric acid solution with constant stirring. The hydrogen peroxide was added dropwise as it reacted violently with the solution. During the dissolution process the reduction potential of the solution was continuously monitored and the addition of hydrogen peroxide stopped when the solution reached the end point at 600 mVolts.

The process proceeded according to the following formula:



        2V2O3 + 4H2SO4 + H2O2 → 4VOSO4 + 4H2O + H2↑.



During the process, the solution first turned green, which is indicative of the presence of V3+ ions, whereafter it turned blue, which is indicative of the presence of VO2+ ions present in the vanadyl sulphate end product.

From the above, it is evident that vanadyl sulphate can readily be made using Hivox (V2O3), which is generally more cost effective, and less hazardous, than the conventional process using V2O5.


Anspruch[de]
Verfahren zur Herstellung einer Vanadylsulfatlösung mit den folgenden Verfahrensschritten: (1) Bereitstellung eines Ausgangsmaterials, welches Vanadiumtrioxid (V2O3) enthält; (2) Inkontaktbringen des Vanadiumtrioxids mit einer Schwefelsäurelösung zur Herstellung einer Vanadiumtrioxidsuspension; und (3) Inkontaktbringen der Vanadiumtrioxidsuspension mit einem starken Oxidationsmittel, welches imstande ist, die Valenz oder den Oxidationszustand des Vanadiums heraufzusetzen, so daß das Vanadiumtrioxid in der Schwefelsäure gelöst wird, um eine Vanadylsulfatlösung (VOSO4) zu erzeugen. Verfahren nach Anspruch 1, wobei das starke Oxidationsmittel ausgewählt ist aus der Gruppe von Wasserstoffperoxid, Natriumperoxid, Kaliumpermanganat, Iod, Kaliumiodat, Kaliumbromat, Brom, Ammoniumpersulfat, Natrium- und Kaliumpersulfat, Cer(IV)-sulfat und Kaliumdichromat. Verfahren nach Anspruch 2, wobei das starke Oxidationsmittel Wasserstoffperoxid ist. Verfahren nach Anspruch 3, wobei das Wasserstoffperoxid tropfenweise zu der Vanadiumtrioxidsuspension hinzugegeben wird. Verfahren nach Anspruch 4, wobei die Zugabe des Wasserstoffperoxids beendet wird, wenn das Reduktionspotential der Vanadiumsulfatlösung einen vorbestimmten Endpunkt erreicht. Verfahren nach Anspruch 5, wobei der Endpunkt bei etwa 600 mVolt liegt.
Anspruch[en]
A process for producing a vanadyl sulphate solution includes the steps of: (1) providing a starting material comprising vanadium trioxide (V2O3); (2) contacting the vanadium trioxide with a sulphuric acid solution to produce a vanadium trioxide suspension; and (3) contacting the vanadium trioxide suspension with a strong oxidising agent that is capable of raising the valency or oxidation state of the vanadium, thereby to dissolve the vanadium trioxide in the sulphuric acid to produce the vanadyl sulphate solution (VOSO4). A process according to claim 1, wherein the strong oxidising agent is selected from the group comprising hydrogen peroxide, sodium peroxide, potassium permanganate, iodine, potassium iodate, potassium bromate, bromine, ammonium persulfate, persulfates of sodium and potassium, cerium (IV) sulphate, and potassium dichromate A process according to claim 2, wherein the strong oxidising agent is hydrogen peroxide. A process according to claim 3, wherein the hydrogen peroxide is added dropwise to the vanadium trioxide suspension. A process according to claim 4, wherein the addition of hydrogen peroxide is stopped when the reduction potential of the vanadium sulphate solution reaches a predetermined end point. A process according to claim 5, wherein the end point is at about 600mVolts.
Anspruch[fr]
Procédé de production d'une solution de sulfate de vanadyle comprenant les étapes consistant à : (1) fournir un matériau de départ comprenant du trioxyde de vanadium (V2O3); (2) mettre en contact le trioxyde de vanadium avec une solution d'acide sulfurique pour produire une suspension de trioxyde de vanadium ; et (3) mettre en contact la suspension de trioxyde de vanadium avec un agent oxydant puissant qui peut augmenter la valence ou l'état d'oxydation du vanadium, pour dissoudre ainsi le trioxyde de vanadium dans l'acide sulfurique afin de produire une solution de sulfate de vanadyle (VOSO4). Procédé selon la revendication 1, dans lequel l'agent oxydant puissant est choisi dans le groupe comprenant le peroxyde d'hydrogène, le peroxyde de sodium, le permanganate de potassium, l'iode, l'iodate de potassium, le bromate de potassium, le brome, le persulfate d'ammonium, les persulfates de sodium et de potassium, le sulfate de cérium (IV) et le dichromate de potassium. Procédé selon la revendication 2, dans lequel l'agent oxydant puissant est le peroxyde d'hydrogène. Procédé selon la revendication 3, dans lequel le peroxyde d'hydrogène est ajouté goutte à goutte à la suspension de trioxyde de vanadium. Procédé selon la revendication 4, dans lequel l'addition de peroxyde d'hydrogène est stoppée lorsque le potentiel de réduction de la solution de sulfate de vanadium atteint un paramètre prédéterminé. Procédé selon la revendication 5, dans lequel le paramètre est d'environ 600 m/volt.






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