WO2000056662A1 - Vanadium oxidation method - Google Patents
Vanadium oxidation method Download PDFInfo
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- WO2000056662A1 WO2000056662A1 PCT/AT2000/000062 AT0000062W WO0056662A1 WO 2000056662 A1 WO2000056662 A1 WO 2000056662A1 AT 0000062 W AT0000062 W AT 0000062W WO 0056662 A1 WO0056662 A1 WO 0056662A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
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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
- 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
Definitions
- the invention relates to a method for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V.
- the pH of the solution is then changed to a range which is favorable for the precipitation of vanadium pentoxide.
- the mother liquor is cleaned.
- cationically dissolved heavy metals are separated from the mother liquor by precipitation.
- a method is to be provided with which it is possible to minimize the waste and waste water problem which arises from the oxidizing leaching of vanadium from feedstocks containing vanadium.
- the object is achieved in that the oxidation is carried out at least partially with elemental chlorine as the oxidizing agent, whereby vanadium compounds of the oxidation state IV and / or V are formed.
- the vanadium to be oxidized is expediently present in a solid which is dispersed or dissolved in a liquid.
- Residues from combustion oil ash
- petroleum processing gasification residues
- vanadium-containing catalysts are predominantly used as the vanadium-containing solid which is used as the starting material in the process according to the invention.
- the solid is preferably dissolved or dispersed in an aqueous solution.
- the solution can be presented as a deionized product.
- electrolyte-containing aqueous solutions for example a sodium chloride, sodium sulfate or HCl solution
- a particularly preferred embodiment of the process according to the invention is characterized in that a solution containing sodium chloride is used as the liquid for dispersing or dissolving the solid.
- chlorine gas is introduced into the solution or dispersion (both physical states can also occur simultaneously), the temperature being not essential.
- V 2 0 3 + 4 H + + CIO " > 2 V0 2+ + Cl " + 2 H 2 0
- the dissolving or oxidizing step can take place either in one pass or in several sub-steps.
- the choice of procedure is primarily determined by the matrix of the feed material.
- the oxidation is carried out in one stage and with elemental chlorine as the oxidizing agent.
- the method according to the invention can, however expediently also be carried out in such a way that the oxidation is carried out in two stages, elemental chlorine being used as the oxidizing agent in at least one stage.
- soluble vanadium of oxidation stage IV into soluble vanadium (V) using chlorine gas as the oxidizing agent in a one-step process.
- soluble vanadium (IV) in a material dispersed or dissolved in a suitable liquid containing vanadium by oxidation with chlorine gas in a one-step process to soluble vanadium (V).
- vanadium (III) in a material dispersed or dissolved in a suitable liquid containing vanadium by oxidation with chlorine gas in a one-step process to soluble vanadium (V).
- soluble vanadium (IV) there is also the possibility of carrying out the oxidation of the above-mentioned starting material in a two-stage process, treatment with chlorine gas in a first stage until the vanadium is present quantitatively as soluble vanadium (IV).
- the solution is separated from the solid residue and can be oxidized to vanadium (V) in a further oxidation step using chlorine gas.
- this two-stage process can also be carried out in such a way that an oxidizing agent other than chlorine gas is used in one of the two stages.
- the chlorine gas used as the oxidizing agent can also be combined with other oxidizing agents in each of the stages described above.
- the transition between the different oxidation levels of the dissolved vanadium is shown optically by the color transition and can be followed spectrophotometrically.
- the vanadium-containing starting material is preferably dispersed or dissolved in a sodium chloride-containing solution and the oxidation of the vanadium up to oxidation level V of the vanadium is carried out with formation of an aqueous solution of vanadiu (V) and then at least a part of the oxidized vanadium is separated from the solution by precipitation , whereby what is liked Polyvanadat and a sodium chloride-containing mother liquor can be obtained.
- the polyvanadate is usually precipitated by setting an optimal pH value for the precipitation with neutralizing agent, e.g. Sodium hydroxide solution and setting an optimal precipitation temperature.
- the polyvanadate can be separated from the mother liquor by filtration. Depending on the precipitation conditions, residual levels of vanadium in the mother liquor of ⁇ 0.5 g / l are achieved in this separation operation. After this separation operation, the mother liquor has a NaCl content of approx. 120 g / 1.
- the elemental chlorine used as the oxidizing agent in the process according to the invention is advantageously produced by electrolysis of a solution containing sodium chloride, free chlorine gas and an anolyte containing CIO " or C10 3 " being formed on the anode and a catholyte containing sodium hydroxide solution on the cathode.
- a solution containing sodium chloride, free chlorine gas and an anolyte containing CIO " or C10 3 " being formed on the anode and a catholyte containing sodium hydroxide solution on the cathode.
- part of the chlorine formed is converted to CIO " or C10 3 " during electrolysis in the anolyte. The proportion depends on which sodium chloride-containing feed solution is used.
- the sodium chloride-containing mother liquor obtained after removal of the precipitated polyvanadate is advantageously used as the sodium chloride-containing feed solution for the electrolysis.
- the chlorine gas required for the oxidation process can thus be produced from the mother liquor containing sodium chloride.
- the mother liquor therefore does not have to be subjected to the complex processes for separating heavy metals and reducing the chloride load by evaporation and crystallization, which are necessary for disposal as waste water.
- the anolyte from the electrolysis is therefore used as a liquid for dispersing or dissolving the vanadium-containing solid which is provided as the starting material for the oxidation.
- C10 " -containing and C10 3 " -containing anolyte can also be returned to the dissolving stage, since both substances are suitable for the oxidizing solution V (III) -containing products.
- the anolyte which is circulated in this way can also contain iron and nickel, the iron being present in iron-containing anolyte as Fe (III), for example as dissolved FeCl 3 .
- Fe (III) iron-containing anolyte
- Both ionogenic metals (Fe and Ni) can be deposited from the mother liquor both before and after the electrolysis, the deposition of Fe (III) by hydroxide formation being complete at a pH of 5.
- Nickel which is chemically neutral in the cycle, can be separated, for example by hydroxide precipitation or carbonate precipitation, to the desired final contents.
- the mother liquor from the polyvanadate precipitation can also be used as catholyte both before and after a partial or complete separation of iron and nickel, the sodium chloride-containing sodium hydroxide solution also being able to be recycled without restriction into the precipitation stage for the polyvanadate precipitation.
- the electrolyzed catholyte is used to precipitate the polyvanadate from the aqueous solution containing vanadium (V) oxidized.
- the process according to the invention thus enables a circuit to be closed with regard to the recycling and recycling of the process water obtained in the process and thereby a practically wastewater-free overall process.
- Electrolytic chlorine production from the mother liquor can also be used for heavy metal precipitation in the cathode compartment by hydroxide formation if required. If necessary, matrix elements of the feed material can be separated from the mother liquor by precipitation with hydroxide formers. Residual vanadium does not interfere in the electrolyte, since the chlorine-saturated anolyte can also be returned to the dissolution and oxidation stages.
- Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method.
- the chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V2 ⁇ 3 had been placed.
- the suspension was composed as follows: 40 g NaCl, 30 g Na 2 S0 4 , 14.9 g V 2 0 3 , 330 ml water.
- the stoichiometric amount of chlorine gas based on the amount of V 2 0 3 presented, was introduced.
- the suspension was filtered and examined for dissolved vanadium. A total of 4.9 g V (IV) was measured.
- V 2 0 3 + 4 H + + CIO " > 2 V0 2+ + Cl " + 2 H 2 0
- Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method.
- the chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V 2 0 3 had been placed.
- the suspension was composed as follows: 60 g NaCl, 45 g Na 2 SO 4 , 22.35 g V 2 0 3 , 500 ml water. It was initiated twice the stoichiometric amount of chlorine gas, based on the amount of V 2 0 3 presented for the oxidation of V 2 0 3 to V0 2 + . After the end of the experiment, polyvanadate precipitation was carried out.
- the vanadium could be precipitated quantitatively as V 2 0 5 except for a residual content of 0.14 g / 1 in the reaction solution.
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Abstract
Description
Verfahren zur Oxidation von VanadiumProcess for the oxidation of vanadium
Die Erfindung betrifft ein Verfahren zur Oxidation von Vanadium in Materialien, welche Vanadium in einer Oxidationsstufe kleiner als V enthalten.The invention relates to a method for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V.
Es ist bekannt, Vanadium der Oxidationsstufe kleiner als IV aus vanadiumoxidhaltigen Einsatzprodukten, die als Feststoff vorliegen, durch oxidierende Laugung zu isolieren. Der Laugungsvorgang wird dabei über das Redoxpotential so geführt, daß das Vanadium in der Oxidationsstufe IV in Lösung geht. Als Grundelektrolyt wird für die Laugung üblicherweise wässrige Schwefelsäure eingesetzt. Nach dem Laugungsvorgang und Abscheidung des unlöslichen Rückstandes durch ein mechanisches Abscheideverfahren wird die Lösung in einem zweiten Oxidationsprozeß unter Einstellung eines geeigneten Redoxpotentials mit Oxidationsmittel weiterbehandelt, bis das Vanadium in die Oxidationsstufe V (im folgenden auch als Vanadium (V) oder V(V) bezeichnet) übergeführt ist. Anschließend wird der pH-Wert der Lösung in einen für die Fällung von Vanadiumpentoxid günstigen Bereich verändert. Nach der Fällung wird die Mutterlauge nachgereinigt. Bei diesem Nachreinigungsvorgang werden aus der Mutterlauge kationisch gelöste Schwermetalle durch Fällung abgetrennt.It is known to isolate vanadium of the oxidation state less than IV from feed products containing vanadium oxide, which are present as a solid, by oxidizing leaching. The leaching process is carried out via the redox potential so that the vanadium goes into solution in oxidation state IV. Aqueous sulfuric acid is usually used as the base electrolyte for leaching. After the leaching process and separation of the insoluble residue by means of a mechanical separation process, the solution is further treated with oxidizing agent in a second oxidation process while setting a suitable redox potential until the vanadium has reached the oxidation state V (hereinafter also referred to as vanadium (V) or V (V) ) is transferred. The pH of the solution is then changed to a range which is favorable for the precipitation of vanadium pentoxide. After the precipitation, the mother liquor is cleaned. In this post-cleaning process, cationically dissolved heavy metals are separated from the mother liquor by precipitation.
Diese Form der Oxidation und Fällung erfordert einen beträchtlichen Einsatz an Oxidationsmitteln und Fällungsmitteln, die nicht regeneriert werden können. Nach Abtrennung des Vanadiumpentoxids muß die Mutterlauge nach aufwendigen Methoden behandelt werden, um sie aus dem Prozeß ausschleusen zu können, wobei die erforderliche Behandlung von weiteren in der Mutterlauge vorliegenden Elementen und Verbindungen sowie von den Emissionsvorschriften abhängt, die für den Austrag der Mutterlauge als Abwasser gelten. Schwermetalle müssen durch Fällung und/oder Ionenaustausch abgetrennt werden. In vielen Anwendungsfällen ist die Mutterlauge auch eisen- und nickelhaltig. Auch hier muß eine Abtrennung durch mehrstufige Fällung und/oder Ionenaustausch erfolgen.This form of oxidation and precipitation requires considerable use of oxidants and precipitants that cannot be regenerated. After the vanadium pentoxide has been separated off, the mother liquor has to be treated by elaborate methods in order to be able to discharge it from the process, the treatment required depending on further elements and compounds present in the mother liquor and on the emission regulations which apply to the discharge of the mother liquor as waste water . Heavy metals have to be separated by precipitation and / or ion exchange. In many applications this is Mother liquor also contains iron and nickel. Here too, separation by multi-stage precipitation and / or ion exchange must take place.
Die vorliegende Erfindung stellt sich daher die Aufgabe, ein Verfahren zur Oxidation von Vanadium in Materialien, welche Vanadium in einer Oxidationsstufe kleiner als V enthalten, bereitzustellen, das diese Schwierigkeiten und Probleme vermeidet. Insbesondere soll ein Verfahren bereitgestellt werden, mit dem es gelingt, das bei der oxidierenden Laugung von Vanadium aus vanadiumhaltigen Einsatzstoffen bestehende Abfall- und Abwasserproblem zu minimieren.It is therefore the object of the present invention to provide a process for the oxidation of vanadium in materials which contain vanadium in an oxidation state less than V, which avoids these difficulties and problems. In particular, a method is to be provided with which it is possible to minimize the waste and waste water problem which arises from the oxidizing leaching of vanadium from feedstocks containing vanadium.
Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß die Oxidation zumindest teilweise mit elementarem Chlor als Oxidationsmittel ausgeführt wird, wobei Vanadiumverbindungen der Oxidationsstufe IV und/oder V gebildet werden.According to the invention the object is achieved in that the oxidation is carried out at least partially with elemental chlorine as the oxidizing agent, whereby vanadium compounds of the oxidation state IV and / or V are formed.
Zweckmäßig liegt das zu oxidierende Vanadium in einem Feststoff vor, der in einer Flüssigkeit dispergiert oder gelöst ist.The vanadium to be oxidized is expediently present in a solid which is dispersed or dissolved in a liquid.
Als vanadiumhaltiger Feststoff, der im erfindungsgemäßen Verfahren als Ausgangsmaterial eingesetzt wird, kommen vorwiegend Rückstände der Verbrennung (Ölaschen) , der Erdölverarbeitung (Vergasungsrückstände) und vanadiumhaltige Katalysatoren zur Anwendung.Residues from combustion (oil ash), petroleum processing (gasification residues) and vanadium-containing catalysts are predominantly used as the vanadium-containing solid which is used as the starting material in the process according to the invention.
Der Feststoff wird bevorzugt in einer wässrigen Lösung gelöst oder dispergiert. Die Lösung kann als Deionat vorgelegt werden. Es unterliegt aber auch die Verwendung elektrolythaltiger wässriger Lösungen, beispielsweise einer Natriumchlorid-, Natriumsulfat- oder HCl-Lösung keiner Einschränkung. Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß als Flüssigkeit zum Dispergieren oder Lösen des Feststoffes eine natriumchloridhaltige Lösung eingesetzt wird. Zur Durchführung der Oxidation wird in die Lösung oder Dispersion (beide Aggregatzustände können auch gleichzeitig auftreten) Chlorgas eingeleitet, wobei die Temperatur nicht wesentlich ist. Niedrige Temperaturen im Bereich der Raumtemperatur werden bevorzugt, da dadurch einerseits eine höhere Chlorlöslichkeit in der Lösung erreicht wird, andererseits aber die Reaktionsgeschwindigkeit ausreichend ist, um eine rasche Umsetzung zu erzielen, und die Oxidationswirkung von Chlor im Redoxsystem C12/C1"//V(<V) /V(V) hoch ist (das Redoxgleichgewicht liegt auf der Seite von V(V) ) .The solid is preferably dissolved or dispersed in an aqueous solution. The solution can be presented as a deionized product. However, the use of electrolyte-containing aqueous solutions, for example a sodium chloride, sodium sulfate or HCl solution, is also not subject to any restrictions. A particularly preferred embodiment of the process according to the invention is characterized in that a solution containing sodium chloride is used as the liquid for dispersing or dissolving the solid. To carry out the oxidation, chlorine gas is introduced into the solution or dispersion (both physical states can also occur simultaneously), the temperature being not essential. Low temperatures in the region of room temperature are preferred, since on the one hand this results in a higher chlorine solubility in the solution, but on the other hand the reaction rate is sufficient to achieve a rapid reaction and the oxidation effect of chlorine in the redox system C1 2 / C1 " // V (<V) / V (V) is high (the redox balance is on the side of V (V)).
Während des Einleitvorganges werden Vanadiumverbindungen, die in einer Oxidationsstufe kleiner als V vorliegen oxidierend gelöst. Abhängig von den Reaktionsbedingungen erfolgt dieser Löse- und Oxidationsschritt nach folgenden Reaktionen:During the introduction process, vanadium compounds which are in an oxidation state less than V are dissolved in an oxidizing manner. Depending on the reaction conditions, this dissolution and oxidation step takes place after the following reactions:
Cl2 + 2 e" 2 Cl* Cl 2 + 2 e " 2 Cl *
Cl -2 f+ _2c rHi22(0 2 CIO" + 4 H+ + 2 e" Cl -2 f + _2c rHi2 2 (0 2 CIO " + 4 H + + 2 e "
V203 + 2 H20 + Cl2 = HV2O5" + 3 H+ + 2 Cl" V 2 0 3 + 2 H 2 0 + Cl 2 = HV2O5 " + 3 H + + 2 Cl "
V203 + 2 H+ + Cl2 => 2 V02+ + H20 + 2 Cl" V 2 0 3 + 2 H + + Cl 2 => 2 V0 2+ + H 2 0 + 2 Cl "
V203 + 4 H+ + CIO" => 2 V02+ + Cl" + 2 H20V 2 0 3 + 4 H + + CIO " => 2 V0 2+ + Cl " + 2 H 2 0
2 V02+ + 5 H20 H3V207 " + 7 H+ + 2 e" 2 V0 2+ + 5 H 2 0 H 3 V 2 0 7 " + 7 H + + 2 e "
V02+ + 3 H20 <=> H2V04 " + 4 H+ + e" V0 2+ + 3 H 2 0 <=> H 2 V0 4 " + 4 H + + e "
V02+ + H20 V0 + + 2 H+ + e" V0 2+ + H 2 0 V0 + + 2 H + + e "
Abhängig vom Einsatzmaterial kann der Löse- oder Oxidationsschritt entweder in einem Durchgang oder in mehreren Teilschritten erfolgen. Die Wahl der Verfahrensführung wird vorwiegend von der Matrix des Einsatzmaterials bestimmt.Depending on the feed material, the dissolving or oxidizing step can take place either in one pass or in several sub-steps. The choice of procedure is primarily determined by the matrix of the feed material.
In einer bevorzugten Ausführungsform wird die Oxidation einstufig und mit elementarem Chlor als Oxidationsmittel ausgeführt. Das erfindungsgemäße Verfahren kann aber zweckmäßig auch so durchgeführt werden, daß die Oxidation zweistufig ausgeführt wird, wobei in mindestens einer Stufe elementares Chlor als Oxidationsmittel eingesetzt wird.In a preferred embodiment, the oxidation is carried out in one stage and with elemental chlorine as the oxidizing agent. The method according to the invention can, however expediently also be carried out in such a way that the oxidation is carried out in two stages, elemental chlorine being used as the oxidizing agent in at least one stage.
So ist es beispielsweise möglich, lösliches Vanadium der Oxidationsstufe IV unter Verwendung von Chlorgas als Oxidationsmittel in einem einstufigen Verfahren in lösliches Vanadium (V) zu überführen. Ebenso kann z.B. Vanadium ( III ) in einem in einer geeigneten Flüssigkeit dispergierten bzw. gelösten vanadiumhaltigen Material durch Oxidation mit Chlorgas in einem einstufigen Verfahren bis zu löslichem Vanadium (V) durchoxidiert werden. Andererseits besteht auch die Möglichkeit, die Oxidation des eben genannten Ausgangsmaterials in einem zweistufigen Verfahren vorzunehmen, wobei in einer ersten Stufe mit Chlorgas so lange behandelt wird, bis das Vanadium quantitativ als lösliches Vanadium (IV) vorliegt. Die Lösung wird vom festen Rückstand getrennt und kann in einem weiteren Oxidationsschritt unter Verwendung von Chlorgas zu Vanadium (V) aufoxidiert werden. Alternativ dazu kann dieses zweistufige Verfahren auch so geführt werden, daß in einer der beiden Stufen ein anderes Oxidationsmittel als Chlorgas eingesetzt wird. Bei technischer Notwendigkeit oder aufgrund besonderer individueller Vorteile kann bei jeder der oben beschriebenen Stufen das als Oxidationsmittel verwendete Chlorgas auch mit weiteren Oxidationsmitteln kombiniert werden.For example, it is possible to convert soluble vanadium of oxidation stage IV into soluble vanadium (V) using chlorine gas as the oxidizing agent in a one-step process. Likewise, e.g. Vanadium (III) in a material dispersed or dissolved in a suitable liquid containing vanadium by oxidation with chlorine gas in a one-step process to soluble vanadium (V). On the other hand, there is also the possibility of carrying out the oxidation of the above-mentioned starting material in a two-stage process, treatment with chlorine gas in a first stage until the vanadium is present quantitatively as soluble vanadium (IV). The solution is separated from the solid residue and can be oxidized to vanadium (V) in a further oxidation step using chlorine gas. Alternatively, this two-stage process can also be carried out in such a way that an oxidizing agent other than chlorine gas is used in one of the two stages. If technically necessary or because of special individual advantages, the chlorine gas used as the oxidizing agent can also be combined with other oxidizing agents in each of the stages described above.
Der Übergang zwischen den verschiedenen Oxidationsstufen des gelösten Vanadiums zeigt sich optisch durch Farbübergang und kann spektrophotometrisch verfolgt werden.The transition between the different oxidation levels of the dissolved vanadium is shown optically by the color transition and can be followed spectrophotometrically.
Vorzugsweise wird das vanadiumhaltige Ausgangsmaterial in einer natriu chloridhaltigen Lösung dispergiert bzw. gelöst und die Oxidation des Vanadiums bis zur Oxidationsstufe V des Vanadiums unter Bildung einer wässrigen Lösung von Vanadiu (V) geführt und dann mindestens ein Teil des oxidierten Vanadiums durch Fällung von der Lösung getrennt, wodurch gefälltes Polyvanadat und eine natriumchloridhaltige Mutterlauge erhalten werden.The vanadium-containing starting material is preferably dispersed or dissolved in a sodium chloride-containing solution and the oxidation of the vanadium up to oxidation level V of the vanadium is carried out with formation of an aqueous solution of vanadiu (V) and then at least a part of the oxidized vanadium is separated from the solution by precipitation , whereby what is liked Polyvanadat and a sodium chloride-containing mother liquor can be obtained.
Die Fällung des Polyvanadats erfolgt üblicherweise durch die Einstellung eines für die Fällung optimalen pH-Wertes mit Neutralisationsmittel, z.B. Natronlauge, und Einstellung einer optimalen Fällungstemperatur. Das Polyvanadat kann durch Filtration von der Mutterlauge getrennt werden. Je nach Fällungsbedingungen werden bei dieser Trennoperation Restgehalte an Vanadium in der Mutterlauge von < 0,5 g/1 erzielt. Die Mutterlauge hat nach dieser Trennoperation einen NaCl-Gehalt von ca. 120 g/1.The polyvanadate is usually precipitated by setting an optimal pH value for the precipitation with neutralizing agent, e.g. Sodium hydroxide solution and setting an optimal precipitation temperature. The polyvanadate can be separated from the mother liquor by filtration. Depending on the precipitation conditions, residual levels of vanadium in the mother liquor of <0.5 g / l are achieved in this separation operation. After this separation operation, the mother liquor has a NaCl content of approx. 120 g / 1.
Das beim erfindungsgemäßen Verfahren als Oxidationsmittel verwendete elementare Chlor wird vorteilhaft durch Elektrolyse einer natriumchloridhaltigen Lösung hergestellt, wobei an der Anode freies Chlorgas und ein CIO"- bzw. C103 "-haltiger Anolyt und an der Kathode ein natronlaugehaltiger Katholyt gebildet wird. Entsprechend der Chemie des Chlors wird bei der Elektrolyse im Anolyt ein Teil des entstehenden Chlors zu CIO" bzw. C103 " umgesetzt. Der Anteil hängt davon ab, welche natriumchloridhaltige Einsatzlösung verwendet wird.The elemental chlorine used as the oxidizing agent in the process according to the invention is advantageously produced by electrolysis of a solution containing sodium chloride, free chlorine gas and an anolyte containing CIO " or C10 3 " being formed on the anode and a catholyte containing sodium hydroxide solution on the cathode. Depending on the chemistry of the chlorine, part of the chlorine formed is converted to CIO " or C10 3 " during electrolysis in the anolyte. The proportion depends on which sodium chloride-containing feed solution is used.
Als natriumchloridhaltige Einsatzlösung für die Elektrolyse wird vorteilhaft die nach Abtrennung des gefällten Polyvanadats erhaltene natriumchloridhaltige Mutterlauge eingesetzt. Damit kann das für den Oxidationsprozeß benötigte Chlorgas aus der natriumchloridhaltigen Mutterlauge hergestellt werden. Die Mutterlauge muß daher nicht den für eine Entsorgung als Abwasser erforderlichen aufwendigen Verfahren zur Abtrennung von Schwermetallen und zur Verringerung der Chloridfracht durch Eindampfen und Kristallisieren unterzogen werden.The sodium chloride-containing mother liquor obtained after removal of the precipitated polyvanadate is advantageously used as the sodium chloride-containing feed solution for the electrolysis. The chlorine gas required for the oxidation process can thus be produced from the mother liquor containing sodium chloride. The mother liquor therefore does not have to be subjected to the complex processes for separating heavy metals and reducing the chloride load by evaporation and crystallization, which are necessary for disposal as waste water.
Durch Kreislaufschließung ist es ferner möglich, die auselektrolysierte Anolytlösung in die Lösestufe für das Einsatzmaterial ohne vollständige Abtrennung des Natriumchlorids zurückzuführen, da Natriumchlorid denBy closing the circuit it is also possible to remove the electrolyzed anolyte solution into the dissolving stage for the feed material without completely separating the Sodium chloride attributed, since sodium chloride the
Lösevorgang nicht beeinträchtigt. Bei dieser besonders vorteilhaften Ausführungsform des Verfahrens wird daher der Anolyt aus der Elektrolyse als Flüssigkeit zum Dispergieren oder Lösen des als Ausgangsstoff für die Oxidation vorgesehenen vanadiumhaltigen Feststoffes eingesetzt. Vorteilhafterweise kann auch C10"-haltiger und C103 "-haltiger Anolyt zur Lösestufe zurückgeführt werden, da beide Substanzen für die oxidierende Lösung V( III) -haltiger Einsatzprodukte geeignet sind.Solving process not affected. In this particularly advantageous embodiment of the method, the anolyte from the electrolysis is therefore used as a liquid for dispersing or dissolving the vanadium-containing solid which is provided as the starting material for the oxidation. Advantageously, C10 " -containing and C10 3 " -containing anolyte can also be returned to the dissolving stage, since both substances are suitable for the oxidizing solution V (III) -containing products.
Weiters kann der so im Kreis geführte Anolyt auch eisen- und nickelhaltig sein, wobei in eisenhaltigem Anolyt das Eisen als Fe(III), zum Beispiel als gelöstes FeCl3, vorliegt. Beide ionogen vorliegenden Metalle (Fe und Ni) können aus der Mutterlauge sowohl vor als auch nach der Elektrolyse abgeschieden werden, wobei die Abscheidung von Fe(III) durch Hydroxidbildung bereits bei einem pH-Wert von 5 vollständig ist. Nickel, das sich im Kreisprozeß chemisch neutral verhält, kann beispielsweise durch Hydroxidfällung oder Carbonatfällung bis zu gewünschten Endgehalten abgetrennt werden.Furthermore, the anolyte which is circulated in this way can also contain iron and nickel, the iron being present in iron-containing anolyte as Fe (III), for example as dissolved FeCl 3 . Both ionogenic metals (Fe and Ni) can be deposited from the mother liquor both before and after the electrolysis, the deposition of Fe (III) by hydroxide formation being complete at a pH of 5. Nickel, which is chemically neutral in the cycle, can be separated, for example by hydroxide precipitation or carbonate precipitation, to the desired final contents.
Abhängig vom Gehalt an Schwermetallen, dem pH-Wert und der Durchführung der anodischen Herstellung von Cl2-Gas kann ein mehr oder minder großer Anteil des Chlors daher als Gas, oder aber auch gelöst als Cl2-haltiger, C10"-haltiger und C103 "- haltiger Anolyt in die Lösestufe zurückgeführt werden.Depending on the content of heavy metals, the pH value and the implementation of the anodic production of Cl 2 gas, a more or less large proportion of the chlorine can therefore be used as a gas, or else as a solution as Cl 2 -containing, C10 " -containing and C10 3 " -containing anolyte are returned to the dissolving stage.
Bei Herstellung des Chlorgases durch Diaphragmenelektrolyse kann die Mutterlauge der Polyvanadatfällung sowohl vor als auch nach einer partiellen oder vollständigen Abtrennung von Eisen und Nickel auch als Katholyt eingesetzt werden, wobei die gebildete natriumchloridhaltige Natronlauge ebenfalls uneingeschränkt in die Fällungsstufe für die Polyvanadatfällung zurückgeführt werden kann. Bei einer bevorzugten Ausführungsform des Verfahrens wird daher der auselektrolysierte Katholyt zur Fällung des Polyvanadats aus der aufoxidiertes Vanadium (V) enthaltenden wässrigen Lösung eingesetzt. Bei der Verwendung von eisen- und nickelhaltigem Katholyt kann durch Bildung der Hydroxidniederschläge beider Verbindungen während des Elektrolysevorganges eine Ausschleusung beider Verbindungen durchgeführt werden.In the production of the chlorine gas by diaphragm electrolysis, the mother liquor from the polyvanadate precipitation can also be used as catholyte both before and after a partial or complete separation of iron and nickel, the sodium chloride-containing sodium hydroxide solution also being able to be recycled without restriction into the precipitation stage for the polyvanadate precipitation. In a preferred embodiment of the method, therefore the electrolyzed catholyte is used to precipitate the polyvanadate from the aqueous solution containing vanadium (V) oxidized. When using iron- and nickel-containing catholyte, both compounds can be discharged by forming the hydroxide deposits of both compounds during the electrolysis process.
Das erfindungsgemäße Verfahren ermöglicht somit eine KreislaufSchließung hinsichtlich der Verwertung und Rückführung der im Verfahren anfallenden Prozeßwässer und dadurch einen praktisch abwasserfreien Gesamtprozeß. Es besteht keinerlei Notwendigkeit, den natriumchloridhaltigen Elektrolyt der Mutterlauge besonders aufzubereiten, da weder das Natriumchlorid in der Natronlauge noch ein prozeßbedingter Schwermetallgehalt in beiden Strömen der Elektrolyse der Mutterlauge hinsichtlich der Verwertung dieser Lösungen im erfindungsgemäßen Verfahren stören.The process according to the invention thus enables a circuit to be closed with regard to the recycling and recycling of the process water obtained in the process and thereby a practically wastewater-free overall process. There is no need to specially prepare the sodium chloride-containing electrolyte of the mother liquor, since neither the sodium chloride in the sodium hydroxide solution nor a process-related heavy metal content in both streams of the electrolysis of the mother liquor interfere with the utilization of these solutions in the process according to the invention.
Die elektrolytische Chlorerzeugung aus der Mutterlauge kann bei Bedarf gleichzeitig zur Schwermetallfällung im Kathodenraum durch Hydroxidbildung genutzt werden. Matrixelemente des Einsatzmaterials können bei Bedarf durch Fällung mit Hydroxidbildnern aus der Mutterlauge abgetrennt werden. Restvanadium stört im Elektrolyt nicht, da auch der chlorgesättigte Anolyt in die Löse- und Oxidationsstufen zurückgeführt werden kann.Electrolytic chlorine production from the mother liquor can also be used for heavy metal precipitation in the cathode compartment by hydroxide formation if required. If necessary, matrix elements of the feed material can be separated from the mother liquor by precipitation with hydroxide formers. Residual vanadium does not interfere in the electrolyte, since the chlorine-saturated anolyte can also be returned to the dissolution and oxidation stages.
Die Erfindung wird in den folgenden Beispielen noch näher erläutert.The invention is explained in more detail in the following examples.
Beispiel 1example 1
In einer Membranelektrolysezelle wurde nach bekannter Methode anodisch Chlorgas und kathodisch Natronlauge hergestellt. Das Chlorgas wurde bei Raumtemperatur in ein Absorptionsgefäß, in dem V2θ3-haltige Suspension vorgelegt worden war, eingeleitet. Die Suspension war wie folgt zusammengesetzt: 40 g NaCl, 30 g Na2S04, 14,9 g V203, 330 ml Wasser. Es wurde die stöchiometrische Menge an Chlorgas, bezogen auf die vorgelegte Menge an V203 eingeleitet. Nach dem Versuchsende wurde die Suspension filtriert und auf gelöstes Vanadium untersucht. Es wurde eine Gesamtmenge von 4,9 g V(IV) gemessen. Der pH-Wert der Suspension war vom neutralen Bereich auf pH = 3 gesunken.Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method. The chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V2θ 3 had been placed. The suspension was composed as follows: 40 g NaCl, 30 g Na 2 S0 4 , 14.9 g V 2 0 3 , 330 ml water. The stoichiometric amount of chlorine gas, based on the amount of V 2 0 3 presented, was introduced. After the end of the experiment, the suspension was filtered and examined for dissolved vanadium. A total of 4.9 g V (IV) was measured. The pH of the suspension had dropped from the neutral range to pH = 3.
Das Ergebnis bestätigt, daß die chemische lösende Oxidation von suspendiertem V(III) mit elementarem Chlor als Oxidationsmittel möglich ist, wobei die Oxidation vorwiegend nach folgenden Reaktionen abläuft:The result confirms that the chemical solvent oxidation of suspended V (III) with elemental chlorine as an oxidizing agent is possible, the oxidation mainly taking place according to the following reactions:
V203 + 2 Cl2 + 2 H20 => 2 V02+ + 3 Cl" + CIO" V 2 0 3 + 2 Cl 2 + 2 H 2 0 => 2 V0 2+ + 3 Cl " + CIO "
2 V203 + 5 Cl2 + H20 => 4 V02+ + 7 Cl" + 3 CIO" + 2 H+ 2 V 2 0 3 + 5 Cl 2 + H 2 0 => 4 V0 2+ + 7 Cl " + 3 CIO " + 2 H +
V203 + 4 H+ + CIO" => 2 V02+ + Cl" + 2 H20V 2 0 3 + 4 H + + CIO " => 2 V0 2+ + Cl " + 2 H 2 0
Beispiel 2Example 2
In einer Membranelektrolysezelle wurde nach bekannter Methode anodisch Chlorgas und kathodisch Natronlauge hergestellt. Das Chlorgas wurde bei Raumtemperatur in ein Absorptionsgefäß, in dem V203-haltige Suspension vorgelegt worden war, eingeleitet. Die Suspension war wie folgt zusammengesetzt: 60 g NaCl, 45 g Na2S04, 22,35 g V203, 500 ml Wasser. Es wurde die doppelte stöchiometrische Menge an Chlorgas, bezogen auf die vorgelegte Menge an V203 für die Oxidation von V203 zu V02 + eingeleitet. Nach dem Versuchsende wurde eine Polyvanadatfällung durchgeführt. Das Vanadium konnte bis auf einen Restgehalt von 0,14 g/1 in der Reaktionslösung quantitativ als V205 gefällt werden. Anodic chlorine gas and cathodic sodium hydroxide solution were produced in a membrane electrolysis cell using a known method. The chlorine gas was introduced at room temperature into an absorption vessel in which a suspension containing V 2 0 3 had been placed. The suspension was composed as follows: 60 g NaCl, 45 g Na 2 SO 4 , 22.35 g V 2 0 3 , 500 ml water. It was initiated twice the stoichiometric amount of chlorine gas, based on the amount of V 2 0 3 presented for the oxidation of V 2 0 3 to V0 2 + . After the end of the experiment, polyvanadate precipitation was carried out. The vanadium could be precipitated quantitatively as V 2 0 5 except for a residual content of 0.14 g / 1 in the reaction solution.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU34076/00A AU3407600A (en) | 1999-03-18 | 2000-03-17 | Vanadium oxidation method |
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|---|---|---|---|
| ATA493/99 | 1999-03-18 | ||
| AT0049399A AT408454B (en) | 1999-03-18 | 1999-03-18 | METHOD FOR OXIDATING VANADIUM |
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| WO2000056662A1 true WO2000056662A1 (en) | 2000-09-28 |
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| PCT/AT2000/000062 Ceased WO2000056662A1 (en) | 1999-03-18 | 2000-03-17 | Vanadium oxidation method |
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|---|---|
| AT (1) | AT408454B (en) |
| AU (1) | AU3407600A (en) |
| WO (1) | WO2000056662A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2266343C2 (en) * | 2003-02-03 | 2005-12-20 | НПО "Ванадий-катализатор" | Method of processing vanadium-containing converter slag |
| RU2437946C2 (en) * | 2010-03-05 | 2011-12-27 | Владиллен Александрович Козлов | Procedure for processing vanadium containing raw material |
| RU2607290C2 (en) * | 2014-05-21 | 2017-01-10 | ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. | Method of calcining vanadium-containing material |
| RU2607292C2 (en) * | 2014-05-21 | 2017-01-10 | ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. | Method for two-step calcination of vanadium-containing material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111733337B (en) * | 2020-07-06 | 2022-05-24 | 攀钢集团研究院有限公司 | Method for preparing vanadium oxide by reducing vanadium solution |
| CN114134346B (en) * | 2021-11-30 | 2022-08-12 | 大连理工大学 | A kind of method for removing sodium-precipitating vanadium by continuous ion membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1474152A (en) * | 1976-04-09 | 1977-05-18 | British Aluminium Co Ltd | Leaching process for separation of calcium and vanadium oxides |
| JPS53117602A (en) * | 1977-03-24 | 1978-10-14 | Toyo Soda Mfg Co Ltd | Separating and recovering method for valuable metals from waste catalyst containing molybdenum |
| US4579721A (en) * | 1984-08-03 | 1986-04-01 | Getty Oil Company | Process for recovering metals from waste |
| US4788044A (en) * | 1986-07-17 | 1988-11-29 | Ente Minerario Siciliano | Method for recovering vanadium from residues from the combustion of petroleum fractions |
| US4851199A (en) * | 1985-01-03 | 1989-07-25 | Union Oil Company Of California | Methods for recovering vanadium from phosphoric acid and vanadium sources |
-
1999
- 1999-03-18 AT AT0049399A patent/AT408454B/en not_active IP Right Cessation
-
2000
- 2000-03-17 WO PCT/AT2000/000062 patent/WO2000056662A1/en not_active Ceased
- 2000-03-17 AU AU34076/00A patent/AU3407600A/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1474152A (en) * | 1976-04-09 | 1977-05-18 | British Aluminium Co Ltd | Leaching process for separation of calcium and vanadium oxides |
| JPS53117602A (en) * | 1977-03-24 | 1978-10-14 | Toyo Soda Mfg Co Ltd | Separating and recovering method for valuable metals from waste catalyst containing molybdenum |
| US4579721A (en) * | 1984-08-03 | 1986-04-01 | Getty Oil Company | Process for recovering metals from waste |
| US4851199A (en) * | 1985-01-03 | 1989-07-25 | Union Oil Company Of California | Methods for recovering vanadium from phosphoric acid and vanadium sources |
| US4788044A (en) * | 1986-07-17 | 1988-11-29 | Ente Minerario Siciliano | Method for recovering vanadium from residues from the combustion of petroleum fractions |
Non-Patent Citations (3)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 84, no. 24, 14 June 1976, Columbus, Ohio, US; abstract no. 170201, CORNELIUS, RICHARD D. ET AL: "Kinetics and mechanism of the oxidation of vanadium (III) by chlorine in aqueous solution" XP002142186 * |
| DATABASE WPI Section Ch Week 197846, Derwent World Patents Index; Class H04, AN 1978-83164A, XP002142187 * |
| INORG. CHEM. (1976), 15(5), 997-1002 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2266343C2 (en) * | 2003-02-03 | 2005-12-20 | НПО "Ванадий-катализатор" | Method of processing vanadium-containing converter slag |
| RU2437946C2 (en) * | 2010-03-05 | 2011-12-27 | Владиллен Александрович Козлов | Procedure for processing vanadium containing raw material |
| RU2607290C2 (en) * | 2014-05-21 | 2017-01-10 | ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. | Method of calcining vanadium-containing material |
| RU2607292C2 (en) * | 2014-05-21 | 2017-01-10 | ПанГан Груп Панжихуа Айрон энд Стил Рисёрч Инститьют Со., Лтд. | Method for two-step calcination of vanadium-containing material |
Also Published As
| Publication number | Publication date |
|---|---|
| ATA49399A (en) | 2001-04-15 |
| AU3407600A (en) | 2000-10-09 |
| AT408454B (en) | 2001-12-27 |
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