WO2016059102A1

WO2016059102A1 - Production of vanadyl sulfate from vanadium pentoxide

Info

Publication number: WO2016059102A1
Application number: PCT/EP2015/073761
Authority: WO
Inventors: Werner Wiedmann
Original assignee: Schmid Energy Systems Gmbh
Priority date: 2014-10-16
Filing date: 2015-10-14
Publication date: 2016-04-21
Also published as: TW201627227A; DE102014115081A1

Abstract

The present invention relates to a method for producing a vanadyl salt. The invention relates to, in particular, the production of a vanadyl salt starting from vanadium pentoxide suspended in water and an acid and to the reduction thereof to form the vanadyl salt with a mild reducing agent. The invention also relates to another method step for obtaining a purified vanadyl salt.

Description

Preparation of vanadyl sulfate from vanadium pentoxide

The present invention relates to a process for the preparation of aqueous vanadyl solutions which are suitable for use in vanadium redox flow batteries. In particular, the present invention relates to the preparation of an aqueous vanadyl solution starting from vanadium pentoxide.

Redox flow batteries (RFBs) are used in particular as backup batteries in the industry. In addition, they are used in electric cars. For the most part, vanadium, sodium bromide and zinc bromine RFBs are used. These are characterized among other things by different energy densities. Of particular interest is the vanadium RFB or VRFB, since vanadium occurs in five oxidation states, four of which are used in the VRFB. A VRFB usually comprises one or more cells, each cell comprising two half-cells, usually separated by a proton exchange membrane. The positive half cell contains vanadium ions of oxidation states +4 and +5 and the negative half cell vanadium ions of oxidation states +2 and +4. The ionic solutions in the individual half cells can be filled up accordingly by means of external tanks and pumps.

A VRFB is characterized in particular by fast reaction to different loads and extremely high overcharge capacities. Energy densities of about 25 watt-hours per kg of electrolyte fluid or more can be achieved. This type of flow battery is also characterized by low self-discharge and low maintenance.

The ion solutions used in the half-cells can be prepared in various ways. The tetravalent vanadium ions can be provided here in the form of vanadyl or vanadium oxide ions. This can be accomplished by reduction of vanadium pentoxide by oxalic acid, carbon monoxide or sulfur dioxide in the presence of an acid such as hydrochloric acid or bromic acid to vanadyl chloride or vanadyl bromide.

For example, WO 02/04353 A2 proposes the synthesis of vanadyl sulfate starting from vanadium pentoxide and vanadium trioxide in the presence of sulfuric acid of a specific concentration. CN 103199292 describes the reduction of vanadium pentoxide to vanadyl sulfate in the presence of sulfuric acid and oxalic acid as the reducing agent.

A disadvantage of the above-mentioned method is that the Komproportionierung made in WO 02/04353 A2 first vanadium compounds in the corresponding oxidation states must be formed and submitted. The other methods are characterized in particular by the use of strong reducing agents, such as sulfur dioxide, and the associated problematic handling.

Against this background, therefore, the object of the present invention is to provide methods by which aqueous vanadyl solutions can be provided simply and quickly. Another task is aqueous Vanadyl solutions are prepared in sufficient quantity and purity to be suitable for use in VRFBs.

This object is achieved by a process for the preparation of a vanadyl salt with the following steps:

Suspending vanadium pentoxide in water and in an acid, and

Reduction of vanadium pentoxide to the vanadyl salt with a mild reducing agent,

Optionally obtaining a purified vanadyl salt.

It has surprisingly been found that starting from vanadium pentoxide

Vanadyl salts with a mild reactant can be obtained. Such mild reactants are characterized by easy handling, in contrast to the strong reducing agents used since then, such as, for example, concentrated sulfur dioxide-containing sulfuric acid. The use of the mild reducing agents herein also enables the simple, rapid and inexpensive preparation of aqueous vanadyl solutions of sufficient purity that they can be used directly in VRFBs. Furthermore, the present process allows the production of vanadyl salts in industrial quantities, for example in batch reactors or continuous reactors, can take place.

A "mild reducing agent" as used herein includes mild chemical

Reducing agents, such as the alcohols and aldehydes described herein, electrical current, ie the electrochemical reduction. The aldehydes or alcohols may be aliphatic and / or aromatic and independently have further aliphatic and / or aromatic side chains. Such "mild reducing agents" are distinguished from strong reducing agents, such as concentrated sulfuric acid, sulfur dioxide and carbon monoxide, by better handling. Furthermore, the use of "mild reducing agents" makes it possible to obtain a vanadylsalicylate which contains other substances, such as by-products or unreacted starting material, in such amounts as not to interfere with the production and operation of a VRFB.

Another advantage of using a mild reducing agent is the low thermal temperature development in the reaction, whereby cooling of the reaction mixture can optionally be avoided. In addition, when using aldehydes and / or alcohols as a mild reducing agent, the reaction mixture can be heated to accelerate the reaction.

A "vanadyl salt" as used herein includes any anions suitable alone or in combination as the counterion to the vanadyl cation, as well as the hydrates of the corresponding vanadyl salts. Exemplary anions include sulfate, carbonate, nitrate, chloride, bromide, etc. The anions are not limited to inorganic anions but also include organic anions such as, for example, alkoxides or carboxylates. The anions may correspond, for example and preferably, to a reaction product of the mild reducing agent after reduction of vanadium pentoxide. Thus, for example, an aldehyde is oxidized as a mild reducing agent to the corresponding carboxylic acid, and subsequently the vanadyl cation can be present in combination with the corresponding carboxylate as the anion. An exemplary and preferred vanadyl salt is vanadyl sulfate pentahydrate. Since the vanadyl ion has a deep blue color in an aqueous solution, the progress of the reaction can be monitored qualitatively and optionally quantitatively, either visually or spectrophotometrically.

Vanadium pentoxide used as the starting material for the reaction of the present invention is well known in the art and can be produced, for example, directly from the elements. Alternatively, it may also be prepared by annealing ammonium metavanadate in air.

The purity of the water used in the reaction is not limited and also includes tap water in addition to distilled and demineralized water. technical Water can also be used as long as the total organic carbon (TOC) is below 5 g / L. Preferably, the TOC value is less than 1 g / l. It is clear that the water used is substantially free of pollutants, ie that the legal limits are maintained with respect to individual compounds.

As the acid used for suspending vanadium pentoxide in water, any mineral acid and / or carboxylic acid may be used. Exemplary mineral acids include sulfuric acid, boric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and fluoroboric acid. The carboxylic acids used may be aliphatic and / or aromatic carboxylic acids, which are optionally provided with aliphatic and / or aromatic side chains. Exemplary carboxylic acids include acetic acid, formic acid and methanesulfonic acid. The concentration of the acid is not particularly limited.

Preferably, the concentration or amount of the acid used is such that the initial vanadium pentoxide is completely suspended. However, this is not necessarily the case. Thus, vanadium pentoxide can only be partially suspended. The reaction of vanadium pentoxide to the vanadyl salt in this case allows the suspension of previously unsuspended present Vanadiumpentoxid. The acids are preferably used in an amount or concentration such that they themselves do not develop a reductive action. For example and preferably, no concentrated sulfuric acid but only dilute sulfuric acid is used. Alternatively, concentrated sulfuric acid may also be used, but preferably at a final concentration such that the acid itself does not exhibit a reductive effect.

A "purified vanadyl salt" includes any vanadyl salt from the above

Reaction steps, i. Suspending vanadium pentoxide in water and in an acid, and reducing vanadium pentoxide to the vanadyl salt with a mild reducing agent having a higher degree of purity by a further process step. A higher degree of purity means that unreacted starting materials, solvents and / or by-products are partially or completely removed. A purified vanadyl salt preferably fulfills process-accompanying TOC determinations.

The term "aliphatic substituent" or "aromatic substituent" refers to radicals composed of carbon and hydrogen. Aromatic substituents include ring structures such as benzene, whereas aliphatic radicals do not comprise ring structures but only linear or branched carbon chains. The present aliphatic or aromatic substituents may optionally have one or more other radicals or functional groups, for example hydroxy, amino or halogen, such as fluorine, chlorine, bromine and iodine. Aliphatic substituents or radicals comprise a chain length of C1 to C20, preferably C1 to C10, C1 to C5, C2 to C4, or C3. The aliphatic radicals can be linear or branched.

The term "comprising" or "comprising" in the context of the present invention denotes an open enumeration and does not exclude addition to the explicitly stated constituents or steps of other constituents or steps.

The expression "consist of" or "consisting of" in the context of the present invention, a closed listing and excludes expressly mentioned ingredients or steps any other ingredients or steps.

The expression "consisting essentially of" or "consisting essentially of" in the context of the present invention denotes a partially closed list and designates compositions which, in addition to the constituents mentioned, only contain further constituents which do not materially change the character of the composition or in quantities that do not materially alter the character of the composition.

In the context of the present invention, when a composition is described using the term "comprising", it expressly includes compositions consisting of or consisting essentially of said constituents.

It is understood that the features of the invention mentioned above and those yet to be explained below are not limited to the particular combination specified, but are also used in other combinations or in isolation, without departing from the scope of the invention.

Further features and advantages of the invention will become apparent from the following

Description of preferred embodiments with reference to the drawings. Show it:

1 shows the time course of the reaction of vanadium pentoxide in 50% aqueous sulfuric acid,

2 shows the temperature profile of the reaction of vanadium pentoxide in sulfuric acid solution or suspension with formaldehyde as a mild reducing agent,

3 TOC measurements in sulfuric acid vanadyl sulfate pentahydrate solution according to special treatment methods to obtain a purified vanadyl sulfate pentahydrate,

Fig. 4 shows the TOC course in acidic Vanadylsulfatpentahydrat solution by air entry at 40 ° C, and

Figure 5 illustrates the energy efficiency of a vanadium redox flux battery operated with vanadyl sulfate pentahydrate prepared in accordance with this invention compared to a commercial VRFB.

In one embodiment, the acid used in the process for producing a vanadyl salt according to the invention is a mineral acid or carboxylic acid. Mineral acids include, for example, sulfuric acid, boric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and fluoroboric acid. A preferred mineral acid is sulfuric acid. Carboxylic acids have aliphatic and / or aromatic radicals, which in turn may be substituted or unsubstituted. Examples of preferred carboxylic acids include acetic acid, formic acid and methanesulfonic acid. More preferably, formic acid is used because when using formaldehyde as the reducing agent as well Formic acid is formed so that unreacted acid and reacted reducing agent correspond and easier purification can take place.

In one embodiment, the acid is sulfuric acid. Preferably, dilute sulfuric acid is used.

In one embodiment, the vanadyl salt is vanadyl sulfate pentahydrate.

In one embodiment, the mild reducing agent is an aldehyde and / or an alcohol. The mild reducing agent is selected, for example, from the group consisting of a substituted or unsubstituted aromatic aldehyde and a substituted or unsubstituted aliphatic aldehyde, a substituted or unsubstituted aromatic alcohol and a substituted or unsubstituted aliphatic alcohol. The aldehyde and / or alcohol preferably have only aliphatic substituents or residues with a chain length of C1 to C20, preferably C1 to C10, C1 to C5, C2 to C4, or C3. It is clear that certain carboxylic acids, for example succinic acid, can also be used as a mild reducing agent. Such carboxylic acids may also have the above-listed substituted or unsubstituted aromatic or substituted or unsubstituted aliphatic radicals.

Preferred mild reducing agents include short chain, linear or branched

Aldehydes and / or alcohols of a chain length from C1 to C5. Other preferred mild reducing agents are formaldehyde, paraldehyde, and succinic acid. Preferably, methanol is not used as the sole reducing agent.

The aldehyde and / or an alcohol used preferably has a low boiling point of, for example, below 100 ° C. and / or does not form a eutectic mixture with water. Residues of such aldehydes and / or alcohols can be readily removed by introducing a heated gas stream. For example, an entry of a heated gas, ie at a temperature above room temperature (22 ° C), from 25 ° C to 80 ° C, preferably 30 ° C to 60 ° C and 40 ° C to 50 ° C, over a Period from 10h to 200h, preferably, 50 to 150 hours, 70 to 100 hours. The heated gas is preferably heated air.

In one embodiment, the reducing agent is formaldehyde. As already mentioned, the simultaneous use of formaldehyde with formic acid as solvent results in the partial or complete removal of formic acid from the reaction mixture in order to obtain a purified vanadyl salt. Residues of formaldehyde or formic acid can furthermore be readily removed by introducing a heated gas stream. For example, an entry of heated air, i. at a temperature above room temperature (22 ° C), from 25 ° C to 80 ° C, preferably 30 ° C to 60 ° C and 40 ° C to 50 ° C, over a period of 10h to 200h, preferably, 50 to 150 hours, 70 to 100 hours.

In one embodiment, the reducing agent is DC. The

Electrochemical reduction is performed using DC of a voltage of up to 200V. Vanadium pentoxide is suspended in one of the abovementioned acids in aqueous solution and reduced in a container separated by a suitable diaphragm or in free electrode spaces without ion-selective space separation on an electrode at the phase boundary to a soluble vanadyl compound in the presence of an anion-forming acid, for example sulfuric acid , Suitable electrode materials include, for example, precious metal or graphite. DC with a voltage of up to 200 V can be used.

Preferably, a voltage of 10 to 150V, 50 to 100V, 80 to 90V, or 70V is used.

In one embodiment, obtaining a purified vanadyl salt comprises a

Filtration step. The filtration step can be performed to remove solid impurities. The filtration step can be carried out with ordinary paper filters or also with columns charged with a filtration material. Further purification steps, such as distillation or recrystallization, may be included. Preferably, a filtration step is performed prior to distillation or recrystallization. Alternatively, a distillation or recrystallization without filtration step respectively. Irrespective of this, blowing in of a heated gas stream, for example air, can take place as described above.

In one embodiment, obtaining a purified vanadyl salt comprises a

Distillation step with a plate evaporator. Plate evaporators are commercially available. Product and heating medium are conducted in countercurrent in corresponding channels. Through intensive heat exchange, the product begins to boil. Evolved vapor drives the residual liquid up into a vapor channel of the plate package. In an optional downstream centrifugal separator residual liquid and vapors are separated. The use of the plate evaporator has proved to be particularly useful when formic acid is used as the acid formic acid and / or as the reducing agent. Formic acid can be removed in the plate evaporator by vacuum distillation from the vanadyl salt mixture. In a plate evaporator made of alternately arranged "hot" and "cold" hollow slabs, the hot plates are sprinkled with the Vanadylsalzansatz. Formic acid with a boiling point of 101 ° C can be removed by distillation at a pressure of 500 mbar at 79 ° C, 250 mbar at 60 ° C, and at 100 mbar at 37 ° C, is deposited in the cold part of the plate evaporator and there via a Gutter removed as condensate. The use of a plate evaporator enables obtaining a purified vanadyl salt on an industrial scale, without the need for another purification step, to obtain a vanadyl salt that meets the requirements of use in a VRFB.

In one embodiment, purified vanadyl salt is provided by a

Process according to any one of the preceding claims. The purified vanadyl salt preferably comprises a TOC of less than 5 g / L, more preferably from 4 g / L to 1 g / L, such as 2 or 3 g / L. The purified vanadyl salt is preferably vanadyl sulfate pentahydrate.

Such a purified vanadyl salt can readily be used in a vanadium redox flux battery. Optionally, and preferably, vanadyl salt prepared by the process of the invention may be used without purification in a VRFB. A VRFB comprises at least one cell, preferably two or more cells, five or more cells, 50 or more cells, or 100 or more cells. Each cell consists of two half-cells, one half cell containing pentavalent vanadium ions, for example vanadium pentoxide, and tetravalent vanadium ions prepared by the process according to the invention and preferably with a plate evaporator, in aqueous, acidic solution, for example aqueous sulfuric acid. The other half cell comprises divalent and trivalent vanadium ions in sulfuric acid solution. Both half-cells are separated by a proton exchange membrane, for example a suitable PTFE membrane, such as a Nafion membrane. The half-cells can be externally supplied by a respective tank with appropriate ion solution and optionally using a pump.

It is understood that the above and the still following

explanatory features are not only used in the combination, but also in other combinations or in isolation, without departing from the scope of the present invention.

The invention is illustrated below by way of examples and in the

explained in more detail below description.

example 1

In the electrochemical reduction 50% sulfuric acid is introduced and solid

Vanadium pentoxide added. The batch is stirred until the vanadium pentoxide is completely suspended. In a container separated by a Nafion membrane as a PTFE diaphragm or in free electrode spaces without ion-selective space separation, vanadium pentoxide is reduced in the presence of sulfuric acid on one of the two noble metal or graphite electrodes at the phase boundary to a soluble vanadyl compound. The first electrode compartment contains a suspension of vanadium pentoxide in dilute sulfuric acid and the second compartment dilute sulfuric acid. By applying 100 V DC, the conversion of vanadium pentoxide to vanadyl sulfate pentahydrate takes place. Example 2

For the reduction of vanadium pentoxide with a mild chemical reducing agent, 1 .364 g of vanadium pentoxide are weighed, combined with 3.493 ml of 50% sulfuric acid in a reaction vessel and suspended by stirring the mixture. In the vanadium pentoxide suspension in sulfuric acid, formaldehyde is added as a mild reducing agent using a dropping funnel over a period of 45 minutes. For this purpose, 614.3 ml of a 37% formalin solution (methanol-stabilized) are measured and added to the suspension as described above. For complete reaction within the specified reaction time of at least 8 h, an approximately 20% excess based on the stoichiometrically calculated amount of formaldehyde should be used.

The liberated heat of reaction was using two grades

Vanadium pentoxide determined. FIG. 1 shows the course of the reaction of vanadium pentoxide over a period of about 20 hours. Curve A shows the conversion of technical grade vandium pentoxide (Todini) with paraldehyde (Merck), curve B the conversion of industrial grade vandium pentoxide with ethanedicarboxylic acid or succinic acid (Merck), curve C the conversion of technical grade vandium pentoxide ( Todini) with formaldehyde (Merck), curve D the reaction of vandium pentoxide (Merck) with formaldehyde (Merck), curve E the conversion of technical grade vandium pentoxide (Todini) with methanol (Merck and curve F the conversion of technical grade vandium pentoxide (Todini) with carbon (Merck).

From Fig. 1 it can be seen that regardless of the quality of Vandiumpentoxids (technical quality or qualitative high-quality starting compound) the fastest complete conversion can be achieved using formaldehyde or para-aldehyde (A, C and D). With succinic acid, a still satisfactory conversion can also be achieved (B). Carbon (powder) also leads to the reaction (F), but methanol is rather unsuitable for the reaction (E). Furthermore, technical grade formaldehyde also shows complete conversion to vanadyl sulfate pentahydrate compared to formaldehyde purchased from Merck. When using Ethandicarbonsäure no 100% substance conversion is achieved and the reaction is delayed. Carbon in powder form leads to a conversion of the educt. The processing of the solution after filtration corresponds to that of commercially available electrolyte. However, as a by-product, lower oxidation states of the vanadyl cation are formed. Although paraldehyde is poorly wetted, the reaction otherwise corresponds to the use of formaldehyde. The use of methanol leads to the formation of hemiacetals as a by-product. Methanol is rather unsuitable as a reducing agent.

The exothermic reaction in terms of peak behavior to reach the maximum

Temperature can be influenced by controlling the rate of addition of formaldehyde, as shown in FIG. Upon rapid addition of formaldehyde, a 2.5 l mixture reacts within a very short time largely to vanadyl sulfate pentahydrate (curve G). The addition of formaldehyde over a longer period requires a long post-reaction time to complete reaction. It can also be seen from FIG. 2 that the control of the temperature can, for example, be carried out to values of 60 ° C. or just above, whereby the formation of decomposition products can be better avoided (curve H).

Example 3

From the reducing agent formaldehyde is formed by the reaction with

Vanadium pentoxide formic acid with a boiling point of 100.5 ° C. In the reaction mixture obtained in Example 2, formaldehyde is removed from the batch by blowing in room air at elevated temperature. The removal of formic acid formed and optionally present formaldehyde residues is carried out by means of TOC determination before and after the batch treatment. From FIG. 3, a comparison of the TOC values at room temperature and 0 h (I), at room temperature after 72 hours of air injection (J), at 40 ° after 72 h and without air injection (K) and 40 ° after 72- hourly Lufteinblasung (L) are removed. The by-products or residues of formaldehyde and formic acid formed can be removed to a large extent by blowing in room air in the heated at 40 ° C approach. The efficiency of the air injection to reduce the pressure value is about 3.1 mg TOC reduction / min at 60 ° C, 0.6 mg TOC reduction / min at room temperature (22 ° C).

From Fig. 4 it can be seen that the TOC curve in acidic

Vanadyl sulfate pentahydrate solution by air entry at 40 ° C to a reduction of 0.5 mg TOC / min results. TOC values less than 5 g / L are readily acceptable in a VRFB. The solid line here represents the connection of the individual measured values, whereas the dashed line shows an interpolated course.

Example 4

Commercial electrolytes were used (Gfe Gesellschaft für Elektromellurgie mb) for the production of a VRFB. Two cells were prepared, the first cell comprising only purchased electrolytes, and the second cell comprising vanadyl sulfate pentahydrate from the previous example, in addition to commercially purchased electrolytes. It can also be seen from Figure 5 that the efficiency of this VRFB (N) is only 5% below the cell operated exclusively with commercial electrolyte (M). The commercial electrolyte exhibits a performance case over the cycles run, while the electrolyte described and purified according to Example 3 described in FIG. 5 tends to show little to no performance degradation.

The preparation of the starting solution required for the VRFB, in particular of

Vanadyl salts, therefore, due to the method described, for example, in the batch process readily be transferred to large volumes. Production by means of continuous processes is also possible, in which suspended vandium pentoxide is added and aqueous solution is removed.

Claims

claims

1 . A process for the preparation of a vanadyl salt, comprising

Suspending vanadium pentoxide in water and in an acid, and

Reduction of vanadium pentoxide to the vanadyl salt with a mild reducing agent, optionally obtaining a purified vanadyl salt.

2. The method according to claim 1, wherein the acid is a mineral acid or carboxylic acid.

A process according to any one of the preceding claims, wherein the acid is sulfuric acid.

4. The method according to any one of the preceding claims, wherein the vanadyl salt is vanadyl sulfate pentahydrate.

A process according to any one of the preceding claims, wherein the mild reducing agent is an aldehyde and / or an alcohol.

6. A process according to any one of the preceding claims wherein the mild reducing agent is selected from the group consisting of a substituted or unsubstituted aromatic aldehyde and a substituted or unsubstituted aliphatic aldehyde, a substituted or unsubstituted aromatic alcohol and a substituted or unsubstituted aliphatic alcohol.

A process according to any one of the preceding claims, wherein the mild reducing agent is formaldehyde.

8. The method according to any one of claims 1 to 4, wherein the mild reducing agent is DC.

9. The method of claim 8, wherein the DC current has a voltage up to 200V.

A process according to any one of the preceding claims, wherein obtaining a purified vanadyl salt comprises a filtration step.

1 1. The method of any one of the preceding claims, wherein obtaining a purified vanadyl salt comprises bubbling a heated gas stream.

A process according to any one of the preceding claims, wherein obtaining a purified vanadyl salt comprises a distillation step with a plate evaporator.