Vanadium extraction

Abstract

A method for extracting vanadium (V) from a vanadium-containing source, the method comprising: (a) leaching the vanadium-containing source with a composition of compounds containing formula (I): wherein R1, R2, R3, and R4 are each independently C 1‑10 Hydrocarbon group; wherein, A + For N + or P + The composition further comprises an oxidizing agent; and the leaching extracts some vanadium from a vanadium-containing source to provide extracted vanadium (V); and (b) recovers the extracted vanadium (V).

Description

Technical Field

[0001] This disclosure relates to a method for extracting vanadium (V) from a vanadium-containing source. More specifically, this disclosure relates to a method for extracting vanadium (V), the method comprising: recovering the extracted vanadium (V), optionally carried out during electrodialysis. Background Technology

[0002] Vanadium is used in the steel industry to produce metallic alloys for reinforcing bars and structural steel; it is also used in the aerospace industry. When added in appropriate amounts, vanadium can reduce the weight of steel by up to 30% and increase its strength by up to 100%. Currently, the steel and titanium industries account for over 90% of global vanadium production.

[0003] In recent years, vanadium redox flow batteries (VRFBs) have attracted considerable attention due to their long cycle life, full discharge capability, low operating costs, rapid response, environmental friendliness, and non-flammability. As intermittent solar and wind power are increasingly deployed into national grids, buffer storage is needed, leading to rapid growth in the global energy storage market. Therefore, global investment in clean energy technologies is expected to significantly increase the demand for vanadium.

[0004] Conventional vanadium refining first involves roasting the raw material with sodium salts such as sodium carbonate or sodium chloride at high temperatures to produce water-soluble vanadium. This is followed by processes including precipitation with ammonium polyvanadate or ammonium metavanadate to separate the solid vanadium (V) from the aqueous phase. Besides the inherently harmful tailings from the salt roasting and water leaching process, this seemingly simple vanadium processing method comes at the cost of releasing harmful gases into the atmosphere, such as sulfur oxides. Furthermore, the release of vanadium (V) into the environment can be hazardous.

[0005] Unfortunately, despite being classified as a potentially toxic metal, vanadium (V) has received limited attention for its toxicity, and research on its geochemistry is also scarce compared to similar trace metals. Recent studies on vanadium pollution and health risks in marine ecosystems indicate that children face the highest health risks. Therefore, primary vanadium production not only has serious environmental impacts but, due to its concentration in specific regions, is also highly susceptible to political and geopolitical decisions.

[0006] Therefore, it is crucial to identify alternative methods for producing vanadium from more readily available sources, such as secondary resource gasification furnace ash, to ensure the implementation of the circular economy and to expand the vanadium supply chain network. Summary of the Invention

[0007] According to a first aspect, a method for extracting vanadium (V) from a vanadium-containing source is provided, the method comprising: (a) Leaching of a vanadium-containing source using a composition containing a compound of formula (I):

[0008] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0009] Among them, A + For N + or P + ; The composition further comprises an oxidizing agent; and The leaching process extracts some vanadium from a vanadium-containing source to provide extracted vanadium (V); and (b) Recover the extracted vanadium (V).

[0010] According to the second aspect, compounds represented by the following formula are provided: H4(Me4N)2V 10 O 28 .5H2O.

[0011] According to the third aspect, the following compound is provided: H3(Me4N)3V 10 O 28 .6H2O.

[0012] According to the fourth aspect, compounds of the second or third aspect are provided, said compounds being obtained by or achievable through the method of the first aspect.

[0013] According to the fifth aspect, use of the composition is provided, said composition comprising a compound of formula (I):

[0014] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0015] Among them, A + For N + or P + ; Used to extract vanadium (V) from vanadium-containing sources. Attached Figure Description

[0016] Figure 1 H4(Me4N)2V was displayed. 10 O 28 X-ray diffraction pattern of .5H2O.

[0017] Figure 2 H3(Me4N)3V was displayed. 10 O 28 X-ray diffraction pattern of .6H2O.

[0018] definition

[0019] The term "at least one" is synonymous with "one or more", that is, one, two, three, four, five, six or more.

[0020] As used herein, the term “about” generally encompasses or refers to a range of values ​​that a person skilled in the art would consider equivalent to the listed values ​​(i.e., having substantially the same function or result and / or achieving the same function or result in the same manner). When the term “about” is used in conjunction with a numerical value, it may (in ascending order of priority) indicate a deviation of 10%, 5%, 2%, 1%, or 0% relative to that value.

[0021] Throughout this specification, the terms "comprising" or "including" mean that the specified components are included, but do not exclude the presence of other components. The terms "consistently made of" or "consistently made of" mean that the specified components are included, but other components are excluded, except for materials present as impurities, materials unavoidably present in the process of providing the components, and components added for purposes other than achieving the technical effects of the invention. Generally, when referring to a composition, a composition consisting essentially of one set of components will contain less than 5% by weight, typically less than 3% by weight, and more typically less than 1% by weight of unspecified components.

[0022] The terms “composed of” or “constituting of” mean that the specified components are included, but the addition of other components is excluded.

[0023] Where appropriate, and depending on the context, the use of the terms “comprising” or “including” may also be understood to encompass or include the meaning of “consistent with” or “made up of”, and may also be understood to include the meaning of “composed of” or “made up of”.

[0024] For the avoidance of ambiguity, when the content of a component in a composition is described as “wt.%” (weight percentage) or “weight %”, it refers to the weight percentage of the specified component relative to the entire composition mentioned. For example, “gasifier ash contains about 10 wt% to about 60 wt% elemental vanadium” means that 10 wt% to 60 wt% of the gasifier ash is provided by elemental vanadium.

[0025] Throughout this specification, the term "solution" is used to define a liquid mixture in which the solute is uniformly distributed in a solvent. Unless otherwise stated, the solvent includes water, i.e., the solution is an aqueous solution. Detailed Implementation

[0026] Extracting vanadium using acids (such as sulfuric acid) requires an organic liquid-liquid extraction step and necessitates a large amount of sulfuric acid to recover the extracted vanadium from the organic solvent. The ammonium polyvanadate precipitation step further necessitates purification of the vanadium. However, alkaline leaching offers a simpler route for vanadium extraction, but alumina and silica pose significant challenges when purifying vanadium (V) from sodium-vanadium systems. A desilication process is required to reduce the silica concentration in the solution, leading to decreased extraction yield and increased process complexity. Furthermore, due to (Si-O-Al)... x The slow formation of H2O compounds means that the desilication process is usually time-consuming.

[0027] Among other things, one object of the present invention is to provide a method for extracting vanadium that overcomes at least one disadvantage of the prior art as pointed out herein or elsewhere, or provides an alternative to existing methods. For example, an object of the present invention could be to provide a method for extracting vanadium that is capable of extracting high-purity vanadium without dissolving alumina and silicon oxide.

[0028] According to various aspects of the present invention, a method for extracting vanadium (V) from a vanadium-containing source, as described in the appended claims, and its use are provided. Other features of the invention will be apparent from the dependent claims and the description below.

[0029] According to a first aspect, a method for extracting vanadium (V) from a vanadium-containing source is provided, the method comprising: (a) Leaching of a vanadium-containing source using a composition containing a compound of formula (I):

[0030] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0031] Among them, A + For N + or P + ; The composition further comprises an oxidizing agent; and The leaching process extracts some vanadium from a vanadium-containing source to provide extracted vanadium (V); and (b) Recover the extracted vanadium (V).

[0032] The method is appropriately performed in the order of (a) followed by (b).

[0033] It has been found that the method disclosed herein can, for example, be used to refine gasifier ash containing more than 20 elements into ultra-high purity (e.g., at least 99% by weight, or at least 99.5% by weight) V2O5, which is ideal for vanadium redox flow batteries.

[0034] Furthermore, it has been found that the method disclosed herein can be used in a closed liquid loop, with solid feedstock and energy (electricity and heat) input, requiring no continuous chemical input, and outputting solid V₂O₅. It has also been found that the byproducts of this method are hydrogen and oxygen, which are themselves considered valuable byproducts.

[0035] The methods disclosed herein can be implemented, for example, in a non-separated electrochemical reactor for oxidation operating at ambient temperature and pressure, and in a membrane-separated electrochemical reactor for electrodialysis operating at near-ambient temperature and pressure. These reactors are scalable and facilitate the production of high-purity V₂O₅.

[0036] The method disclosed herein enables one-pot extraction and purification of vanadium (V) without co-extraction of alumina or silica. Electrolysis of the vanadium-rich liquid allows for the simultaneous recovery of the solvent and vanadium (V). The method uses only water and optionally produces hydrogen and oxygen as byproducts. Since no other byproducts are generated, no wastewater treatment is required.

[0037] In this article, the vanadium source may be referred to as the vanadium source, either otherwise or alternatively.

[0038] Vanadium sources can be industrial or environmental. Vanadium sources can include vanadium compounds from various sources and in various oxidation states. Vanadium compounds vary significantly depending on the source of the feedstock. Mineral sources contain vanadium present in the spinel structure of chromium, specifically in compositions such as (Fe,Mg,Mn)(V,Cr)₂O₄ or (Fe,Mn)₂(V,Ti)O₄. Some compounds are introduced during secondary vanadium source production. For example, Ca₂V₂O₇ may be found if the feedstock comes from iron and steel production, as limestone is one of the key consumables in steel production. However, refinery feedstocks may contain NaVO₃·H₂O, VOSO₄(H₂O)₆, FeVO₄, VO₂, or typically mixtures of cations and vanadates, such as (Mg, Ca, Na, K, Fe)⁻V₂O₇·xH₂O.

[0039] Industrial or environmental sources of vanadium can be, for example, bottom ash or fly ash, petroleum boiler ash, gasifier ash, alumina slag, and waste catalysts from sulfuric acid production units.

[0040] Industrial or environmental sources of vanadium may contain at least about 10 wt% elemental vanadium, suitably at least about 15 wt% elemental vanadium, for example at least about 20 wt% or at least about 25 wt% elemental vanadium, for example at least about 30 wt% elemental vanadium, such as about 35 wt% elemental vanadium. Methods for determining the elemental vanadium content are known in the art. For example, the vanadium content can be determined by inductively coupled plasma mass spectrometry (ICP-MS).

[0041] Where appropriate, industrial or environmental sources are gasifier ash.

[0042] The composition of gasifier ash can vary depending on the type of raw material (i.e., the material to be gasified) and the specific gasification process employed. Gasifier ash typically contains compounds such as silica, alumina, iron, calcium oxide, potassium, sodium, sulfur, chlorine, trace metals such as zinc and copper, carbon, and various minerals such as Ca3V2O8, Ca2V2O7, Ca(VO3)2, Ni3V2O8, and Fe2V4O. 13 FeVO4 and Fe(VO3)2.

[0043] The gasifier ash may contain at least about 10% by weight of elemental vanadium, preferably at least about 15% by weight of elemental vanadium, such as at least about 20% by weight or at least about 25% by weight of elemental vanadium, such as at least about 30% by weight of elemental vanadium, such as about 35% by weight of elemental vanadium.

[0044] Suitablely, the gasifier ash contains about 10% to about 60% by weight of elemental vanadium, such as about 15% to about 55% by weight of elemental vanadium, such as about 20% to about 50% by weight of elemental vanadium, such as about 25% to about 45% by weight of elemental vanadium, such as about 35% to about 45% by weight of elemental vanadium.

[0045] Vanadium can originate from metallic ores containing vanadium. Unlike metals such as copper, nickel, or zinc, vanadium does not tend to accumulate in concentrated deposits. This is due to V 3+ with Fe 3+ The cations have very similar properties, resulting in vanadium typically existing in small amounts within iron minerals. One such vanadium mineral is vanadium magnetite (FeV₂O₄), which forms a mineral series with chromite (FeCr₂O₄) and magnetite (Fe₃O₄). Most vanadium production occurs during the extraction of titanomagnetite, which can be obtained directly from titanomagnetite ore / concentrate or indirectly from the slag produced during the smelting of these ores. Timomagnetite ore is usually associated with mafic igneous rocks and is found in large quantities.

[0046] The first aspect of the method includes: leaching a vanadium-containing source with a composition containing a compound of formula (I):

[0047] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0048] Among them, A + For N + or P + ; R1, R2, R3, and R4 can each be the same. R1, R2, R3, and R4 can each be different.

[0049] As used herein, the term "hydrocarbon group" is used in its common meaning as is well known to those skilled in the art. Specifically, it refers to a group that primarily possesses hydrocarbon characteristics. Examples of hydrocarbon groups include: (i) Hydrocarbon groups, i.e., aliphatic (which may be saturated or unsaturated, straight or branched, such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl) substituents, and aromatic substituents, aliphatic and alicyclic substituents, and cyclic substituents, wherein the ring is completed by another part of the molecule (e.g., two substituents together form a ring). (ii) A substituted hydrocarbon group, i.e., a substituent containing a non-hydrocarbon group, wherein, in the context of this invention, the non-hydrocarbon group does not alter the primary hydrocarbon properties of the substituent (e.g., halogen (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, amino, alkylamino, nitro, nitroso, and sulphoxy). (iii) Heterosubstituents, that is, in the context of this invention, substituents that have predominantly hydrocarbon characteristics but contain elements other than carbon in a ring or chain originally composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass substituents such as pyridyl, furanyl, thiophene, and imidazolyl.

[0050] Suitablely, R1, R2, R3, and R4 are each independently unsubstituted C. 1-10 Alkyl group. Suitably, R1, R2, R3, and R4 are each independently a substituted C1. 1-10 Alkyl, wherein the substituent is selected from: halogen (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, amino, alkylamino, nitro, nitroso, and thiooxy.

[0051] Suitablely, R1, R2, R3, and R4 are each independently unsubstituted C. 1-10 Aryl group. Suitablely, R1, R2, R3, and R4 are each independently substituted C. 1-10 Aryl, wherein the substituent is selected from: halogen (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, amino, alkylamino, nitro, nitroso, and thiooxy.

[0052] R1, R2, R3, and R4 can each be independently an unsubstituted C. 1-10 Alkyl groups, preferably unsubstituted C14 groups 1-9 Alkyl groups, for example, unsubstituted C4 groups 1-8 Alkyl, or unsubstituted C 1-7 Alkyl groups, such as unsubstituted C4 groups 1-5 Alkyl group. Suitably, R1, R2, R3, and R4 may each be an unsubstituted C1 group independently. 1-5 alkyl.

[0053] Appropriately, R1, R2, R3, and R4 are each the same.

[0054] In one example, R1, R2, R3, and R4 are each butyl. The compound of formula (I) is suitably tetrabutylphosphonium hydroxide or tetrabutylammonium hydroxide.

[0055] Suitablely, R1, R2, R3 and R4 are each propyl. Suitablely, R1, R2, R3 and R4 are each independently ethyl.

[0056] In one example, R1, R2, R3, and R4 are each methyl groups. The compound of formula (I) is suitably tetramethylammonium hydroxide (TMA) or tetramethylphosphonium hydroxide.

[0057] The composition is suitably an aqueous composition and suitably further comprises water. The compound of formula (I) is suitably water-soluble. The compound of formula (I) is suitably water-soluble at room temperature.

[0058] "Water-soluble" is used in its usual sense to refer to compounds that are soluble in water.

[0059] The United States Pharmacopeia (USP) has established the following definitions to limit solubility: Descriptive term: approximate volume of solvent (in mL / g of substance). Very soluble less than 1 Easily soluble 1 to 10 Soluble 10 to 30 Slightly soluble (30 to 100) Slightly soluble (100 to 1,000) Very slightly soluble (1,000 to 10,000) Almost insoluble above 10,000 Compounds of formula (I) are suitably soluble in water. Compounds of formula (I) are readily soluble in water.

[0060] In the method of the first aspect, the composition further comprises an oxidizing agent.

[0061] An oxidant is appropriately provided to oxidize vanadium compounds with an oxidation state lower than 5 produced by heat treatment of carbonaceous vanadium-containing feedstock back to vanadium (V).

[0062] The oxidizing agent can be any suitable oxidizing agent. For example, the oxidizing agent can be any thermodynamic criterion that satisfies its equilibrium electrode potential. E 氧化 / 还原 > E V V / V IV Any oxidizing agent.

[0063] Examples of suitable oxidants include, but are not limited to: oxygen (O2); hydrogen peroxide (H2O2); potassium permanganate (KMnO4); sodium chlorate (NaClO3); chlorine (Cl2); sodium hypochlorite (NaClO); nitric acid (HNO3); peracetic acid (PAA); potassium iodate (KIO3); bromine (Br2); iodine (I2); ozone (O3); sodium peroxide (Na2O2); peroxides (such as organic peroxides); permanganates (e.g., potassium permanganate, sodium permanganate); and persulfates (e.g., ammonium persulfate, sodium persulfate).

[0064] Oxidizing agents may include chlorite (ClO2) - ), chlorate anion (ClO3) - ) and / or hypochlorite anion (ClO) - For example, oxidants can be selected from the following group: sodium chlorite, sodium chlorate, sodium hypochlorite, hypochlorous acid, and potassium chlorate.

[0065] Oxidizing agents can also be selected from "active chlorine" (Cl2 (aq), Cl3) - HClO, ClO - ), active bromine or active iodine. "Active" refers to chlorine, bromine or iodine that is easily oxidized.

[0066] The composition may contain more than one oxidizing agent.

[0067] Optionally, (a) leaching of the vanadium-containing source (e.g., industrial or environmental samples) is carried out at elevated temperatures, such as from about 50°C to about 120°C, or from about 80°C to about 100°C. Optionally, (a) leaching of the vanadium-containing source is not carried out under autoclaving conditions.

[0068] The method may further include: (a2) The extracted vanadium (V) is separated into liquid and solid. Optionally, this can be done by centrifugation or vacuum filtration.

[0069] Appropriately, (a2) is performed after (a) and before (b).

[0070] The method for separating the extracted vanadium (V) into liquid and solid can be any conventional solid-liquid separation method known in the art, such as centrifugation and vacuum filtration.

[0071] The extracted vanadium (V) is suitably separated into liquid and solid states, providing both solid extracted vanadium (V) and a solution containing the extracted vanadium (V) (also referred to herein as an extracted vanadium (V) solution), i.e., the method may further include: (a2) Separate the extracted vanadium (V) into solid extracted vanadium (V) and a solution containing extracted vanadium (V).

[0072] The method may further include: preparing the extracted vanadium (V) from the solid into a solution, and enriching the solution with vanadium (V) to form a vanadium (V)-rich solution. This operation can be performed to increase the vanadium (V) concentration in the solution to a desired value.

[0073] Vanadium (V)-rich solutions can come into contact with ammonium chloride to form ammonium metavanadate precipitate.

[0074] Ammonium metavanadate can decompose into vanadium oxide (V).

[0075] The first approach includes: (b) Recover the extracted vanadium (V).

[0076] Suitablely, step (b) includes: recovering the extracted vanadium (V) as a precipitate, optionally during electrodialysis.

[0077] Suitablely, the extracted vanadium (V) is recovered during electrodialysis, wherein the electrodialysis is carried out in an electrodialysis cell comprising: The anolyte, comprising a solution of the extracted vanadium (V); and Cathode electrolyte; and Cation permeation membrane.

[0078] Suitablely, the cathode electrolyte comprises a compound of formula (I) as described herein.

[0079] Suitablely, step (b) includes: precipitating the extracted vanadium (V) in the anolyte, for example by water oxidation-induced electrolytic acidification.

[0080] Suitablely, step (b) includes: regenerating the compound of formula (I) in a cathodic electrolyte, for example by reduction by water-binding electrodialysis.

[0081] In one example, the cathode electrolyte comprises tetramethylammonium hydroxide. In another example, the cathode electrolyte comprises tetrabutylphosphonium hydroxide.

[0082] Any suitable cation exchange membrane can be used. Examples of such membranes include Nafion™ (DuPont Inc.), such as Nafion™ 424 and Nafion™ 324.

[0083] Cation permeation membranes enable the selective migration of cations from the anolyte to the catholyte (such as TMA). +(Selective migration), while simultaneously reducing the water at the cathode to hydrogen and hydroxide ions, which are blocked by the cation permeation membrane and cannot be transported in reverse.

[0084] Suitably, the electrodialysis cell also includes a supporting electrolyte in the anolyte. Any suitable supporting electrolyte can be used. Suitable supporting electrolytes include acids with a pH of 2 to 6. For example, the supporting electrolyte can be sulfuric acid. Suitably, the electrodialysis cell also includes tetramethylammonium hydroxide in the catholyte.

[0085] The method may further include: (c) The solution containing the extracted vanadium (V) is mixed with other compounds such as ammonium salts, optionally with ammonium sulfate, to form a precipitate, such as ammonium metavanadate.

[0086] Suitablely, step (c) is performed after step (b).

[0087] Other compounds can be ammonium salts. Any suitable ammonium salt can be used. Suitablely, the ammonium salt is ammonium chloride. Suitablely, the ammonium salt is ammonium sulfate.

[0088] Other compounds may be acids. Any suitable acid may be used. Suitably, the acid is hydrochloric acid, sulfuric acid, or phosphoric acid.

[0089] Suitablely, other compounds (such as ammonium salts, optionally ammonium salts) are mixed with a solution containing the extracted vanadium (V) until the pH reaches about 7.

[0090] A solution containing the extracted vanadium (V) mixed with other compounds such as ammonium salts (optionally, with ammonium sulfate) will form a precipitate. Suitably, the precipitate is a compound containing both ammonium and vanadium (V). Suitably, the precipitate is ammonium metavanadate (NH4VO3).

[0091] The method may further include: (d) Decompose the precipitate formed in step (b) and / or step (c) into vanadium oxide (V).

[0092] Methods of decomposition are known in the art. For example, the precipitate can be decomposed into vanadium oxide (V) (V₂O₅) by thermal decomposition.

[0093] This method may include the precipitation and / or deposition of an organovanadium compound in the anode chamber onto the anode. Suitably, the same electrochemical equipment is used, and depending on the bulk pH of the anolyte, the organovanadium compound may be deposited onto the anode or precipitated in the anode chamber.

[0094] Organovanadium compounds can be H4(Me4N)2V 10 O 28 .5H2O or H3(Me4N)3V 10 O28 .6H2O.

[0095] Organovanadium compounds can decompose into vanadium oxide (V).

[0096] Therefore, in one instance, the method of the first aspect includes: (a) Leaching of vanadium-containing industrial or environmental samples with a composition containing tetramethylammonium hydroxide. The leaching process involves extracting vanadium from an industrial or environmental sample to provide a solution containing the extracted vanadium. (a2) Separate the solution containing the extracted vanadium into a liquid and a solid to provide the extracted vanadium (V) in solid form and the solution containing the extracted vanadium (V); (b) During the electrodialysis process, the extracted vanadium (V) is recovered as the principal product. (c) Mixing the solution containing the extracted vanadium (V) with an ammonium salt, optionally with ammonium sulfate, to form a precipitate; and (d) Decompose the precipitate formed in step (b) and / or step (c) into vanadium oxide (V).

[0097] Suitablely, the extracted vanadium can be vanadium oxide (V). The purity of vanadium oxide (V) can be at least about 95% by weight, such as at least about 97% by weight, for example at least about 99% by weight. The purity of the extracted vanadium can be determined using inductively coupled plasma mass spectrometry (ICP-MS).

[0098] According to the second aspect, compounds represented by the following formula are provided: H4(Me4N)2V 10 O 28 .5H2O.

[0099] The compounds of the second aspect may include XRD peaks at 2θ with the following characteristic peaks: approximately 9.05° ± 0.20°; approximately 9.32° ± 0.20°; approximately 10.19° ± 0.20°; approximately 10.91° ± 0.20°; approximately 11.42° ± 0.20°; approximately 12.37° ± 0.20°; approximately 14.44° ± 0.20°; approximately 15.37° ± 0.20°; approximately 16.00° ± 0.20°; approximately 19.99° ± 0.20°; approximately 22.86° ± 0.20°; approximately 24.09° ± 0.20°; approximately 25.59° ± 0.20°; approximately 28.05° ± 0.20°; approximately 44.41° ± 0.20°; and approximately 50.43° ± 0.20°.

[0100] According to the third aspect, the following compound is provided: H3(Me4N)3V 10 O 28 .6H2O.

[0101] The compounds of the third aspect may include XRD peaks at 2θ with the following characteristic peaks: approximately 7.90° ± 0.20°; approximately 8.11° ± 0.20°; approximately 8.85° ± 0.20°; approximately 9.17° ± 0.20°; approximately 9.57° ± 0.20°; approximately 11.00° ± 0.20°; approximately 11.80° ± 0.20°; approximately 12.18° ± 0.20°; approximately 13.12° ± 0.20°; approximately 14.41° ± 0.20°; approximately 15.30° ± 0.20°; approximately 16.02° ± 0.20°; approximately 17.93° ± 0.20°; approximately 19.76° ± 0.20°; approximately 21.83° ± 0.20°; approximately 24.46° ± 0.20°; approximately 25.02° ± 0.20°; approximately 26.97° ± 0.20°; approximately 27.89° ± 0.20° and approximately 29.29° ± 0.20°.

[0102] The compounds in the second and third aspects have the general formula H. x (Me4N) y V 10 O 28 .zH2O.

[0103] XPS can be used to determine the ratio of x to y.

[0104] TGA can be used to determine water content.

[0105] According to the fourth aspect, a compound according to the second or third aspect is provided, said compound being obtained by or obtainable by the method of the first aspect.

[0106] According to the fifth aspect, use of the composition is provided, said composition comprising a compound of formula (I):

[0107] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0108] Among them, A + For N + or P + ; Used to extract vanadium (V) from vanadium sources.

[0109] The vanadium source and the composition comprising a compound of formula (I) are as described with respect to the first aspect. Suitably, the compound of formula (I) is water-soluble, as described with respect to the first aspect.

[0110] Specifically, compositions comprising compounds of formula (I) may further comprise oxidizing agents, as described with respect to the first aspect.

[0111] Suitably, a use of a composition can be provided, said composition comprising: Compounds of formula (I):

[0112] R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and

[0113] Among them, A + For N + or P + ;as well as

[0114] Oxidizing agent Used to extract vanadium (V) from vanadium sources.

[0115] Suitablely, the use of the fifth aspect provides vanadium in the form of vanadium oxide (V) with a purity of at least about 95% by weight, such as at least about 97% by weight, for example at least about 99% by weight.

[0116] The features described above with respect to one of the foregoing aspects are equally applicable to other aspects after necessary modifications to the details. For example, the features described above with respect to the method of the first aspect of the invention are equally applicable to the use according to the fifth aspect after necessary modifications to the details.

[0117] While some preferred embodiments have been shown and described, those skilled in the art will understand that various modifications and variations can be made without departing from the scope of the invention as defined by the appended claims.

[0118] The optional features described herein may be used alone or in combination as appropriate, particularly in accordance with the combinations set forth in the appended claims. Optional features of various aspects or exemplary embodiments of the invention described herein are also to be understood, where appropriate, to be applicable to any other aspect or exemplary embodiment of the invention. In other words, those skilled in the art who read this specification should understand that optional features of various exemplary embodiments of the invention are interchangeable and combinable between different exemplary embodiments.

[0119] Please note that all papers and documents related to this application, submitted at the same time as or before this specification, and made publicly available with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0120] All features disclosed in this specification (including any appended claims and drawings) and / or all steps of any method or process so disclosed may be combined in any way, except for combinations in which at least some of such features and / or steps are mutually exclusive.

[0121] Unless otherwise stated, the features disclosed in this specification (including any appended claims and drawings) may be replaced by alternative features having the same, equivalent, or similar purpose. Therefore, unless otherwise stated, the disclosed features are merely one example of a series of equivalent or similar features. The invention is not limited to the details of the above-described embodiments. The invention extends to any new type or any new combination of the features disclosed in this specification (including any appended claims and drawings), or to any new type or any new combination of any method or process step so disclosed.

[0122] Example

[0123] Example 1

[0124] Add 20g of gasification furnace ash containing approximately 39% by weight of elemental vanadium to 200ml of 2.78M tetramethylammonium hydroxide solution. Here, 4g of sodium chlorite is added as an oxidant. To eliminate sodium ion impurities in the process, active chlorine or ClO can be added directly to the solution instead. x The compound was then heated to 90°C while stirring and maintained for 540 minutes. The liquid and solid were separated by conventional methods such as centrifugation or vacuum filtration. Vanadium (V) recovery was achieved at 82% under oxidizing conditions and 63% under non-oxidizing conditions. The resulting solution was used as feedstock for an electrochemical recovery process.

[0125] Example 2

[0126] 1 ml of sulfuric acid (11 M) was added as a supporting electrolyte to 120 ml of a tetramethylammonium hydroxide solution containing 0.89 M vanadium (V). This solution was then poured into the anode chamber of the electrochemical reactor. At the start of the experiment, the cathode electrolyte contained 23 mM tetramethylammonium hydroxide to provide ionic conductivity. The anode electrolyte was electrolyzed to near-neutral pH. The resulting solution was mixed with an ammonium salt, such as ammonium sulfate, until a white precipitate of ammonium metavanadate was formed. Optionally, ammonium metavanadate can be thermally decomposed into >99 wt% V₂O₅ and NH₃ + H₂O. The recovered ionic liquid was removed from the cathode chamber and set aside for recycling in the vanadium (V) leaching process.

[0127] Example 3

[0128] 1 ml of sulfuric acid (11 M) was added as a supporting electrolyte to 120 ml of a tetramethylammonium hydroxide solution containing 0.89 M vanadium (V). This solution was then poured into the anode chamber of the electrochemical reactor. The cathode electrolyte, initially containing 23 mM tetramethylammonium hydroxide, provided the initial ionic conductivity. The anode electrolyte was electrolyzed until pH 2 was reached, at which point compounds containing vanadium and ionic liquid cations (organovanadium compounds) precipitated in the anode chamber. Similar compounds may deposit on the anode. Depending on the nature of the ionic liquid, any organovanadium compound can thermally decompose to produce >99% V₂O₅ and gaseous products. Alternatively, the organovanadium compound was mixed with an ammonium sulfate solution until a white precipitate of ammonium metavanadate was formed. Optionally, ammonium metavanadate can decompose to >99% V₂O₅ and NH₃ + H₂O. The recovered ionic liquid was removed from the cathode chamber and set aside for recycling in the vanadium (V) leaching process.

[0129] The organovanadium compound formed in Example 3 was filtered and dried at room temperature.

[0130] XRD data was collected from an X'Pert 3 XRD machine.

[0131] The XRD pattern of the organovanadium compound formed in Example 3 is as follows: Figure 1 and Figure 2 As shown.

[0132] Figure 1 H4(Me4N)2V was displayed. 10 O 28 X-ray diffraction pattern of .5H2O.

[0133] Table 1

[0134] Figure 1 The peaks shown are summarized in Table 1.

[0135] Figure 2 H3(Me4N)3V was displayed. 10 O 28 X-ray diffraction pattern of .6H2O.

[0136] Table 2

[0137] Figure 2 The peaks shown are summarized in Table 2.

[0138] Example 4

[0139] For a continuous process, a tetramethylammonium hydroxide solution containing 0.89 M vanadium (V) is continuously added to the anode chamber. The pH of the anolyte is maintained near neutral. The resulting anolyte is mixed with an ammonium salt, such as ammonium sulfate, until a white precipitate of ammonium metavanadate is formed. Optionally, ammonium metavanadate can be thermally decomposed into >99% V₂O₅ and NH₃ + H₂O. The regenerated ionic liquid is continuously removed, and water is added to the cathode chamber.

[0140] Example 5

[0141] This embodiment aims to recover vanadium (V) from the residue to the greatest extent possible. 10g of the post-reaction solid (residue) is mixed with 100ml of methanol at room temperature for half an hour. The solid and liquid are separated using conventional methods. The solution is circulated 4-5 times to enrich the vanadium (V) content in the methanol solution. A concentrated ammonium chloride methanol solution is slowly added to the circulated solution until no more white precipitate of ammonium metavanadate forms. Optionally, ammonium metavanadate can be thermally decomposed into >99% V₂O₅ and NH₃ + H₂O.

[0142] Example 6

[0143] The descriptions of reactions 1 through 17 are listed below: 1. Half-reaction of mixed (lower oxidation state) vanadium oxides to vanadium (V) 2. The half-reaction of hypochlorite to chloride 3. Overall Redox Reactions

[0144] 4. Vanadium (V) dissolution at high pH

[0145] 5. Chlorine gas is generated at the anode.

[0146] 6. Water reduction at the cathode

[0147] 7. Chemical reaction between dissolved chlorine and water

[0148] 8. Hypochlorous acid dissociation reaction

[0149] 9. Vanadium pentoxide dissolution reaction

[0150] 10. Water oxidation reaction at the anode

[0151] 11. Vanadium (V) condensation reaction

[0152] 12. Water reduction at the cathode

[0153] 13. Overall Electrolysis Process

[0154] 14. Ammonium metavanadate precipitation reaction

[0155] 15. The calcination reaction of ammonium metavanadate to vanadium pentoxide.

[0156] 16. Ammonia Recovery

[0157] 17. Total Vanadium Recovery Process

[0158] This method includes tetramethylammonium chloride (TMA) + Cl - In the presence of [a substance], ash is mixed in an electrochemical reactor equipped with a stainless steel AISI 316 cathode and a Ti / RuO2 anode. At pH 9-10, tetramethylammonium hypochlorite (TMA) is produced. + ClO - This process oxidizes vanadium oxides in their lower oxidation states (reactions 1 and 2). The resulting TMA... + Cl - In-situ conversion back to TMA + ClO - The circuit was completed (reactions 5-8). Subsequently, the pH of the solution was raised to >14 by passing concentrated tetramethylammonium hydroxide solution, and vanadium (V) was leached into the solution (reactions 4 and 9). The leachate was then fed into a membrane-separated electrochemical reactor, where H4TMA2V... 10 O 28 Deposits form on the anode surface. Deposits formed between pH 5 and 6 are subsequently removed mechanically, followed by suspension in an ammonia-methanol solution to remove TMA from the vanadate. + Ions. However, NH4VO3 is calcined at 550°C to produce ultra-high purity vanadium pentoxide.

[0159] Non-separated reactor

[0160] In-situ oxidation reaction

[0161] Example 7

[0162] For electrolysis using an anodic (a) redox couple (O|R) and a cathode (c) redox couple (O'|R'), the reactor potential difference (U) is: Equation 18 It possesses the activation and transport overpotential at the thermodynamic equilibrium electrode potential (E), anode (a), and cathode (c). ), and the current I flows through a path length d i and cross-sectional area A iThe conductivity is i The component resulting from the ohmic potential loss during phase i. By convention, the negative sign indicates an anti-spontaneous process.

[0163] This process produces TMA per ton of product via reaction (22). + (molar mass) M TMA + 84 g mol -1 ) specific energy consumption (kW ht) TMA + -1 (Among them, electronic stoichiometry) e,TMA + In this case, 1) is: Equation 19 It is linearly correlated with the reactor potential difference U, and also with the charge yield of the desired reaction (22). Equation 25) is inversely proportional, that is, TMA + Ions and H + Ion competition is the transport process through a cation permeation membrane; F represents the Faraday constant (96,485 A s mol). -1 ).

[0164] Therefore, the purpose of the electrochemical reactor is to enable TMA + Ions selectively migrate from the anolyte to the catholyte through a cation permeation membrane, and the electric field strength across the membrane ( This provides the driving force. The transport rate can be approximated using the Nernst-Planck equation for flux density: Equation 20 Of these, the last term can be considered negligible within the membrane due to convective flow. Although the first term indicates that the migration transport rate increases linearly with the transmembrane electric field strength, this rate is ultimately limited by mass transport into the membrane (rather than across it). A current density greater than the current density limited by the mass transport rate leads to a decrease in charge yield. Equation 25), and therefore, the increase in electricity (Equation 19) and cost dominates the operating cost of the process and the cost of a particular V2O5 product.

[0165] The application of an electric field requires an external electrode pair, where electrochemical oxidation (at the anode) and reduction (at the cathode) occur. If no electroactive substances are present in the aqueous electrolyte solution, the above reactions are: water is oxidized to oxygen and protons via reaction (21) and reduced to hydrogen and hydroxide ions via reaction (26). In addition to the non-equilibrium contribution to the reactor potential difference U due to the current, this also requires an equilibrium potential difference of 1.23 V at 298 K in equation (18). The corresponding process chemistry is described by reactions (21-33) below, where the net total reaction is (33).

[0166] However, by feeding hydrogen generated from the cathode to the (gas diffusion) anode, the hydrogen is oxidized to protons at the anode via reaction (34). The absence of oxygen release eliminates the requirement for a balance potential difference, reduces the operating potential difference of the reactor (Equation 18), and thus, according to Equation (19), reduces specific energy consumption. The corresponding process chemistry is described below by reactions (34-46), with the net total reaction being (46).

[0167] Chemical Process for Recovering V2O5 via Hydrolysis and Electrodialysis

[0168] anode: Reaction 21

[0169] Cation permeation membrane: maximize: ; j TMA + Reaction 22 Minimize: ; j H + Reaction 23 Current density: j 总 = j TMA + + j H + Equation 24 TMA + Charge yield: Equation 25 cathode: Reaction 26 Leaching: Reaction 27

[0170] Homogeneous solution (3 < pH < 6): Reaction 28

[0171] Overall electrolysis process: Reaction 29

[0172] Ammonium vanadate precipitation Reaction 30

[0173] Calcination of ammonium vanadate at 550℃ / V₂O₅ production Reaction 31

[0174] Ammonia cycle is achieved through water absorption. Reaction 32

[0175] Overall process chemical procedures: Reaction 33

[0176] Chemical Process for V2O5 Recovery Using Electrodialysis with Hydrogen Oxidation Gas Diffusion Anode

[0177] Gas diffusion anode: Reaction 34

[0178] Cation permeation membrane: maximize: ; j TMA + Reaction 35 Minimize: ; j H + Reaction 36 Current density: j 总 = j TMA + + j H + Reaction 37 TMA + Charge yield: Reaction 38 cathode: Reaction 39 Leaching: Reaction 40

[0179] Homogeneous solution (3 < pH < 6): Reaction 41

[0180] Overall electrolysis process: Reaction 42

[0181] Ammonium vanadate precipitation Reaction 43

[0182] Calcination of ammonium vanadate at 550℃ / V₂O₅ production Reaction 44

[0183] Ammonia cycle is achieved through water absorption. Reaction 45

[0184] Overall process chemical procedures: Reaction 46

[0185] Example 8

[0186] One gram of sodium vanadate was mixed with 15 ml of a solution containing 1 M total sulfate and 2.78 M total tetramethylammonium cations, equilibrated with hydroxide ions. The mixture was stirred until no solid residue remained in the vial. While stirring, approximately 35 ml of methanol was added to the solution until white sodium sulfate crystals formed. The methanol was removed by rotary evaporation, and the resulting solution was used to recover high-purity vanadium, as described in Example 4.

[0187] This research was supported by the Engineering and Physical Sciences Research Council [Grant Nos. EP / P51052X / 1 and EP / X52556X / 1].

Claims

1. A method for extracting vanadium (V) from a vanadium-containing source, the method comprising: (a) Leaching of a vanadium-containing source using a composition containing a compound of formula (I): R1, R2, R3, and R4 are each independently represented by C. 1-10 hydrocarbon group; and Among them, A + For N + or P + ; The composition further comprises an oxidizing agent; and The leaching process extracts some vanadium from a vanadium-containing source to provide extracted vanadium (V); and (b) Recover the extracted vanadium (V).

2. The method as described in claim 1, wherein, The vanadium content is from: (a) Industrial or environmental sources of vanadium, Choose any location The industrial or environmental source is selected from: bottom ash or fly ash, petroleum boiler ash, gasifier ash, alumina slag, and waste catalyst from sulfuric acid production units; suitably, the industrial or environmental source is gasifier ash; or (b) Vanadium-containing metal ores.

3. The method as claimed in claim 1 or claim 2, wherein, R1, R2, R3, and R4 are all the same. Optionally, R1, R2, R3, and R4 are each independently unsubstituted C. 1-10 Alkyl, suitably, wherein R1, R2, R3 and R4 are each methyl, or wherein R1, R2, R3 and R4 are each butyl.

4. The method as described in any of the preceding claims, wherein, The compound of formula (I) is tetrabutylphosphonium hydroxide.

5. The method according to any one of claims 1-4, wherein, The compound of formula (I) is tetramethylammonium hydroxide.

6. The method as described in any of the preceding claims, wherein, Oxidizing agents include chlorites, chlorates, or hypochlorites, such as sodium chlorite, sodium chlorate, or sodium hypochlorite.

7. The method as described in any of the preceding claims, wherein, The oxidizing agent is selected from: active chlorine, active bromine, active iodine, or ClO. x .

8. The method as described in any of the preceding claims, wherein, (a) Leaching of industrial or environmental samples is carried out at elevated temperatures, such as from about 50°C to about 120°C, or from about 80°C to about 100°C.

9. The method as described in any one of the preceding claims, further comprising: (a2) The extracted vanadium is separated into liquid and solid. Optionally, this can be done by centrifugation or vacuum filtration.

10. The method as described in any of the preceding claims, wherein, (b) includes precipitating the extracted vanadium (V) during electrodialysis, suitably wherein the electrodialysis is carried out in an electrodialysis cell comprising: The anolyte comprises a solution containing the extracted vanadium (V); and Cathode electrolyte; and Cation permeation membrane.

11. The method as described in any of the preceding claims, wherein, The cathode electrolyte contains a compound of formula (I), preferably tetramethylammonium hydroxide.

12. The method of claim 10 or 11, wherein, The electrodialysis process also includes a supporting electrolyte in the anolyte, which is preferably sulfuric acid.

13. The method as described in any of the preceding claims, further comprising: (c) The solution containing the extracted vanadium (V) is mixed with an ammonium salt, optionally with ammonium sulfate, to form a precipitate, such as ammonium metavanadate.

14. The method of claim 13, further comprising: (d) Decompose the precipitate into vanadium oxide (V).

15. The method as described in any of the preceding claims, wherein, Organovanadium compounds precipitate and / or deposit onto the anode in the anode chamber. Optionally, the organovanadium compound is H4(Me4N)2V 10 O 28 .5H2O or H3(Me4N)3V 10 O 28 .6H2O; and / or Optionally, the organovanadium compound decomposes into vanadium oxide (V).

16. The method of claim 9, wherein, The extracted vanadium (V) from the solid is made into a solution and enriched to form a vanadium-rich solution.

17. The method of claim 17, wherein, The vanadium (V)-rich solution is brought into contact with ammonium sulfate to form ammonium metavanadate precipitate.

18. The method of claim 18, wherein, Ammonium metavanadate decomposes into vanadium oxide (V).

19. The method as described in any of the preceding claims, the method comprising: (a) Leaching of vanadium-containing industrial or environmental samples with a composition comprising tetramethylammonium hydroxide and sodium hydroxide. The leaching process involves extracting vanadium from an industrial or environmental sample to provide a solution containing the extracted vanadium. (a2) Separate the solution containing the extracted vanadium into liquid and solid; (b) During the electrodialysis process, the extracted vanadium (V) liquid is recovered as a vanadium (V) precipitate; (c) Mixing the solution containing the extracted vanadium (V) with an ammonium salt, optionally with ammonium sulfate, to form a precipitate; and (d) Decompose the precipitate formed in (b) and / or (c) into vanadium oxide (V).

20. The method of any one of claims 15, 18, or 19, wherein, The purity of vanadium oxide (V) is at least about 95% by weight, such as at least about 97% by weight, for example at least about 99% by weight.

21. A compound with the following formula: H4(Me4N)2V 10 About 28 .5H2O。 22. A compound with the following formula: H3(Me4N)3V 10 About 28 .6H2O。 23. The compound of claim 21 or claim 22, which is obtained by the method of any one of claims 1 to 20 or can be obtained by the method of any one of claims 1 to 20.

24. Use of the composition, wherein the composition comprises a compound of formula (I): R1, R2, R3, and R4 are each independently C 1-10 hydrocarbon group; and in, A + For N + or P + ; Used to extract vanadium (V) from vanadium sources.

25. The use as described in claim 24, wherein, The compound of formula (I) is water soluble.

26. The use as described in claim 24 or 25, wherein, Vanadium is extracted in the form of vanadium oxide (V) with a purity of at least about 95% by weight, such as at least about 97% by weight, for example at least about 99% by weight.

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