TW202031594A - Method for purifying vanadium oxide - Google Patents
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本發明有關自包含陽離子成分之氧化釩原料精製氧化釩之方法。The present invention relates to a method for refining vanadium oxide from vanadium oxide raw materials containing cationic components.
燃燒飛灰或使用過之氫化脫硫觸媒中含有釩或鎳等之有用元素，而期望釩能儘可能回收有效利用。釩的用途主要分為鋼鐵用之添加劑與化學品用之原料。鋼鐵用時係添加於工具鋼、高速鋼、高張力鋼、不鏽鋼、橋樑之建築用鋼及耐熱鋼等，以化學品使用於脫硝觸媒、硫酸製造觸媒、橡膠聚合觸媒及顏料等之原料。最近則被利用作為鈦合金、氫吸存合金、形狀記憶合金及二次電池等之新素材或新材料之重要構成成分，其使用量亦增大。Combustion fly ash or used hydrodesulfurization catalyst contains useful elements such as vanadium or nickel, and it is expected that vanadium can be recycled and used effectively. The uses of vanadium are mainly divided into additives for steel and raw materials for chemicals. Steel is added to tool steel, high-speed steel, high-tensile steel, stainless steel, construction steel for bridges, and heat-resistant steel, etc. It is used in denitration catalysts, sulfuric acid manufacturing catalysts, rubber polymerization catalysts, and pigments. The raw materials. Recently, it has been used as an important component of new materials or new materials in titanium alloys, hydrogen storage alloys, shape memory alloys, and secondary batteries, and its use has also increased.
作為自此等釩予以回收之方法，已採用將鹼性或酸性水溶液作為萃取液，萃取出固體物質中之釩成分後，於包含所得釩之混合溶液中添加硫酸銨或氯化銨等之銨鹽予以中和而沉澱/回收之方法(例如專利文獻1~4)。As a method of recovering vanadium from such vanadium, an alkaline or acidic aqueous solution has been used as an extracting liquid. After the vanadium component in the solid material is extracted, ammonium sulfate or ammonium chloride is added to the mixed solution containing the obtained vanadium. A method of salt neutralization and precipitation/recovery (for example,
於包含釩、鉬等重金屬之混合溶液中，添加硫酸銨或氯化銨等之銨鹽時，析出偏釩酸銨並沉澱。When an ammonium salt such as ammonium sulfate or ammonium chloride is added to a mixed solution containing heavy metals such as vanadium and molybdenum, ammonium metavanadate is precipitated and precipitated.
接著，藉由對該偏釩酸銨之沉澱進行各種處理，而將釩以五氧化二釩之狀態回收。 已知該中間生成物的偏釩酸銨的純度不高時，所得五氧化二釩含有雜質即鈉(專利文獻5)。Then, by performing various treatments on the precipitation of the ammonium metavanadate, the vanadium is recovered in the state of vanadium pentoxide. It is known that when the purity of the intermediate product ammonium metavanadate is not high, the obtained vanadium pentoxide contains sodium as an impurity (Patent Document 5).
五氧化二釩中存在雜質的鈉時，於製造特殊鋼等之際，作成熔融狀態時會突沸，且會使所製造之特殊鋼變脆，有對特殊鋼本身之強度造成不良影響之可能性。When there is impurity sodium in vanadium pentoxide, it will suddenly boil in the molten state when manufacturing special steel, etc., and the manufactured special steel will become brittle, which may adversely affect the strength of the special steel itself. .
而且，於成為固體狀之五氧化二釩中混入之鈉難以去除，因此為了獲得高純度之五氧化二釩，而檢討以偏釩酸銨之狀態去除雜質之方法(專利文獻5)或為了提高偏釩酸銨之純度而重複鹽析。In addition, the sodium mixed in the solid vanadium pentoxide is difficult to remove. Therefore, in order to obtain high-purity vanadium pentoxide, the method of removing impurities in the state of ammonium metavanadate (Patent Document 5) or to improve The purity of ammonium metavanadate is repeated salting out.
又，亦提案將五氧化二釩暫時溶解於硫酸中，使釩成為5價釩，與鹼性陰離子交換樹脂接觸而吸附釩後，自該樹脂解吸之方法(專利文獻6)。 [先前技術文獻] [專利文獻]In addition, a method of temporarily dissolving vanadium pentoxide in sulfuric acid to convert vanadium into pentavalent vanadium, contacting with a basic anion exchange resin to adsorb vanadium, and desorbing from the resin (Patent Document 6). [Prior Technical Literature] [Patent Literature]
[專利文獻1] 日本特開2000-247644號公報 [專利文獻2] 日本特開2005-298925號公報 [專利文獻3] 日本特開平10-114525號公報 [專利文獻4] 日本特開昭63-100019號公報 [專利文獻5] 日本特開2012-036024號公報 [專利文獻6] 日本特開2002-193620號公報[Patent Document 1] JP 2000-247644 A [Patent Document 2] JP 2005-298925 A [Patent Document 3] Japanese Patent Application Laid-Open No. 10-114525 [Patent Document 4] JP 63-100019 A [Patent Document 5] JP 2012-036024 A [Patent Document 6] JP 2002-193620 A
[發明欲解決之課題][The problem to be solved by the invention]
自如燃燒灰或廢觸媒之含較多雜質之原料回收釩時，最終會獲得含陽離子成分之氧化釩，而有對特殊鋼製造步驟或所得特殊鋼本身之強度造成不良影響之可能性等之問題。以過去檢討之精製方法，釩的回收量少，處理效率低，有陽離子去除不充分之情況。 [用以解決課題之手段]When recovering vanadium from raw materials containing more impurities such as burning ash or waste catalyst, vanadium oxide containing cationic components will be finally obtained, which may adversely affect the special steel manufacturing process or the strength of the obtained special steel itself, etc. problem. With the refining method reviewed in the past, the recovery of vanadium is small, the treatment efficiency is low, and the removal of cations may be insufficient. [Means to solve the problem]
本發明為解決上述課題而積極檢討之結果，發現藉由對包含陽離子成分之氧化釩原料進行特定之浸漬步驟，可提高釩之回收率，且可製造陽離子成分被減低之精製氧化釩，因而完成本發明。As a result of active review of the present invention to solve the above-mentioned problems, it was found that by performing a specific impregnation step on the vanadium oxide raw materials containing cationic components, the recovery rate of vanadium can be improved, and refined vanadium oxide with reduced cationic components can be produced. this invention.
本發明之構成如下。 [1] 一種氧化釩之精製方法，其具有將包含陽離子成分之氧化釩原料於110℃以上浸漬於0.9N以上之酸性水溶液之步驟。 [2] 如[1]之氧化釩之精製方法，其中前述步驟中，將前述氧化釩原料以前述氧化釩原料中之釩量相對於前述酸性水溶液之容量成為0.02 g/mL以上0.7 g/mL以下之方式進行浸漬。 [3] 如[1]或[2]之氧化釩之精製方法，其中前述步驟中，前述酸性水溶液之氫離子量n(H+ )、構成前述氧化釩原料中之陽離子成分之陽離子總量n(Cz+ )與陽離子之電荷z之間，滿足下述關係式， 關係式n(H+ )/{n(Cz+ )×z}≧1。 [4] 如[1]至[3]中任一項之氧化釩之精製方法，其中前述陽離子係包含選自鈉離子、銨離子、鉀離子、鋰離子、鈣離子、鎂離子、鋇離子所成之群之1者以上。 [5] 如[1]至[4]中任一項之氧化釩之精製方法，其中前述酸性水溶液係包含硫酸、鹽酸、磷酸、硝酸、乙酸中之任一者以上之水溶液。 [6] 如[1]至[5]中任一項之氧化釩之精製方法，其中前述氧化釩原料中之陽離子成分係於2~20質量%之範圍內。 [7] 如[1]至[6]中任一項之氧化釩之精製方法，其中前述步驟中，將前述氧化釩原料於110~300℃之水溶液中於0.1~100MPa之加壓下進行浸漬。 [發明效果]The structure of the present invention is as follows. [1] A method for purifying vanadium oxide, which has the step of immersing a vanadium oxide raw material containing cationic components in an acidic aqueous solution of 0.9N or more at 110°C or higher. [2] The method for purifying vanadium oxide as in [1], wherein in the foregoing step, the amount of vanadium in the vanadium oxide raw material relative to the capacity of the acidic aqueous solution becomes 0.02 g/mL or more and 0.7 g/mL Impregnation is performed in the following way. [3] The method for purifying vanadium oxide as in [1] or [2], wherein in the foregoing step, the amount of hydrogen ions in the acidic aqueous solution n(H + ), the total amount of cations constituting the cation component in the vanadium oxide raw material n Between (C z+ ) and the charge z of the cation, the following relational expression is satisfied, the relational expression n(H + )/{n(C z+ )×z}≧1. [4] The method for purifying vanadium oxide as described in any one of [1] to [3], wherein the aforementioned cations include those selected from sodium ion, ammonium ion, potassium ion, lithium ion, calcium ion, magnesium ion, and barium ion. More than 1 in a group. [5] The method for purifying vanadium oxide according to any one of [1] to [4], wherein the aforementioned acidic aqueous solution is an aqueous solution containing at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and acetic acid. [6] The method for purifying vanadium oxide according to any one of [1] to [5], wherein the cationic component in the vanadium oxide raw material is in the range of 2-20% by mass. [7] The method for purifying vanadium oxide according to any one of [1] to [6], wherein in the foregoing step, the vanadium oxide raw material is immersed in an aqueous solution at 110-300°C under a pressure of 0.1-100 MPa . [Invention Effect]
依據本發明，氧化釩之回收率高，且可獲得陽離子含量被減低之精製氧化釩。使用此精製方法，與自燃燒灰或廢觸媒回收釩組合，不僅回收率變高，且釩之利用性亦顯著提升。According to the present invention, the recovery rate of vanadium oxide is high, and refined vanadium oxide with reduced cation content can be obtained. Using this refining method, combined with the recovery of vanadium from self-burning ash or waste catalyst, not only increases the recovery rate, but also significantly improves the utilization of vanadium.
以下針對本發明之實施形態加以說明，但本發明並非限定於該等記載。 (原料) 本發明之釩化合物之精製方法中使用之精製前的氧化釩原料係將燃燒灰或使用過之廢觸媒浸漬於酸或鹼性溶液中，以硫酸等之酸或鹼對該浸出液即含釩液進行pH調整而得。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these descriptions. (raw material) The vanadium oxide raw material used in the refining method of the vanadium compound of the present invention is to immerse the combustion ash or the used waste catalyst in an acid or alkaline solution, and the leaching solution contains vanadium with an acid or alkali such as sulfuric acid. The solution is obtained by adjusting the pH.
例如藉由如本案申請人於國際公開2017/208471號說明書中之具有鹼浸出步驟、過濾步驟、pH調整步驟、熟成步驟及分離步驟之製造方法而調製。For example, it is prepared by a manufacturing method having an alkali leaching step, a filtration step, a pH adjustment step, an aging step, and a separation step in the specification of International Publication No. 2017/208471 by the applicant in this case.
鹼浸出步驟係於鹼性溶液中浸漬燃燒灰或廢觸媒。藉由浸漬於鹼性溶液，將燃燒灰或廢觸媒中之釩離子浸出於鹼性溶液中。所謂「鹼性溶液」意指pH為8以上之溶液。以下，將pH大於6小於8之pH區域稱為中性，將pH為6以下之pH區域稱為酸性。又，本發明之pH，係實施各步驟時之溫度下的pH，於未特別記載溫度之情況係室溫下之值。The alkaline leaching step involves immersing combustion ash or waste catalyst in an alkaline solution. By immersing in alkaline solution, vanadium ions in combustion ash or waste catalyst are immersed in alkaline solution. The so-called "alkaline solution" means a solution with a pH of 8 or higher. Hereinafter, the pH region where the pH is greater than 6 and less than 8 is referred to as neutral, and the pH region where the pH is below 6 is referred to as acidic. In addition, the pH in the present invention is the pH at the temperature when each step is carried out, and when the temperature is not specifically described, it is the value at room temperature.
構成鹼性溶液之材料並未特定。可使用例如氫氧化鈉、碳酸鈉、氫氧化鉀等。該等鉀之濃度並未特別限定，可為例如0.007~16 mol/L，較佳0.007~5mol/L。The material constituting the alkaline solution is not specified. For example, sodium hydroxide, sodium carbonate, potassium hydroxide, etc. can be used. The concentration of potassium is not particularly limited, and may be, for example, 0.007-16 mol/L, preferably 0.007-5 mol/L.
燃燒灰係火力發電廠等之以鍋爐等燃燒燃料時產生之燃燒殘渣。燃燒殘渣大致區分被區分為飛灰與爐灰。飛灰大多以電集塵機收集，亦稱為EP灰。一般作為燃料使用之化石燃料中包含釩。因此，燃燒後之飛灰及爐灰亦包含釩。燃燒灰中包含飛灰及爐灰兩者。又自脫硫反應塔排出之使用過的氫化脫硫觸媒亦被使用於用以獲得本發明之氧化釩原料。Combustion ash is the combustion residue produced when the boiler burns fuel in thermal power plants. The combustion residue is roughly divided into fly ash and furnace ash. Fly ash is mostly collected by electric dust collector, also known as EP ash. Fossil fuels generally used as fuel contain vanadium. Therefore, the fly ash and furnace ash after combustion also contain vanadium. The combustion ash includes both fly ash and furnace ash. The used hydrodesulfurization catalyst discharged from the desulfurization reaction tower is also used to obtain the vanadium oxide raw material of the present invention.
例如飛灰包含60~95質量%之未燃燒碳、0~20質量%之硫酸銨、及其他金屬。作為其他金屬包含0~5質量%銨、0~1質量%鋇、0~5質量%鈣、0~0.5質量%鈷、0~3質量%鉻、0~20質量%鐵、0~3質量%鎂、0~1質量%錳、0~3質量%鈉、0~20質量%鎳、0~3質量%鈦、0.01~30質量%釩、0~20質量%矽、進而0~0.1質量%其他微量金屬。該等比率係隨燃燒燃料時之爐內溫度、投入物質差異而異。For example, fly ash contains 60-95% by mass of unburned carbon, 0-20% by mass of ammonium sulfate, and other metals. Contains 0~5 mass% ammonium, 0~1 mass% barium, 0~5 mass% calcium, 0~0.5 mass% cobalt, 0~3 mass% chromium, 0~20 mass% iron, 0~3 mass% as other metals % Magnesium, 0 to 1 mass% manganese, 0 to 3 mass% sodium, 0 to 20 mass% nickel, 0 to 3 mass% titanium, 0.01 to 30 mass% vanadium, 0 to 20 mass% silicon, and then 0 to 0.1 mass % Other trace metals. These ratios vary with the temperature in the furnace and the difference in the input materials when the fuel is burned.
將燃燒灰或廢觸媒浸漬於所準備之鹼性溶液中。自其中浸出釩離子，而獲得浸出液。以下將添加燃燒灰或廢觸媒後之鹼性溶液漿料稱為「浸出液漿料」，該溶液部稱為「浸出液」。Immerse combustion ash or waste catalyst in the prepared alkaline solution. Vanadium ions are leached from it to obtain a leachate. Hereinafter, the alkaline solution slurry after adding combustion ash or waste catalyst is called "leaching liquid slurry", and the solution part is called "leaching liquid".
添加燃燒灰之鹼性溶液於添加燃燒灰前之狀態，pH較佳為10以上。 燃燒灰或廢觸媒若浸漬於pH為3以下之強酸性水溶液中，則釩離子與鐵離子一起浸出，而根據用途有產生不良影響之情況。但，鐵等之影響較少之情況下，可將燃燒灰或廢觸媒浸漬於酸性水溶液中調製浸出液。The pH of the alkaline solution before adding the combustion ash is preferably 10 or higher. If the combustion ash or waste catalyst is immersed in a strong acidic aqueous solution with a pH of 3 or less, vanadium ions and iron ions will be leached together, which may have adverse effects depending on the application. However, when the influence of iron is small, the leaching solution can be prepared by immersing combustion ash or waste catalyst in an acidic aqueous solution.
燃燒灰或廢觸媒中所含之釩不僅為5價者，亦包含4價或3價之釩。5價釩容易浸出於溶液中，但4價或3價釩則不易浸出於溶液中。使用氧化劑將4價或3價釩進行氧化處理使成為5價狀態，可增加釩離子於浸出液中之浸出量。The vanadium contained in the combustion ash or waste catalyst is not only pentavalent, but also tetravalent or trivalent vanadium. The pentavalent vanadium is easily leached out of the solution, but the tetravalent or trivalent vanadium is not easily leached into the solution. Oxidizing the tetravalent or trivalent vanadium with an oxidant to make it into a pentavalent state can increase the amount of vanadium ions leached in the leaching solution.
作為氧化劑可較佳地使用次鹵酸及其鹽、亞鹵酸及其鹽、鹵酸及其鹽、過鹵酸及其鹽、過錳酸及其鹽、鉻酸及其鹽、過氧化氫等。As the oxidant, hypohalous acid and its salt, halo acid and its salt, halogen acid and its salt, perhalogen acid and its salt, permanganic acid and its salt, chromic acid and its salt, hydrogen peroxide can be preferably used. Wait.
根據需要，將鹼浸出步驟所得之浸出液漿料進行過濾。藉由過濾浸出液漿料，可將經浸出釩離子之浸出液與含不溶分之鐵等之燃燒灰分離。According to need, the leachate slurry obtained in the alkali leaching step is filtered. By filtering the leachate slurry, the leachate from which vanadium ions have been leached can be separated from the combustion ash containing insoluble iron.
pH調整步驟中，於過濾後之浸出液中添加酸，將浸出液作成酸性。所用之酸並未特別限定。可使用例如鹽酸、硫酸、磷酸等之無機酸，亦可使用高次羧酸或酚等之有機酸。In the pH adjustment step, acid is added to the filtered leachate to make the leachate acidic. The acid used is not particularly limited. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid can be used, and organic acids such as higher carboxylic acids or phenols can also be used.
圖1係顯示5價之釩離子溶解度與pH之關係的相圖。圖1所示之V2 O5 區域為固體區域，於V2 O5 區域析出固體。亦即藉由使溶液之pH未達4而析出釩化合物。Figure 1 is a phase diagram showing the relationship between the solubility of 5 valent vanadium ions and pH. The V 2 O 5 region shown in Figure 1 is a solid region, and solids are precipitated in the V 2 O 5 region. That is, by making the pH of the solution less than 4, the vanadium compound is precipitated.
pH調整後之pH較佳為1.3~2.9。依據相圖，於pH=0~未達4之區域，具有固體析出之V2 O5 之區域，但pH調整後之pH若在上述範圍內，容易產生釩化合物之析出。The pH after pH adjustment is preferably 1.3 to 2.9. According to the phase diagram, in the region of pH=0 to less than 4, there is a region where solids precipitate V 2 O 5 , but if the pH after pH adjustment is within the above range, the precipitation of vanadium compounds is likely to occur.
熟成步驟中，於pH調整後之浸出液中析出物析出之前，於一定條件下放置。依據相圖，於V2 O5 之區域析出固體。然而，實際上浸出液雖說滿足V2 O5 之區域內之條件，但不能解釋為析出物立即析出。In the maturation step, it is placed under certain conditions before the precipitates in the pH-adjusted leachate precipitate. According to the phase diagram, solids precipitate in the V 2 O 5 region. However, although the leachate actually satisfies the conditions in the V 2 O 5 region, it cannot be interpreted as an immediate precipitation of precipitates.
於pH處於1.3~29之階段，認為5價釩離子以釩酸離子(VO2 + )及十釩酸離子(V10 O26 (OH)24 - )等之形態，以過飽和狀態存在。可理解為隨著時間經過，自水合離子等引起脫水聚合，可為5價氧化釩之骨架，產生結晶。氧化劑亦可於酸性條件下使用，可使氧化釩作為固形分析出。At a stage at pH 1.3 to 29, the pentavalent vanadium ions that vanadate ion (VO 2 +) ions and decavanadate (V 10 O 26 (OH) 24 -) form, etc., in the presence of a supersaturated state. It can be understood that as time elapses, self-hydrated ions cause dehydration and polymerization, which can be the skeleton of pentavalent vanadium oxide and crystallize. The oxidizing agent can also be used under acidic conditions, so that vanadium oxide can be analyzed as a solid form.
熟成步驟中，將pH調整後之浸出液於特定溫度條件下保持特定時間。pH調整後之浸出液之pH與pH剛調整後之pH相同，較佳為1.3~2.9。In the maturation step, the pH-adjusted leachate is kept at a specific temperature for a specific time. The pH of the leaching solution after pH adjustment is the same as the pH immediately after the pH adjustment, preferably 1.3 to 2.9.
又熟成步驟中之溫度較佳為20℃以上200℃以下，更佳為20℃以上且未達100℃。溫度低時析出需要的時間變長。另一方面溫度高時快速引起析出。In addition, the temperature in the maturing step is preferably 20°C or more and 200°C or less, more preferably 20°C or more and less than 100°C. When the temperature is low, the time required for precipitation becomes longer. On the other hand, precipitation occurs quickly when the temperature is high.
本發明中使用之氧化釩原料由於係將燃燒灰或廢觸媒於鹼或酸中浸出之含釩液根據需要進行pH調整，以氧化劑進行氧化處理者，故氧化釩通常以固體析出。通常本發明中，作為漿料使用，但亦可為藉由過濾所得之濾餅，且亦可為其乾燥粉體。The vanadium oxide raw material used in the present invention is a vanadium-containing liquid obtained by leaching combustion ash or waste catalyst in alkali or acid to adjust the pH as needed and oxidize with an oxidant, so vanadium oxide is usually precipitated as a solid. Generally, in the present invention, it is used as a slurry, but it can also be a filter cake obtained by filtration, and it can also be a dry powder.
該氧化釩原料中，作為浸出液之成分，或於pH調整之際，由於使用鹼，故主要的陽離子成分被納入。陽離子成分中，除了鹼成分以外，亦包含處理所使用之礦石等所含之鈣或鎂等之成分，但不限定於此。In this vanadium oxide raw material, as a component of the leaching solution, or during pH adjustment, an alkali is used, so the main cationic component is included. In addition to the alkali component, the cationic component also includes components such as calcium or magnesium contained in the ore used for processing, but is not limited to this.
前述氧化釩原料中之陽離子成分通常於2~20質量%，較佳3~7質量%之範圍。若為該範圍，則可容易地調整後述酸性水溶液之溶解。The cation component in the vanadium oxide raw material is usually in the range of 2-20% by mass, preferably 3-7% by mass. If it is this range, the dissolution of the acidic aqueous solution mentioned later can be adjusted easily.
陽離子成分 原料之氧化釩中所含之陽離子成分係於水溶液中包含選自鈉離子、銨離子、鉀離子、鋰離子、鈣離子、鎂離子、鋇離子所成之群之1者以上者。通常包含上述浸出步驟之浸出液或pH調整步驟中使用之鈉離子或銨離子。Cationic components The cation component contained in the vanadium oxide of the raw material contains at least one member selected from the group consisting of sodium ion, ammonium ion, potassium ion, lithium ion, calcium ion, magnesium ion, and barium ion in the aqueous solution. It usually contains the sodium ion or ammonium ion used in the leaching solution of the above-mentioned leaching step or the pH adjustment step.
依據本發明，可提供過去非常困難之可減低鈉等之陽離子成分之方法。 (酸性水溶液) 本發明中，將前述原料之氧化釩溶解於酸性水溶液中。詳細方法於後述，因此此處針對酸性水溶液的組成加以說明。 水性水溶液若為解離氫離子H+ 者則可為任何水溶液。一般使用硫酸或硝酸，但亦可使用鹽酸或磷酸、乙酸。According to the present invention, it is possible to provide a method for reducing cationic components such as sodium, which was very difficult in the past. (Acid aqueous solution) In the present invention, vanadium oxide of the aforementioned raw material is dissolved in an acid aqueous solution. The detailed method is described later, so the composition of the acidic aqueous solution will be described here. The aqueous aqueous solution can be any aqueous solution if it is the dissociated hydrogen ion H + . Generally, sulfuric acid or nitric acid is used, but hydrochloric acid, phosphoric acid, and acetic acid can also be used.
酸性水溶液之濃度 包含陽離子之氧化釩已知非常不易溶解於酸中。作為酸性水溶液之酸當量濃度，較佳為0.9N以上，更佳為2N以上，又更佳為5N以上。未達0.9N時，釩化合物之溶解度低，或溶解速度非常慢而難以溶出陽離子，故難以自原料減低陽離子。Concentration of acidic aqueous solution Vanadium oxide containing cations is known to be very difficult to dissolve in acid. The acid equivalent concentration of the acidic aqueous solution is preferably 0.9N or more, more preferably 2N or more, and still more preferably 5N or more. When it is less than 0.9N, the solubility of the vanadium compound is low, or the dissolution rate is very slow and it is difficult to dissolve cations, so it is difficult to reduce the cations from the raw material.
酸性水溶液與前述含陽離子之氧化釩之混合，較佳為氧化釩原料中之釩換算含量相對於前述酸性水溶液之容量成為0.02 g/mL以上0.7 g/mL以下，更佳為0.05 g/mL以上0.12 g/mL以下。酸性水溶液具有使陽離子溶出同時使氧化釩溶解之角色。The mixing of the acidic aqueous solution and the aforementioned cation-containing vanadium oxide is preferably such that the vanadium-converted content of the vanadium oxide raw material is 0.02 g/mL or more and 0.7 g/mL or less, more preferably 0.05 g/mL or more relative to the capacity of the aforementioned acidic aqueous solution Below 0.12 g/mL. The acidic aqueous solution has the role of dissolving cations while dissolving vanadium oxide.
又，本發明中，氫離子之量與氧化釩原料中之陽離子量較佳滿足特定關係。 亦即酸性水溶液之氫離子量n(H+ )(mol)、前述包含陽離子之氧化釩原料中所含之陽離子總量n(Cz+ )(mol)與陽離子之電荷z之間，較佳滿足下述關係式， 關係式n(H+ )/{n(Cz+ )×z}≧1。 又，此處所謂陽離子總量係鈉離子、銨離子、鉀離子、鋰離子、鈣離子、鎂離子、鋇離子之合計量。Furthermore, in the present invention, the amount of hydrogen ions and the amount of cations in the vanadium oxide raw material preferably satisfy a specific relationship. That is, the amount of hydrogen ions in the acidic aqueous solution n(H + ) (mol), the total amount of cations contained in the vanadium oxide raw material containing cations n(C z+ ) (mol) and the charge z of the cations are preferably between The following relational expression, the relational expression n(H + )/{n(C z+ )×z}≧1. In addition, the total amount of cations referred to herein is the total amount of sodium ions, ammonium ions, potassium ions, lithium ions, calcium ions, magnesium ions, and barium ions.
將n(H+ )/{n(Cz+ )×z}設為A時，A為1以上，較佳為5以下，更佳為10以上，又更佳為15以上。A越大越可充分去除陽離子。銨離子以外之陽離子係使用ICP發光分光分析法(ICP法)測定。又銨離子係藉由離子層析(IC)法分析，陽離子總量係藉由將前述之ICP發光分光分析法所得之值與銨離子之量相加而求出。When n(H + )/{n(C z+ )×z} is set to A, A is 1 or more, preferably 5 or less, more preferably 10 or more, and still more preferably 15 or more. The larger A is, the more cations can be fully removed. Cations other than ammonium ions are measured by ICP emission spectrometry (ICP method). The ammonium ion was analyzed by ion chromatography (IC), and the total amount of cations was calculated by adding the value obtained by the aforementioned ICP emission spectrophotometric method to the amount of ammonium ion.
為了使陽離子溶出，酸性水溶液相對於含陽離子之氧化釩原料為多量較佳。另一方面，就溶出後作為氧化釩而再沉澱而言較佳酸性水溶液為少量。氧化釩(V2 O5 )已知一般如圖1所示，pH低於2時溶解度變高。然而，本發明中藉由上述關係式及特定混合量，即使pH較低亦可作為固體回收氧化釩，進而可減低原料之陽離子。In order to dissolve cations, it is preferable that the acidic aqueous solution has a large amount relative to the cation-containing vanadium oxide raw material. On the other hand, in terms of reprecipitation as vanadium oxide after elution, a small amount of acidic aqueous solution is preferable. Vanadium oxide (V 2 O 5 ) is generally known as shown in Figure 1. When the pH is lower than 2, the solubility becomes higher. However, in the present invention, based on the above-mentioned relational formula and specific mixing amount, vanadium oxide can be recovered as a solid even if the pH is low, thereby reducing the cation of the raw material.
(氧化釩之精製方法) 其次說明本發明之氧化釩之精製方法。圖2以概略流程圖顯示本發明之精製方法。 本發明之釩化合物之精製方法(以下簡稱為本發明方法)係使酸性水溶液作用於氧化釩原料之含鈉等之陽離子之氧化釩，使氧化釩暫時溶解。此時，雜質之陽離子亦同時溶解於水溶液中。(Refining method of vanadium oxide) Next, the refining method of vanadium oxide of the present invention will be explained. Figure 2 shows the refining method of the present invention in a schematic flow chart. The purification method of the vanadium compound of the present invention (hereinafter referred to as the method of the present invention) is to make an acidic aqueous solution act on the vanadium oxide containing sodium and other cations of the vanadium oxide raw material to temporarily dissolve the vanadium oxide. At this time, the impurity cations are also dissolved in the aqueous solution.
其次本發明中作為陽離子經減低之氧化釩而析出並回收，藉此獲得經精製之氧化釩。 本發明之方法中，將氧化釩原料之含陽離子之氧化釩與酸性水溶液一起放入高壓釜等之密封容器中，設定於特定時間、高溫之條件。此時，含陽離子之氧化釩暫時溶解於酸性水溶液。此時之溫度較佳為110℃以上，較佳為140℃以上，又更佳為180℃以上。低於110℃時，溶解速度變慢而不實用。邊攪拌邊溶解時，有反應更易進行之優點。又，壓力並未特別限定，但較佳於水的蒸氣壓以上之加壓下進行。亦即，較佳於0.1~100MPa之加壓下進行。Secondly, in the present invention, the reduced vanadium oxide as a cation is precipitated and recovered, thereby obtaining refined vanadium oxide. In the method of the present invention, the cation-containing vanadium oxide of the vanadium oxide raw material is put into a sealed container such as an autoclave together with an acidic aqueous solution, and set at a specific time and high temperature conditions. At this time, the vanadium oxide containing cations is temporarily dissolved in the acidic aqueous solution. The temperature at this time is preferably 110°C or higher, preferably 140°C or higher, and more preferably 180°C or higher. When the temperature is lower than 110°C, the dissolution rate becomes slow and it is not practical. When dissolving while stirring, the reaction is easier to proceed. In addition, the pressure is not particularly limited, but it is preferably performed under a pressure higher than the vapor pressure of water. That is, it is preferably performed under a pressure of 0.1-100 MPa.
溫度上限，鑒於生產效率或反應器之耐久性等，較佳為300℃。 加熱時間並未特別限定，係隨酸性水溶液之溫度、酸濃度、酸性水溶液之液量而變化。加熱時間，作為標準期望為1小時以上，更佳3小時以上。若為3小時以上，則認為反應進行，含陽離子之氧化釩大致溶解。尤其溶解較慢時，若攪拌則溶解變快而較佳。The upper temperature limit is preferably 300°C in view of the production efficiency or the durability of the reactor. The heating time is not particularly limited, and it varies with the temperature, acid concentration, and liquid volume of the acidic aqueous solution. The heating time is expected to be 1 hour or more as a standard, more preferably 3 hours or more. If it is more than 3 hours, the reaction is considered to proceed and the cation-containing vanadium oxide is almost dissolved. Especially when the dissolution is slow, it is better to dissolve faster if stirring.
又，即使溫度較低，藉由攪拌等之條件或加熱條件，氧化釩變容易溶解，故加熱處理時之溫度、時間、攪拌等，係根據氧化釩之溶解狀態而適當選擇。In addition, even if the temperature is low, vanadium oxide is easily dissolved under conditions such as stirring or heating, so the temperature, time, stirring, etc. during the heat treatment are appropriately selected according to the dissolution state of vanadium oxide.
加熱處理後，冷卻至室溫可獲得固體。該固體為氧化釩。若成為陽離子經減低之五氧化二釩則呈現漂亮的黃色。又，所得固體亦可藉由使用例如過濾器加壓之過濾等而回收，隨後將回收之固體以不易溶解五氧化二釩之水或酸等進行洗淨。After the heat treatment, cool to room temperature to obtain a solid. The solid is vanadium oxide. Vanadium pentoxide with reduced cations will show a beautiful yellow color. In addition, the obtained solids can also be recovered by using, for example, filtration under pressure with a filter, and then the recovered solids are washed with water or acid that does not easily dissolve the vanadium pentoxide.
又，回收之五氧化二釩固體亦可適當乾燥，進而根據需要進行粉碎或分級等之處理。 如上述，燃燒灰或使用過之廢觸媒於酸或鹼性溶液中浸出之含釩液藉由硫酸等之酸或鹼進行pH調整所得之粗氧化釩作為原料，進行前述精製方法，藉此可提供自燃燒灰或使用過廢觸媒回收精製氧化釩之方法。 [實施例]In addition, the recovered vanadium pentoxide solid can also be dried appropriately, and then subjected to treatment such as pulverization or classification as necessary. As mentioned above, the vanadium-containing liquid obtained by leaching combustion ash or used waste catalyst in acid or alkaline solution is used as raw material for crude vanadium oxide obtained by pH adjustment with acid or alkali such as sulfuric acid, and the aforementioned purification method is carried out, thereby It can provide methods to recover refined vanadium oxide from combustion ash or used waste catalyst. [Example]
以下藉由實施例具體說明本發明，但本發明並非限定於該等實施例。
[實施例1]
準備Na2
V6
O16
・3H2
O作為含鈉之氧化釩原料。將其秤量2.778g (0.0042mol)，投入具有鐵氟龍(註冊商標)內筒之不鏽鋼製高壓釜中。且添加1.87mL之4.5mol/L硫酸(9N)。此時，硫酸具有之H+
與氧化釩中之Na+
的莫耳比(H+
/Cz+
)計算值為2。關閉高壓釜，以2小時升溫至200℃，於200之烘箱中保持8小時。降溫係耗費12小時左右自然放冷(此時稱為『反應8小時』或『反應時間為8小時』)。原本的5價氧化釩顏色為紅色，但反應後處於高壓釜內之固體為黃色。將其過濾，以水洗淨，回收固體。Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. [Example 1] Na 2 V 6 O 16 ·3H 2 O was prepared as a raw material of sodium-containing vanadium oxide. Weigh 2.778 g (0.0042 mol), and put it into a stainless steel autoclave with a Teflon (registered trademark) inner cylinder. And add 1.87mL of 4.5mol/L sulfuric acid (9N). At this time, the molar ratio (H + /C z+ ) of H + in sulfuric acid to Na + in vanadium oxide is calculated as 2. The autoclave was closed, the temperature was raised to 200°C in 2 hours, and it was kept in an oven of 200 for 8 hours. The cooling system takes about 12 hours to let it cool naturally (this time is called "
[實施例2~21、比較例1~2] 實施例2~21、比較例1~2係使用含表1所示之陽離子之氧化釩原料，以表1之條件進行與實施例1同樣處理，獲得氧化釩。 又，進行攪拌之實施例、比較例，於加熱期間(升溫時及保持之間)放入攪拌子以約200rpm進行攪拌。[Examples 2 to 21, Comparative Examples 1 to 2] Examples 2 to 21 and Comparative Examples 1 to 2 used vanadium oxide raw materials containing the cations shown in Table 1, and performed the same treatment as in Example 1 under the conditions of Table 1 to obtain vanadium oxide. In addition, in the examples and comparative examples in which the stirring was performed, a stirrer was placed during the heating period (when the temperature was raised and between the holding period) and stirred at about 200 rpm.
結果彙總示於表1。使原料及回收之固體個別乾燥，藉由ICP-AES(型號Vista-Pro日立高科技公司製)測定釩含量。 又實施例1~21及比較例1~2之陽離子總量確認為表1所示之陽離子種係其他陽離子為可忽略之含量，針對表1記載之陽離子種算出n(H+ )/[n(Cz+ )×z]。各陽離子含量係將原料溶解於硝酸，銨離子係使用離子層析儀(型號DIONEX INTEGRION，Thermo Scientific製)測定，銨離子以外係使用ICP-AES(型號Vista-Pro日立高科技公司製)測定。The results are summarized in Table 1. The raw materials and recovered solids are individually dried, and the vanadium content is determined by ICP-AES (model Vista-Pro manufactured by Hitachi High-Tech Co., Ltd.). In addition, the total amount of cations in Examples 1-21 and Comparative Examples 1-2 are confirmed to be the cationic species shown in Table 1. Other cations are negligible contents, and n(H + )/[n is calculated for the cationic species described in Table 1. (C z+ )×z]. The content of each cation was measured by dissolving the raw material in nitric acid, and the ammonium ion was measured by an ion chromatography (model DIONEX INTEGRION, manufactured by Thermo Scientific), and the ammonium ion was measured by ICP-AES (model Vista-Pro manufactured by Hitachi High-Technologies).
釩的回收率(質量%)係回收之氧化釩中所含之釩質量相對於原料中所含之釩質量之比以百分比表示者。且陽離子去除率係將回收之氧化釩中所含之陽離子對於釩之質量相對於原料中所含之陽離子對於釩之質量之比以百分比表示者作為殘存率(質量%)，自100%減去該殘存率所得之差作為陽離子去除率。The recovery rate of vanadium (mass %) is the ratio of the mass of vanadium contained in the recovered vanadium oxide to the mass of vanadium contained in the raw material expressed as a percentage. And the cation removal rate is the ratio of the mass of cations contained in the recovered vanadium oxide to the mass of vanadium to the mass of cations contained in the raw material expressed as a percentage as the residual rate (mass%), subtracted from 100% The difference obtained from this residual rate is used as the cation removal rate.
實施例1~21之釩回收率均為50質量%以上。又，陽離子去除率於比較例中為40質量%以下，相對於此，實施例均為50質量%以上。The vanadium recovery rates of Examples 1-21 are all 50% by mass or more. In addition, in the comparative example, the cation removal rate was 40% by mass or less, while the examples were all 50% by mass or more.
[實施例22~37、比較例3~6] 使用藉由國際公開2017/208471號中記載之方法對燃燒灰進行鹼萃取所得之氧化釩(以下稱為釩濾餅)作為含鈉之氧化釩。又，實施例22~30、36及37、比較例4使用同樣燃燒灰進行鹼萃取之氧化釩。又，實施例31~35、比較例3、5及6係使用分別使用與實施例22~30等之燃燒灰不同批次之燃燒灰，進行與實施例22同樣之鹼萃取所得之氧化釩(釩濾餅)。[Examples 22 to 37, Comparative Examples 3 to 6] Vanadium oxide (hereinafter referred to as vanadium filter cake) obtained by alkali extraction of combustion ash by the method described in International Publication No. 2017/208471 is used as sodium-containing vanadium oxide. In addition, Examples 22-30, 36 and 37, and Comparative Example 4 used the same vanadium oxide that was subjected to alkali extraction with combustion ash. In addition, Examples 31 to 35, Comparative Examples 3, 5, and 6 used different batches of combustion ash from the combustion ash of Examples 22 to 30, etc., and performed the same alkali extraction as in Example 22 to obtain vanadium oxide ( Vanadium filter cake).
該等所得之各釩濾餅以表2所示之條件進行處理，隨後冷卻至室溫，回收鈉經減低之氧化釩固體。原料之釩濾餅及回收之固體分別乾燥，藉由ICP-AES(型號Vista-Pro日立高科技公司製)測定釩及鈉之含量。又實施例22~37之陽離子總量藉與實施例1同樣方法，測定鈉以外之陽離子量之結果，確認為相對於鈉離子為可忽視之含量，針對鈉離子算出n(H+ )/[n(Cz+ )×z]。 又，比較例3~6與實施例22~37同樣，以表2所示之條件進行自燃燒灰所得之釩濾餅之溶出。又比較例3~6之陽離子總量藉與實施例1同樣方法測定鈉以外之陽離子量之結果，確認為相對於鈉離子為可忽視之含量，針對鈉離子算出n(H+ )/[n(Cz+ )×z]。 自該等測定結果算出釩回收率與鈉去除率。結果示於表2。The vanadium filter cakes obtained were processed under the conditions shown in Table 2, and then cooled to room temperature to recover the vanadium oxide solid with reduced sodium. The vanadium filter cake of the raw material and the recovered solid were dried separately, and the content of vanadium and sodium was determined by ICP-AES (model Vista-Pro manufactured by Hitachi High-Tech Co., Ltd.). In addition, the total amount of cations in Examples 22 to 37 was measured in the same manner as in Example 1, and the results of measuring the amount of cations other than sodium were confirmed to be negligible relative to sodium ions, and n(H + )/[ n(C z+ )×z]. In addition, in Comparative Examples 3 to 6, the same as in Examples 22 to 37, the vanadium filter cake obtained from the combustion ash was eluted under the conditions shown in Table 2. In addition, the total amount of cations in Comparative Examples 3 to 6 was determined by measuring the amount of cations other than sodium in the same manner as in Example 1. It was confirmed that the content was negligible relative to sodium ions, and n(H + )/[n (C z+ )×z]. Calculate the vanadium recovery rate and sodium removal rate from these measurement results. The results are shown in Table 2.
判知比較例3~6之試料，處理後之鈉去除率較低，實施例22~37，鈉去除率較高。 [產業上之可利用性]It is judged that the samples of Comparative Examples 3-6 have a lower sodium removal rate after treatment, and Examples 22-37 have a higher sodium removal rate. [Industrial availability]
本發明之氧化釩之精製方法係最適於自包含鈉等之陽離子之氧化釩之狀態，獲得陽離子量經減低之氧化釩之情況的方法。且比以往方法成本抑制為更低。The refining method of vanadium oxide of the present invention is the most suitable method for obtaining vanadium oxide with reduced cation content from the state of vanadium oxide containing cations such as sodium. And the cost is lower than the previous method.
[圖1]係顯示5價之釩離子溶解度與pH之關係的相圖。 [圖2]係顯示本發明之精製方法概略之流程圖。[Figure 1] A phase diagram showing the relationship between the solubility of 5-valent vanadium ions and pH. [Figure 2] is a flow chart showing the outline of the refining method of the present invention.
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