JPH08273692A - Manufacture of vanadium type electrolyte - Google Patents
Manufacture of vanadium type electrolyteInfo
- Publication number
- JPH08273692A JPH08273692A JP7097902A JP9790295A JPH08273692A JP H08273692 A JPH08273692 A JP H08273692A JP 7097902 A JP7097902 A JP 7097902A JP 9790295 A JP9790295 A JP 9790295A JP H08273692 A JPH08273692 A JP H08273692A
- Authority
- JP
- Japan
- Prior art keywords
- vanadium
- temperature
- oxide
- solution
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、レドックス電池に用い
られる高濃度のバナジウム系電解液の製造法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-concentration vanadium-based electrolytic solution used in a redox battery.
【０００２】[0002]
【従来の技術】最近、環境汚染の問題が深刻化するにつ
れ、各種エネルギ−のなかで比較的クリ−ンな電気エネ
ルギ−の利用が増大している。この電気エネルギ−は、
汎用性が高く、消費時の環境汚染もないので、将来さら
に需要が増加することが考えられるが、この電気エネル
ギ−の適当な貯蔵法が開発されていないため、十分に利
用することができていないのが現状である。2. Description of the Related Art Recently, as the problem of environmental pollution becomes more serious, the use of relatively clean electric energy among various kinds of energy is increasing. This electrical energy is
Since it has high versatility and there is no environmental pollution during consumption, it is expected that demand will increase further in the future, but since adequate storage method of this electric energy has not been developed, it can be fully used. The current situation is that there are none.
【０００３】[0003]
【発明が解決しようとする課題】このため、電気エネル
ギ−の貯蔵法として、各種の二次電池が研究開発されて
いるが、なかでも操作性が良く、大容量の電池であるレ
ドックス電池が注目されている。このレドックス電池
は、液状の正・負極の電池活性物質を液透過型の電解槽
に入れ、酸化・還元反応により充・放電を行うものであ
り、従来の二次電池に比べて寿命が長く、信頼性および
安全性が高い等の利点がある。For this reason, various secondary batteries have been researched and developed as a method for storing electric energy. Among them, redox batteries, which are batteries with good operability and large capacity, are of particular interest. Has been done. This redox battery is one in which liquid positive and negative battery active substances are placed in a liquid-permeable electrolytic cell and charged and discharged by an oxidation / reduction reaction, which has a longer life than conventional secondary batteries. There are advantages such as high reliability and safety.
【０００４】上記レドックス電池としては、クロム２
価、３価対鉄２価、３価系をレドックス対とするもの、
クロム、塩素系のレドックス対を用いるもの等、種々の
ものが提案されているが、未だ十分実用に耐えるものは
得られていない。As the redox battery, chromium 2 is used.
, Trivalent vs. iron divalent, trivalent redox pair,
Various materials have been proposed, such as those using a redox pair of chromium or chlorine, but none have been obtained that can withstand practical use.
【０００５】上記レドックス電池のうち、硫酸溶液に溶
解したバナジウムイオン対を正・負極液としたレドック
ス電池は、１．５Ｖ程度の出力電圧を得られるので、エ
ネルギ−密度が高く効率的であるが、高価なバナジウム
を用いるため、実用上問題がある。これを改良するもの
として、メタバナジン酸アンモニウムまたは五酸化バナ
ジウムを無機酸存在下に亜硫酸などで還元し、得られた
飽和液に濃硫酸等の無機酸を添加し、ついでバナジウム
化合物を追加するバナジウム系電解液の製法が提案され
ている（特開平５−３０３９７３号公報参照）が、この
方法は、工程が煩雑で、安定した電解液の製造が比較的
困難であるという問題がある。そこで、本発明は、レド
ックス電池用の高濃度のバナジウム溶液を比較的容易か
つ安価に製造する方法を提供することを課題としてい
る。Among the redox batteries described above, the redox battery using a vanadium ion pair dissolved in a sulfuric acid solution as a positive and negative electrode liquid can obtain an output voltage of about 1.5 V, so that it has high energy density and is efficient. However, since expensive vanadium is used, there is a practical problem. To improve this, ammonium metavanadate or vanadium pentoxide is reduced with sulfurous acid or the like in the presence of an inorganic acid, an inorganic acid such as concentrated sulfuric acid is added to the obtained saturated solution, and then a vanadium compound is added to the vanadium compound. Although a method for producing an electrolytic solution has been proposed (see Japanese Patent Laid-Open No. 5-303973), this method has a problem that the steps are complicated and stable production of an electrolytic solution is relatively difficult. Therefore, it is an object of the present invention to provide a method for producing a high-concentration vanadium solution for a redox battery relatively easily and inexpensively.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、本発明は次のような構成とした。すなわち、本発明
にかかるバナジウム系電解液の製造方法は、原料である
バナジウム酸化物を還元雰囲気中で加熱してＶ2 Ｏ3 ま
たはＶ2 Ｏ4 を主成分とするバナジウム酸化物に還元す
る工程と、得られたバナジウム酸化物を硫酸溶液に溶解
させる工程とを有することを特徴としている。In order to solve the above problems, the present invention has the following constitution. That is, the method for producing a vanadium-based electrolytic solution according to the present invention is a step of heating vanadium oxide as a raw material in a reducing atmosphere to reduce vanadium oxide containing V 2 O 3 or V 2 O 4 as a main component. And a step of dissolving the obtained vanadium oxide in a sulfuric acid solution.
【０００７】上記原料であるバナジウム酸化物として
は、バナジン酸アンモニウムを密閉容器に入れて加熱分
解させることにより得られる酸化物を使用するのが経済
的である。As the vanadium oxide as the above-mentioned raw material, it is economical to use an oxide obtained by placing ammonium vanadate in a closed container and thermally decomposing it.
【０００８】以下、この製法について具体例をあげつつ
詳細に説明する。本発明で使用するバナジウム酸化物
は、例えば、廃触媒から回収されたバナジウム化合物の
分解によって得られる。この廃触媒からの回収によって
得られるバナジウム化合物としては、メタバナジン酸ア
ンモニウム（ＮＨ4 ＶＯ3 ）が一般的であるが、これを
使用する場合は、得られたメタバナジン酸アンモニウム
を耐熱性を有する密閉容器に入れて加熱分解する。The manufacturing method will be described in detail below with reference to specific examples. The vanadium oxide used in the present invention is obtained, for example, by decomposing a vanadium compound recovered from a waste catalyst. Ammonium metavanadate (NH 4 VO 3 ) is generally used as the vanadium compound obtained by recovery from the spent catalyst, but when using this, the obtained ammonium metavanadate is a heat-resistant closed container. Put in and decompose by heating.
【０００９】分解温度は４４０〜４７０℃とするのが好
ましく、この温度で７時間以上保持することにより、メ
タバナジン酸アンモニウム自身のアンモニアが簡単に分
解し、このアンモニアによって還元が行われる。分解後
は適当な温度、例えば室温程度に冷却して中間製品であ
るバナジウム酸化物を取り出す。The decomposition temperature is preferably 440 to 470 ° C. By keeping the temperature at this temperature for 7 hours or more, the ammonia of ammonium metavanadate itself easily decomposes and the reduction is carried out by this ammonia. After the decomposition, the vanadium oxide as an intermediate product is taken out by cooling to an appropriate temperature, for example, about room temperature.
【００１０】上記メタバナジン酸アンモニウムの分解に
よって得られる酸化物は、通常、Ｖ6 Ｏ13を主成分とす
るものである。この酸化物をボ−トに入れて、還元性雰
囲気、例えば水素雰囲気の電気炉中で還元すると低級の
バナジウム酸化物が得られる。この酸化物は、還元条件
（加熱温度等）を調節することによってＶ2 Ｏ3 とする
こともＶ2 Ｏ4 とすることも可能である。The oxide obtained by decomposing ammonium metavanadate usually contains V 6 O 13 as a main component. When this oxide is put in a boat and reduced in an electric furnace in a reducing atmosphere such as a hydrogen atmosphere, a lower vanadium oxide is obtained. This oxide can be made into V 2 O 3 or V 2 O 4 by adjusting the reducing conditions (heating temperature etc.).
【００１１】次に、上記還元によって得られた酸化物に
硫酸溶液を加えて８０〜１２０℃に加温し、硫酸溶液に
溶解する。硫酸溶液の濃度（重量％）は、３０％以上と
するのが適当であり、５０％以上が好ましく、５０〜７
０％とするのがより好ましい。この場合、バナジウムの
濃度は実用的な範囲内で任意の濃度に調節することが可
能であるが、１〜３モル程度が好ましい。十分に溶解し
たら、ろ過し、バナジウム溶液のレドックス電池用電解
液を得る。なお、出発原料であるバナジウム化合物とし
てＶ2 Ｏ5 を使用する場合は、図１の破線で示すよう
に、そのまま水素還元工程からスタ−トすればよい。Next, a sulfuric acid solution is added to the oxide obtained by the above reduction, heated to 80 to 120 ° C., and dissolved in the sulfuric acid solution. The concentration (% by weight) of the sulfuric acid solution is suitably 30% or more, preferably 50% or more, and 50 to 7
It is more preferably 0%. In this case, the concentration of vanadium can be adjusted to any concentration within a practical range, but it is preferably about 1 to 3 mol. When sufficiently dissolved, the solution is filtered to obtain a redox battery electrolyte solution of vanadium solution. When V 2 O 5 is used as the vanadium compound as the starting material, the hydrogen reduction step may be started as it is, as shown by the broken line in FIG.
【００１２】[0012]
【実施例】図１の工程図にしたがって、廃触媒から回収
した固形物であるバナジン酸アンモニウム（メタバナジ
ン酸アンモニウム）を出発原料としてレドックス電池用
電解液を製造した。まず、メタバナジン酸アンモニウム
６０００ｇを黒鉛の密閉容器に入れ、電気炉中で昇温、
加熱した。昇温は、室温から４７０℃まで２０分をかけ
て行った。[Examples] According to the process chart of FIG. 1, a redox battery electrolyte was produced using ammonium vanadate (ammonium metavanadate), which is a solid substance recovered from a waste catalyst, as a starting material. First, 6000 g of ammonium metavanadate was placed in a graphite airtight container and heated in an electric furnace.
Heated. The temperature was raised from room temperature to 470 ° C. over 20 minutes.
【００１３】引き続き、４４０〜４７０℃の温度で７．
５時間保持し、分解を行った。分解後は密閉容器を取り
出して冷却し、内部の中間製品である低級酸化物Ｖ6 Ｏ
13粉末を取り出した。得られた酸化物Ｖ6 Ｏ13の重量は
５２８０ｇであった。Subsequently, at a temperature of 440 to 470 ° C., 7.
It was held for 5 hours for decomposition. After decomposition removed and cooled closed containers, lower oxides V 6 O is an internal intermediate product
13 powder was taken out. The weight of the obtained oxide V 6 O 13 was 5280 g.
【００１４】次に、得られたＶ6 Ｏ13粉末を小分けして
水素還元用のボ−トに入れ、水素（気流）雰囲気の電気
炉で７００℃に昇温し、その温度で４０〜６０分かけて
還元を行った。水素流量は、電気炉のボ−ト挿入用還元
パイプ１本当たり２．０ｍ3／ｈｒであった。水素還元
を終えた粉末は冷却し、バナジウム酸化物Ｖ2 Ｏ3 を得
た。得られた酸化物の重量は３７７０ｇであった。Next, the obtained V 6 O 13 powder was divided into small pieces and put in a boat for hydrogen reduction, and the temperature was raised to 700 ° C. in an electric furnace in a hydrogen (air flow) atmosphere, and the temperature was 40 to 60. The reduction was carried out in minutes. The hydrogen flow rate was 2.0 m 3 / hr per one reduction pipe for inserting a boat in an electric furnace. The powder after hydrogen reduction was cooled to obtain vanadium oxide V 2 O 3 . The weight of the obtained oxide was 3770 g.
【００１５】このバナジウム酸化物Ｖ2 Ｏ3 １０００ｇ
に純水４５００ｍｌと濃硫酸５３５０ｇを加えて８０〜
１２０℃に加温した。最適加温温度は１２０℃であっ
た。溶解したバナジウム溶液をろ過し、所望の製品であ
る３価のバナジウム溶液からなるレドックス電池用電解
液を得た。得られた電解液のバナジウム濃度は、５１〜
１５３ｇ／ｌ（１〜３モル）の範囲で任意に設定可能で
あった。1000 g of this vanadium oxide V 2 O 3
Add 4500 ml of pure water and 5350 g of concentrated sulfuric acid to 80 ~
Heated to 120 ° C. The optimum heating temperature was 120 ° C. The dissolved vanadium solution was filtered to obtain an electrolyte solution for a redox battery, which was a desired product and consisted of a trivalent vanadium solution. The vanadium concentration of the obtained electrolytic solution is 51-
It could be arbitrarily set within the range of 153 g / l (1 to 3 mol).
【００１６】このレドックス電池用電解液の製法によれ
ば、安価なバナジン酸アンモニウムを用いて、高濃度の
バナジウム溶液を簡単に製造することができるので、経
済的である。According to this method for producing a redox battery electrolyte, a high-concentration vanadium solution can be easily produced using inexpensive ammonium vanadate, which is economical.
【００１７】[0017]
【発明の効果】以上に説明した如く、本発明にかかるレ
ドックス電池用電解液の製法は、原料となるバナジウム
の酸化物を一旦水素還元した後、濃硫酸溶液に溶解する
ものであるから、高濃度のバナジウム系レドックス電池
用電解液を経済的かつ容易に製造することが可能となっ
た。As described above, according to the method for producing an electrolyte for a redox battery according to the present invention, the oxide of vanadium as a raw material is once hydrogen-reduced and then dissolved in a concentrated sulfuric acid solution. It has become possible to economically and easily manufacture a concentrated vanadium-based redox battery electrolyte.
【図１】本発明の実施例を表す製造工程図である。FIG. 1 is a manufacturing process diagram showing an embodiment of the present invention.
Claims (2)
中で加熱して、Ｖ2 Ｏ3 またはＶ2Ｏ4 を主成分とする
バナジウム酸化物に還元する工程と、得られたバナジウ
ム酸化物を硫酸溶液に溶解させる工程とを有することを
特徴とするバナジウム系電解液の製造方法。1. A step of heating a vanadium oxide as a raw material in a reducing atmosphere to reduce the vanadium oxide containing V 2 O 3 or V 2 O 4 as a main component, and the obtained vanadium oxide. And a step of dissolving the solution in a sulfuric acid solution.
て加熱分解させ、バナジウム酸化物を得る工程と、該分
解によって得られたバナジウム酸化物を還元雰囲気中で
加熱して、Ｖ2 Ｏ3 またはＶ2 Ｏ4 を主成分とするバナ
ジウム酸化物に還元する工程と、該還元によって得られ
たバナジウム酸化物を硫酸溶液に溶解させる工程とを有
することを特徴とするバナジウム系電解液の製造方法。2. A step of placing ammonium vanadate in a closed container and thermally decomposing it to obtain vanadium oxide, and heating the vanadium oxide obtained by the decomposition in a reducing atmosphere to produce V 2 O 3 or V 2. A method for producing a vanadium-based electrolytic solution, comprising: a step of reducing vanadium oxide containing 2 O 4 as a main component; and a step of dissolving the vanadium oxide obtained by the reduction in a sulfuric acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09790295A JP3525231B2 (en) | 1995-03-30 | 1995-03-30 | Method for producing vanadium-based electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09790295A JP3525231B2 (en) | 1995-03-30 | 1995-03-30 | Method for producing vanadium-based electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08273692A true JPH08273692A (en) | 1996-10-18 |
| JP3525231B2 JP3525231B2 (en) | 2004-05-10 |
Family
ID=14204669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09790295A Expired - Fee Related JP3525231B2 (en) | 1995-03-30 | 1995-03-30 | Method for producing vanadium-based electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3525231B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187720A (en) * | 2000-12-15 | 2002-07-05 | Chiyoda Corp | Method of manufacturing high purity vanadium compound from carbonaceous residue containing vanadium |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9525164B1 (en) | 2016-04-29 | 2016-12-20 | King Abdulaziz University | Method of reducing vanadium pentoxide to vanadium(III) oxide |
-
1995
- 1995-03-30 JP JP09790295A patent/JP3525231B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187720A (en) * | 2000-12-15 | 2002-07-05 | Chiyoda Corp | Method of manufacturing high purity vanadium compound from carbonaceous residue containing vanadium |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3525231B2 (en) | 2004-05-10 |
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