JP2723175B2 - Method of extracting metals contained in petroleum-based combustion ash - Google Patents
Method of extracting metals contained in petroleum-based combustion ashInfo
- Publication number
- JP2723175B2 JP2723175B2 JP3214195A JP3214195A JP2723175B2 JP 2723175 B2 JP2723175 B2 JP 2723175B2 JP 3214195 A JP3214195 A JP 3214195A JP 3214195 A JP3214195 A JP 3214195A JP 2723175 B2 JP2723175 B2 JP 2723175B2
- Authority
- JP
- Japan
- Prior art keywords
- combustion ash
- petroleum
- vanadium
- nickel
- based combustion
- 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.)
- Expired - Lifetime
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
【０００１】[0001]
【産業上の利用分野】本発明は、火力発電所等から排出
される石油系燃焼灰からそれに含まれる金属を抽出する
方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 extracting metals contained in petroleum-based combustion ash discharged from a thermal power plant or the like.
【０００２】[0002]
【従来技術及びその問題点】重油や、石油系のピッチ、
石油アスファルト等の石油系燃料を燃焼して得られる燃
焼灰には、バナジウムやニッケル等の金属が含まれてい
る。このような石油系燃焼灰から金属を抽出する方法に
ついては、ソーダ焙焼して、バナジウムを可溶性塩に変
えて、温水で浸出して、バナジウムを抽出する方法及び
水浸出によりバナジウムを抽出する方法が実施されてい
る。しかし、ソ−ダ焙焼法はエネルギ−コストが高い上
に、ニッケルを回収することができない。また、水浸出
法は金属成分の浸出率が低いなどの難点があり、効率の
よい抽出法の開発が期待されている。一方、火力発電所
から排出される燃焼灰は産業廃棄物として適切な処理が
要求されているが、この燃焼灰からバナジウムやニッケ
ルなどの有価金属を効率よく安価に抽出し回収すること
は、資源の有効利用及び発電コスト低減のためにも重要
である。[Prior art and its problems] Heavy oil, petroleum pitch,
Combustion ash obtained by burning petroleum fuel such as petroleum asphalt contains metals such as vanadium and nickel. Regarding the method of extracting metal from such petroleum-based combustion ash, the method of roasting soda, changing vanadium into a soluble salt, leaching with warm water, extracting vanadium and extracting vanadium by water leaching are described. Has been implemented. However, the soda roasting method has a high energy cost and cannot recover nickel. Further, the water leaching method has disadvantages such as a low leaching rate of metal components, and development of an efficient extraction method is expected. On the other hand, combustion ash discharged from thermal power plants is required to be appropriately treated as industrial waste, but extracting and recovering valuable metals such as vanadium and nickel from this combustion ash efficiently and inexpensively is a resource It is also important for effective utilization of power and reduction of power generation cost.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、石油系燃焼
灰からそれに含まれる金属を効率よく、かつ経済的に抽
出する方法を提供することをその課題とする。An object of the present invention is to provide a method for efficiently and economically extracting metals contained in petroleum-based combustion ash from the ash.
【０００４】本発明者は、前記課題を解決すべく鋭意研
究を重ねた結果、過酸化水素を含む酸性水溶液に燃焼灰
を加えて、攪拌するという簡単な操作によって、燃焼灰
からバナジウムやニッケル等の有価金属が効率よく抽出
されることを見いだし、本発明を完成するに至った。す
なわち、本発明によれば、バナジウム及びニッケルを含
む石油系燃焼灰を過酸化水素を含む酸性水溶液で抽出処
理することを特徴とする石油系燃焼灰からそれに含まれ
るバナジウム及びニッケルを抽出する方法が提供され
る。The inventor of the present invention has conducted intensive studies to solve the above-mentioned problems. As a result, a simple operation of adding combustion ash to an acidic aqueous solution containing hydrogen peroxide and stirring the resulting mixture is used to convert vanadium, nickel, etc. from the combustion ash. Was found to be efficiently extracted, and the present invention was completed. That is, according to the present invention, there is provided a method of extracting vanadium and nickel contained in petroleum-based combustion ash from petroleum-based combustion ash, which comprises extracting the petroleum-based combustion ash containing vanadium and nickel with an acidic aqueous solution containing hydrogen peroxide. Provided.
【０００５】石油系燃焼灰としては、重油、石油系ピッ
チ、石油系アスファルト、あるいはそれらを水中に分散
させたもの等の石油系燃料を燃焼して得られた燃焼灰で
ある。このような燃焼灰には、バナジウムやニッケル等
の有価金属が含まれる。燃焼灰中の金属の形態は、通
常、酸化物や硫酸塩等である。本発明で好ましく用いら
れる燃焼灰は、石油系燃料を用いる火力発電所から排出
される燃焼灰である。[0005] The petroleum-based combustion ash is combustion ash obtained by burning a petroleum-based fuel such as heavy oil, petroleum-based pitch, petroleum-based asphalt, or those obtained by dispersing them in water. Such combustion ash contains valuable metals such as vanadium and nickel. The form of the metal in the combustion ash is usually an oxide, a sulfate, or the like. The combustion ash preferably used in the present invention is combustion ash discharged from a thermal power plant using petroleum-based fuel.
【０００６】本発明で用いる抽出剤は、過酸化水素を含
む酸性水溶液である。この酸性水溶液におけるｐＨは、
通常、０．５〜３．０、好ましくは１〜２．５の範囲で
ある。また、この酸性水溶液中に含まれる過酸化水素の
濃度は、０．１〜１０重量％、好ましくは０．５〜６重
量％の範囲である。本発明で用いる酸性水溶液は、塩
酸、硫酸、硝酸、リン酸、酢酸、シュウ酸、クエン酸等
の無機酸や有機酸を含む水溶液である。水溶液中の酸濃
度は、０．０１〜５重量％、好ましくは０．１〜２重量
％である。[0006] The extractant used in the present invention is an acidic aqueous solution containing hydrogen peroxide. The pH in this acidic aqueous solution is
Usually, it is in the range of 0.5 to 3.0, preferably 1 to 2.5. The concentration of hydrogen peroxide contained in the acidic aqueous solution is in the range of 0.1 to 10% by weight, preferably 0.5 to 6% by weight. The acidic aqueous solution used in the present invention is an aqueous solution containing an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, or citric acid or an organic acid. The acid concentration in the aqueous solution is 0.01 to 5% by weight, preferably 0.1 to 2% by weight.
【０００７】前記抽出剤を用いて燃焼灰からそれに含ま
れる金属を抽出するには、燃焼灰と抽出剤を接触させれ
ばよい。この場合の接触方法としては、燃焼灰を抽出剤
中に浸漬する方法や、燃焼灰を充填した塔に抽出剤を流
通させる方法等がある。抽出温度は、常温で十分である
が、必要に応じて、３０〜９０℃の加温を採用すること
もできる。[0007] In order to extract the metal contained in the combustion ash from the combustion ash by using the extractant, the combustion ash may be brought into contact with the extractant. As a contact method in this case, there are a method of immersing the combustion ash in the extractant, a method of flowing the extractant through a tower filled with the combustion ash, and the like. As for the extraction temperature, normal temperature is sufficient, but if necessary, heating at 30 to 90 ° C can be adopted.
【０００８】前記の抽出処理により、燃焼灰に含まれる
金属は、抽出剤に抽出される。この抽出剤に抽出された
金属を抽出剤から分離回収するには、従来公知の各種の
方法を採用することができる。例えば、抽出剤のｐＨを
７〜９、好ましくは約８に調節した後、アンモニウム塩
（例えば、硫酸アンモニウム、塩酸アンモニウム、硝酸
アンモニウム等）を加えることにより、抽出剤中のバナ
ジウムをバナジン酸アンモニウムとして沈殿分離させる
ことができ、このバナジン酸アンモニウムを沈殿分離し
た後の残液は、これを冷却することにより、抽出剤中の
ニッケル塩をアンモニウム複塩として晶析分離させるこ
とができる。[0008] By the above-mentioned extraction treatment, the metals contained in the combustion ash are extracted into the extractant. In order to separate and recover the metal extracted from the extractant from the extractant, various conventionally known methods can be employed. For example, after adjusting the pH of the extractant to 7-9, preferably about 8, an ammonium salt (for example, ammonium sulfate, ammonium chloride, ammonium nitrate, etc.) is added to precipitate and separate vanadium in the extractant as ammonium vanadate. The remaining liquid after precipitation and separation of ammonium vanadate can be cooled and cooled to crystallize and separate the nickel salt in the extractant as an ammonium double salt.
【０００６】[0006]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。なお、以下の実験において、試料として用いた燃
焼灰は火力発電所から排出されたバナジウム６．９４
％、ニッケル１．６２％、アンモニウムイオン７．６８
％、硫酸イオン５７．４％の組成（重量％）のものであ
る。Next, the present invention will be described in more detail with reference to examples. In the following experiment, combustion ash used as a sample was vanadium 6.94 discharged from a thermal power plant.
%, Nickel 1.62%, ammonium ion 7.68
% And a sulfate ion content of 57.4% (% by weight).
【０００７】実施例１ 塩酸、硫酸、硝酸によりそれぞれｐＨ１．５に調整した
２ｗｔ％の過酸化水素を含む水溶液中に、燃焼灰を固形
分濃度１０ｇ／ｄｍ3で加え、常温において、攪拌しな
がら１時間浸出したときのバナジウム抽出率とニッケル
の抽出率を測定した。その結果、塩酸でｐＨを１．５に
調整した水溶液では、それぞれ９８．９％及び９９．２
％、硫酸ではそれぞれ９８．９％及び９９．２％、硝酸
では、それぞれ９９．２％及び９９．３％であった。バ
ナジウム及びニッケルとも酸の種類による抽出率の差は
ほとんどなかった。Example 1 Combustion ash was added at a solid concentration of 10 g / dm 3 to an aqueous solution containing 2 wt% of hydrogen peroxide adjusted to pH 1.5 with hydrochloric acid, sulfuric acid and nitric acid, respectively, and stirred at room temperature while stirring. The extraction rates of vanadium and nickel when leaching for 1 hour were measured. As a result, in an aqueous solution adjusted to pH 1.5 with hydrochloric acid, 98.9% and 99.2% were obtained, respectively.
%, 98.9% and 99.2% for sulfuric acid, and 99.2% and 99.3% for nitric acid, respectively. There was almost no difference in extraction rate between vanadium and nickel depending on the type of acid.
【０００８】実施例２ 過酸化水素を２ｗｔ％含む水溶液を、硫酸により、ｐＨ
１．０、１．５、２．０及び２．５にそれぞれ調整した
水溶液中に、燃焼灰を、固形分濃度１０ｇ／ｄｍ3で加
え、１時間浸出したときのバナジウム抽出率とニッケル
抽出率を測定した。バナジウム抽出率は、それぞれ、９
９．１％、９８．９％、９８．８％及び９７．５％で、
ニッケル抽出率は、それぞれ、９９．５％、９９．２
％、９８．９％及び９５．７％であった。バナジウム、
ニッケルとも抽出率が最も高かったのはｐＨ１．０の水
溶液であったが、ｐＨ２．０の場合の抽出率との差は、
バナジウムが０．３％、ニッケルが０．６％とわずかで
あった。Example 2 An aqueous solution containing 2 wt% of hydrogen peroxide was adjusted to pH with sulfuric acid.
The combustion ash was added to the aqueous solutions adjusted to 1.0, 1.5, 2.0 and 2.5, respectively, at a solid content concentration of 10 g / dm 3 , and the vanadium extraction rate and nickel extraction rate when leached for 1 hour Was measured. The vanadium extraction rate was 9
At 9.1%, 98.9%, 98.8% and 97.5%,
The nickel extraction rates were 99.5% and 99.2, respectively.
%, 98.9% and 95.7%. vanadium,
The extraction rate of nickel was the highest in the aqueous solution at pH 1.0, but the difference from the extraction rate at pH 2.0 was
The vanadium content was as low as 0.3% and the nickel content was as low as 0.6%.
【０００９】実施例３ 過酸化水素濃度が０．５ｗｔ％、１ｗｔ％、２ｗｔ％、
４ｗｔ％及び６ｗｔ％のｐＨ２．５の硫酸酸性水溶液中
に、燃焼灰を固形分濃度１０ｇ／ｄｍ3で加え、１時間
浸出したときのバナジウム抽出率は、それぞれ、９４．
５％、９５．８％、９８．８％、９９．２％及び９９．
３％で、ニッケル抽出率は、それぞれ、９４．６％、９
６．５％、９８．１％、９８．７％及び９８．８％であ
った。Example 3 When the concentration of hydrogen peroxide is 0.5 wt%, 1 wt%, 2 wt%,
Combustion ash was added to 4 wt% and 6 wt% aqueous sulfuric acid solutions having a pH of 2.5 at a solid concentration of 10 g / dm 3 , and the leaching rate for 1 hour was 94.94%.
5%, 95.8%, 98.8%, 99.2% and 99.
At 3%, the nickel extraction rates were 94.6% and 9 respectively.
6.5%, 98.1%, 98.7% and 98.8%.
【００１０】[0010]
【発明の効果】本発明による過酸化水素を含む酸性水溶
液により石油系燃焼灰からそれに含まれる金属を抽出す
る方法は、常温で実施することができるため、エネルギ
−コストが低く、操作が容易であるなどの優れた長所を
持っている。また、火力発電所から排出される燃焼灰か
らバナジウムやニッケル等の有価金属を回収することに
より、発電コストの低減に貢献することができる。The method for extracting metals contained in petroleum-based combustion ash with an acidic aqueous solution containing hydrogen peroxide according to the present invention can be carried out at room temperature, so that the energy cost is low and the operation is easy. There are excellent advantages such as. Further, by recovering valuable metals such as vanadium and nickel from the combustion ash discharged from the thermal power plant, it is possible to contribute to a reduction in power generation costs.
Claims (2)
灰を過酸化水素を含む酸性水溶液で抽出処理することを
特徴とする石油系燃焼灰からそれに含まれるバナジウム
及びニッケルを抽出する方法。1. A method for extracting vanadium and nickel contained in petroleum-based combustion ash from petroleum-based combustion ash, which comprises extracting the petroleum-based combustion ash containing vanadium and nickel with an acidic aqueous solution containing hydrogen peroxide.
２．５であることを特徴とする請求項１の石油系燃焼灰
からそれに含まれるバナジウム及びニッケルを抽出する
方法。2. The pH of an acidic aqueous solution containing hydrogen peroxide is 1 to 2.
2. The method according to claim 1, wherein vanadium and nickel contained in the petroleum-based combustion ash are extracted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214195A JP2723175B2 (en) | 1995-02-21 | 1995-02-21 | Method of extracting metals contained in petroleum-based combustion ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214195A JP2723175B2 (en) | 1995-02-21 | 1995-02-21 | Method of extracting metals contained in petroleum-based combustion ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08217449A JPH08217449A (en) | 1996-08-27 |
| JP2723175B2 true JP2723175B2 (en) | 1998-03-09 |
Family
ID=12350629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3214195A Expired - Lifetime JP2723175B2 (en) | 1995-02-21 | 1995-02-21 | Method of extracting metals contained in petroleum-based combustion ash |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2723175B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH693612A5 (en) * | 1999-09-16 | 2003-11-14 | Von Roll Umwelttechnik Ag | Method About Check of residues from waste incineration in deponierbares material. |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041615A (en) * | 1983-08-12 | 1985-03-05 | Green Cross Corp:The | Preparation of colony stimulating factor |
| JPH0461709A (en) * | 1990-06-28 | 1992-02-27 | Fujikura Ltd | Anti-lightning eccentric composite wire and manufacture of the same |
-
1995
- 1995-02-21 JP JP3214195A patent/JP2723175B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08217449A (en) | 1996-08-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |