JP2001192747A - Method for treating petroleum-base combustion ash - Google Patents
Method for treating petroleum-base combustion ashInfo
- Publication number
- JP2001192747A JP2001192747A JP37327499A JP37327499A JP2001192747A JP 2001192747 A JP2001192747 A JP 2001192747A JP 37327499 A JP37327499 A JP 37327499A JP 37327499 A JP37327499 A JP 37327499A JP 2001192747 A JP2001192747 A JP 2001192747A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- filtrate
- sulfuric acid
- concentration
- extraction
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石油系燃焼灰から
バナジウムやニッケルなどの有価金属を分離回収する方
法において、燃焼灰のスラリー濾液からニッケルを効率
良く抽出する処理方法に関し、共存するマグネシウム等
を殆ど抽出せずにニッケルを選択的に抽出できる処理方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating and recovering valuable metals such as vanadium and nickel from petroleum-based combustion ash, and to a method for efficiently extracting nickel from a slurry filtrate of combustion ash. The present invention relates to a processing method capable of selectively extracting nickel while hardly extracting nickel.
【０００２】[0002]
【従来の技術】火力発電所や各種工業プラントのボイラ
ー等は重油や石油コークス等の重質油系燃料を用いるも
のが多く、現在、多量の燃焼灰が排出されている。これ
らの大部分は埋め立て処分されているが、この燃焼灰に
はバナジウム等の有価金属が含有されており、環境汚染
の防止および再資源化の観点から、その有効利用が求め
られている。2. Description of the Related Art Many boilers and the like of thermal power plants and various industrial plants use heavy oil-based fuels such as heavy oil and petroleum coke, and at present, a large amount of combustion ash is discharged. Most of these are disposed of in landfills, but this combustion ash contains valuable metals such as vanadium, and effective utilization of these metals is required from the viewpoint of preventing environmental pollution and recycling.
【０００３】このような重油灰等の石油系燃焼灰から有
価金属を回収する方法が従来知られており、石油系燃焼
灰またはその処理物のスラリーを固液分離した後に、そ
の固形分をアンモニア浸出し、その浸出濾液を溶媒抽出
処理することによってニッケルやバナジムを回収する方
法が本出願によって先に提案されている(特開平11-2072
93号)。この溶媒抽出方法によれば浸出濾液の液性を酸
性とアルカリ性に転々と切り替える必要がなく、一貫し
てアルカリ性下で抽出処理できるので処理作業の負担が
少なく、しかも効率よくニッケル等を回収できる利点を
有している。[0003] A method of recovering valuable metals from such petroleum-based combustion ash such as heavy oil ash has been conventionally known. After solid-liquid separation of a slurry of the petroleum-based combustion ash or a treated product thereof, the solid content is converted to ammonia. Leaching, a method of recovering nickel and vanadium by subjecting the leached filtrate to solvent extraction has been previously proposed by the present application (JP-A-11-2072).
No. 93). According to this solvent extraction method, there is no need to switch the liquid property of the leached filtrate between acidic and alkaline, and the extraction can be performed consistently under alkaline, so that the burden of the processing operation is small, and nickel and the like can be efficiently recovered. have.
【０００４】この溶媒抽出方法において、ニッケル抽出
溶媒としてリン酸系溶媒(D2EHPA:2-ethylhexylphsphori
c acid等)が従来から知られている。ところが、このリ
ン酸系溶媒は、ニッケルとマグネシウムの共存系ではニ
ッケル抽出の際にマグネシウムの大部分が随伴して抽出
されると云う問題がある。すなわち、リン酸系抽出剤で
はマグネシウムの抽出ｐＨ域は弱酸性から中性の範囲に
及ぶ。一方、ニッケルの抽出ｐＨ域は約６以上であり、
マグネシウムの抽出域の一部と重複しているため、ニッ
ケル抽出の際にマグネシウムの大部分が随伴して抽出さ
れ、両者を分離できない。このため、リン酸系抽出剤を
用い両者を分離して抽出するには、ニッケルが抽出しな
い低ｐＨ側で先ずマグネシウムを抽出して浸出濾液から
除き、次に浸出濾液のｐＨを上げてニッケルを抽出する
二段階の処理が必要になる。In this solvent extraction method, a phosphate solvent (D2EHPA: 2-ethylhexylphsphori) is used as a nickel extraction solvent.
c acid, etc.) are conventionally known. However, this phosphoric acid-based solvent has a problem that in the coexistence system of nickel and magnesium, most of magnesium is extracted accompanying nickel during nickel extraction. That is, in the case of the phosphoric acid-based extractant, the extraction pH range of magnesium ranges from weakly acidic to neutral. On the other hand, the extraction pH range of nickel is about 6 or more,
Since it overlaps with a part of the magnesium extraction area, most of the magnesium is extracted accompanying the nickel extraction, and the two cannot be separated. Therefore, in order to separate and extract both using a phosphoric acid-based extractant, magnesium is first extracted and removed from the leaching filtrate on the low pH side where nickel is not extracted, and then the pH of the leaching filtrate is raised to remove nickel. Two stages of extraction are required.
【０００５】[0005]
【発明の解決課題】本発明は、石油系燃焼灰の処理方法
について、リン酸系抽出剤を用いた溶媒処理における上
記問題を解決したものであり、ニッケルとマグネシウム
の共存系に対してマグネシウムを殆ど随伴せずにニッケ
ルを抽出することができる両者の分離効果に優れた抽出
処理方法を提供するものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in the solvent treatment using a phosphoric acid-based extractant in a method for treating petroleum-based combustion ash. An object of the present invention is to provide an extraction method capable of extracting nickel with almost no accompanying effect and having an excellent separation effect between the two.
【０００６】[0006]
【課題を解決する手段】本発明は、（１）石油系燃焼灰
またはその処理物の濾液から溶媒抽出によってニッケル
を抽出する処理方法において、バーサチック酸を抽出液
として用い、濾液を弱アルカリ性として、濾液に含まれ
るニッケルをバーサチック酸に抽出することを特徴とす
る石油系燃焼灰の処理方法に関する。According to the present invention, there is provided (1) a process for extracting nickel from a filtrate of petroleum-based combustion ash or a processed product thereof by solvent extraction, wherein versatic acid is used as an extract and the filtrate is made weakly alkaline. The present invention relates to a method for treating petroleum-based combustion ash, which comprises extracting nickel contained in a filtrate into versatic acid.
【０００７】本発明の上記処理方法は、（２）ニッケル
を抽出したバーサチック酸を希硫酸で洗浄することによ
り、ニッケルに随伴して抽出されたマグネシウムを希硫
酸中に洗い出し、次に濃硫酸で洗浄することにより濃硫
酸中にニッケルを逆抽出する処理方法を含む。According to the above-mentioned treatment method of the present invention, (2) the versatic acid from which nickel has been extracted is washed with dilute sulfuric acid, whereby magnesium extracted with nickel is washed out into dilute sulfuric acid, and then the concentrated magnesium is extracted with concentrated sulfuric acid. Includes a treatment method for back-extracting nickel into concentrated sulfuric acid by washing.
【０００８】上記処理方法は、好ましくは、（３）濾液
のｐＨを７.５〜８.５とし、濃度１０g/l以上のバーサ
チック酸を用いて抽出を行い、また（４）バーサチック
酸の洗浄を濃度０.０１〜５g/lの希硫酸を用いてｐＨ２
〜４の酸性下で行い、逆抽出を濃度１００〜３００g/l
の濃硫酸を用いてｐＨ１以下での強酸性下で行う処理方
法である。The above-mentioned treatment method preferably comprises (3) extracting the filtrate with a pH of 7.5 to 8.5, performing extraction using a versatic acid having a concentration of 10 g / l or more, and (4) washing the versatic acid. Is adjusted to pH 2 using dilute sulfuric acid at a concentration of 0.01 to 5 g / l.
酸性 4 under acidic conditions and back extraction at a concentration of 100-300 g / l
This is a treatment method performed under strong acidity at pH 1 or lower using concentrated sulfuric acid.
【０００９】また、本発明は、（５）(イ)石油系燃焼灰
またはその処理物を水性スラリーにする水浸出工程、
(ロ)水性スラリーの濾液を酸性下で加熱してバナジウム
化合物を析出させ、これを濾別回収するバナジウム回収
工程、(ハ)上記水性スラリーの固形分にアンモニア水を
加えて中性ないしアルカリ性下で酸化処理して含有金属
を液中に浸出させるアンモニア浸出工程、(ニ)アンモニ
ア浸出濾液にニッケル抽出溶媒を加えてニッケルを抽出
する工程を有する処理方法において、ニッケル抽出溶媒
としてバーサチック酸を用い、アンモニア浸出濾液を弱
アルカリ性として、濾液に含まれるニッケルをバーサチ
ック酸に抽出することを特徴とする石油系燃焼灰の処理
方法に関する。Further, the present invention provides (5) (a) a water leaching step of converting petroleum-based combustion ash or a treated product thereof into an aqueous slurry,
(B) a vanadium compound is precipitated by heating the filtrate of the aqueous slurry under acidic conditions to precipitate a vanadium compound, and the vanadium compound is filtered and collected; (c) ammonia water is added to the solid content of the aqueous slurry to obtain a neutral or alkaline solution. Ammonia leaching step of oxidizing and leaching the contained metal into the liquid, (d) in a treatment method having a step of extracting nickel by adding a nickel extraction solvent to the ammonia leached filtrate, using versatic acid as a nickel extraction solvent, The present invention relates to a method for treating petroleum-based combustion ash, characterized in that the ammonia-leached filtrate is made weakly alkaline and nickel contained in the filtrate is extracted into versatic acid.
【００１０】上記(５)の処理方法は、水浸出の際に水性
スラリーの濾液を水浸出工程に循環して再使用し、アン
モニア浸出の際に、空気導入して固液分離した後に過酸
化水素を添加する二段階の酸化処理を行い、過酸化水素
添加後の濾液を空気酸化工程に循環して再使用し、その
空気酸化後の濾液を溶媒抽出工程に導く処理方法を含
む。In the treatment method (5), the filtrate of the aqueous slurry is circulated and reused in the water leaching step during water leaching, and is subjected to peroxidation after air-injection and solid-liquid separation during ammonia leaching. Including a treatment method in which a two-stage oxidation treatment for adding hydrogen is performed, the filtrate after the addition of hydrogen peroxide is circulated to the air oxidation step and reused, and the filtrate after the air oxidation is led to the solvent extraction step.
【００１１】[0011]
【発明の実施の態様】以下、本発明を実施態様に基づい
て詳細に説明する。本発明の処理方法の概略を図１に示
す。図示するように、本発明は石油系燃焼灰からバナジ
ウムやニッケルなどを回収し、さらにはその残渣をセメ
ント原料として利用することができる処理方法に関す
る。本発明の処理対象である石油系燃焼灰とは、タール
質燃料、アスファルト、およびこれらをエマルジョン化
したもの、重油、石油コークス、石油ピッチ等の石油系
燃料を燃焼した際に生じる塵灰である。具体的は、発電
所や各種工業プラントのボイラー等から排出される集塵
灰等である。なお、通常、燃焼灰には未燃カーボンが含
まれているがこれは除去して処理するのが好ましい。未
燃カーボンは燃焼灰のスラリーを攪拌して静置すると液
面に浮遊し、これを掻き取りあるいは流し出すことによ
り容易に除去することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. FIG. 1 shows an outline of the processing method of the present invention. As shown in the drawings, the present invention relates to a processing method capable of recovering vanadium, nickel, and the like from petroleum-based combustion ash, and further using the residue as a cement raw material. The petroleum-based combustion ash to be treated according to the present invention is tar-based fuel, asphalt, and those obtained by emulsifying these, heavy oil, petroleum coke, and dust ash generated when a petroleum-based fuel such as petroleum pitch is burned. . Specific examples include dust ash discharged from boilers and the like of power plants and various industrial plants. Normally, unburned carbon is contained in the combustion ash, but it is preferable to remove and treat it. The unburned carbon floats on the liquid surface when the combustion ash slurry is stirred and allowed to stand, and can be easily removed by scraping or pouring the slurry.
【００１２】図示する本発明の処理方法は、石油系燃焼
灰またはその処理物を水浸出する工程(Ａ)、水浸出スラ
リーの濾液からバナジウムを回収する工程(Ｂ)、水浸出
の固形分にアンモニア水を加えて中性ないしアルカリ性
下で酸化処理しつつ含有金属を液中に浸出させるアンモ
ニア浸出工程(Ｃ)、アンモニア浸出濾液にニッケル抽出
溶媒を加えてニッケルを抽出する溶媒抽出工程(Ｄ)を有
している。以下、各工程について説明する。The treatment method of the present invention shown in the drawings comprises a step (A) of leaching petroleum-based combustion ash or its treated product with water, a step (B) of recovering vanadium from a filtrate of a water leaching slurry, Ammonia leaching step of leaching the contained metal into the solution while oxidizing under neutral or alkaline conditions by adding ammonia water (C), and solvent extraction step of extracting nickel by adding a nickel extraction solvent to the ammonia leaching filtrate (D) have. Hereinafter, each step will be described.
【００１３】(Ａ)水浸出工程 石油系燃焼灰に水や硫酸を加えて水性スラリーにし、液
中にバナジウム等を浸出させる。この水性スラリーを固
液分離し、その濾液をバナジウム回収工程に送る。この
水浸出工程において、水性スラリーを濾過して固形分を
アンモニア浸出工程に送る一方、濾液を水浸出工程に循
環して再使用することにより濾液中のバナジウム濃度を
高めると良い。濾液中のバナジウム濃度を高めることに
よってその回収率が向上する。 (A) Water leaching step Water or sulfuric acid is added to petroleum-based combustion ash to form an aqueous slurry, and vanadium or the like is leached into the liquid. This aqueous slurry is subjected to solid-liquid separation, and the filtrate is sent to a vanadium recovery step. In this water leaching step, it is preferable to increase the vanadium concentration in the filtrate by filtering the aqueous slurry and sending the solid matter to the ammonia leaching step, and circulating the filtrate to the water leaching step and reusing it. Increasing the concentration of vanadium in the filtrate improves its recovery.
【００１４】濾液を水浸出工程に循環する基準は、水性
スラリーから固液分離された濾液中のニッケル濃度が１
００ppm以下およびマグネシウム濃度が３０００ppm以下
となる範囲内である。マグネシウム濃度がこれより高く
なると硫酸マグネシウムアンモニウム等の影響によりマ
グネシウムが析出するので好ましくない。また、この濾
液はバナジウム回収工程に送られるので、ニッケル濃度
が上記範囲を超えると溶媒抽出工程で回収されるニッケ
ル量が減少する。The criterion for circulating the filtrate in the water leaching step is that the nickel concentration in the filtrate separated from the aqueous slurry by solid-liquid separation is 1%.
It is within the range of not more than 00 ppm and the magnesium concentration is not more than 3000 ppm. If the magnesium concentration is higher than this, magnesium precipitates under the influence of magnesium ammonium sulfate and the like, which is not preferable. Further, since this filtrate is sent to the vanadium recovery step, if the nickel concentration exceeds the above range, the amount of nickel recovered in the solvent extraction step decreases.
【００１５】(Ｂ)バナジウム回収工程 水浸出工程の上記濾液にアンモニアを加えてｐＨ２〜４
に調整し、好ましくは８０〜９０℃に加熱することによ
り酸化バナジウムを析出させる。なお、この酸化バナジ
ウムを回収して炭酸ナトリウムや塩素酸ナトリウムを加
え、液性を弱酸性に調整して酸化バナジウムを溶解し、
液中の未溶解物を濾別した後に、この濾液にアンモニア
ないしアンモニア塩を加え、この濾液を７５〜８５℃程
度に加熱してバナジン酸アンモニウムを再び沈殿させる
ことにより、不純物の少ないバナジウム化合物を回収す
ることができる。 (B) Vanadium recovery step Ammonia is added to the above filtrate in the water leaching step to adjust the pH to 2-4.
And heating to preferably 80 to 90 ° C. to precipitate vanadium oxide. In addition, this vanadium oxide is collected, sodium carbonate or sodium chlorate is added, and the solution is adjusted to a slightly acidic solution to dissolve the vanadium oxide.
After filtering off undissolved matter in the liquid, ammonia or an ammonium salt is added to the filtrate, and the filtrate is heated to about 75 to 85 ° C. to precipitate ammonium vanadate again, whereby a vanadium compound with less impurities is removed. Can be recovered.
【００１６】(Ｃ)アンモニア浸出工程 上記水浸出工程で固液分離した固形分にアンモニアと水
を加えて中性ないしアルカリ性下で酸化処理することに
より固形分に残留する金属分を液中に浸出させる。この
固形分にはニッケルが含まれ、また水浸出で分離できな
かったバナジウムが含まれている。なお、石油系燃焼灰
には多量の硫黄分が含まれているので、これを水性スラ
リーにすると硫黄分が溶出して酸性の溶液となるが、こ
れにアンモニアを加えてスラリーをｐＨ７〜９の弱アル
カリ性(中性〜アルカリ性)に調整する。アンモニアの添
加は常温下で良く、加熱する必要はない。 (C) Ammonia leaching step Ammonia and water are added to the solid content that has been solid-liquid separated in the water leaching process, and the mixture is subjected to an oxidation treatment under neutral or alkaline conditions, whereby metal components remaining in the solid content are leached into the liquid. Let it. This solid contains nickel and vanadium that could not be separated by water leaching. Since petroleum-based combustion ash contains a large amount of sulfur, if this is converted to an aqueous slurry, the sulfur is eluted to form an acidic solution. However, ammonia is added to the slurry to adjust the pH to 7 to 9. Adjust to slightly alkaline (neutral to alkaline). Ammonia can be added at room temperature, and does not need to be heated.
【００１７】なお、このアンモニア浸出において二段階
の酸化処理を行うことによりニッケルおよびバナジウム
の浸出率を高めることができる。この酸化処理は、アン
モニアを添加して中性〜アルカリ性に調整したスラリー
に、空気を導入して攪拌し、スラリーに含まれるニッケ
ルやバナジウム等を酸化する。この一段目の空気酸化の
後にスラリーを固液分離し、その固形分に必要に応じて
アンモニアを再度添加して液性を中性〜アルカリ性に調
整し、これに過酸化水素を添加して二段目の酸化処理を
行う。過酸化水素を添加したときには必要に応じてスラ
リーを攪拌すると良い。By performing the two-stage oxidation treatment in the ammonia leaching, the leaching rate of nickel and vanadium can be increased. In this oxidation treatment, air is introduced into the slurry adjusted to be neutral to alkaline by adding ammonia and stirred to oxidize nickel, vanadium and the like contained in the slurry. After the first-stage air oxidation, the slurry is subjected to solid-liquid separation, and if necessary, ammonia is added again to the solid content to adjust the liquid property to neutral to alkaline. The second stage oxidation treatment is performed. When adding hydrogen peroxide, the slurry may be agitated as needed.
【００１８】上記酸化処理において、好ましくは、アン
モニア浸出スラリーの液性をｐＨ７〜９に調整して空気
酸化と過酸化水素による酸化を行い、スラリーの酸化還
元電位が１００〜１５０mVになる範囲で空気酸化で終了
し、次いで過酸化水素を添加して酸化処理を行い、スラ
リーの酸化還元電位が１５０mV以上になるようにその添
加量を調整する。空気酸化のみでは液の酸化還元電位が
短時間で１５０mV以上になるのは難しいので、この範囲
まで空気酸化を行い、その次に、スラリーの酸化還元電
位が１５０mV以上になるまで過酸化水素を加えて酸化す
る。In the above-mentioned oxidation treatment, preferably, the liquid property of the ammonia leaching slurry is adjusted to pH 7 to 9 to perform air oxidation and oxidation with hydrogen peroxide, and the air is oxidized so that the oxidation-reduction potential of the slurry becomes 100 to 150 mV. The oxidation is completed, and then oxidation treatment is performed by adding hydrogen peroxide, and the addition amount is adjusted so that the oxidation-reduction potential of the slurry becomes 150 mV or more. Since it is difficult for the oxidation-reduction potential of the liquid to reach 150 mV or more in a short time by air oxidation alone, perform air oxidation to this range, and then add hydrogen peroxide until the oxidation-reduction potential of the slurry becomes 150 mV or more. Oxidize.
【００１９】二段階の酸化処理を行うことにより、スラ
リーに含まれる酸化し易い状態の金属分が最初の空気酸
化によって液中に浸出する。この空気酸化では浸出せず
に固形分に残留している金属分を次の過酸化水素の酸化
処理によって液中に浸出させる。なお、最初に空気酸化
を行うので過酸化水素による酸化処理の負担が軽減され
る。二段目の過酸化水素による酸化処理の後に固液分離
を行い、その濾液の全量を一段目の空気酸化に循環す
る。この濾液の全量を空気酸化に返送することにより、
アンモニア浸出工程全体の液量を増加せずに浸出効果を
高めることができる。一方、過酸化水素による酸化処理
後の固形分にはシリカ、アルミナや事前に除去されなか
った未燃カーボンなどが含まれており、これをセメント
原料として利用することができる。By performing the two-stage oxidation treatment, the easily oxidized metal contained in the slurry is leached into the liquid by the first air oxidation. In this air oxidation, the metal remaining in the solid content without being leached is leached into the liquid by the next oxidation treatment of hydrogen peroxide. Since the air oxidation is performed first, the load of the oxidation treatment with hydrogen peroxide is reduced. After the second-stage oxidation treatment with hydrogen peroxide, solid-liquid separation is performed, and the entire amount of the filtrate is circulated to the first-stage air oxidation. By returning the entire amount of this filtrate to air oxidation,
The leaching effect can be enhanced without increasing the amount of liquid in the entire ammonia leaching step. On the other hand, the solid content after the oxidation treatment with hydrogen peroxide contains silica, alumina, unburned carbon that has not been removed in advance, and the like, and can be used as a cement raw material.
【００２０】酸化処理を伴うアンモニア浸出によって、
水浸出では溶出しなかった焼却灰中のニッケルおよびバ
ナジウムが溶出し、その浸出効果が格段に向上する。具
体的には、酸化処理を行わないアンモニア浸出の場合に
はバナジウムの浸出率は３０〜４０％であるが、酸化処
理を併用したアンモニア浸出ではバナジウムの浸出率は
９０％以上に大幅に向上する。これはバナジウムの価数
が多くなり中性からアルカリ性下でイオン化し易い形態
に転換するためと思われる。またニッケルの浸出率は、
スラリーが酸性(ｐＨ３〜５程度)のときには２０〜３０
％台であるが、中性〜アルカリ性(ｐＨ７〜９)では約７
０〜１００％に達し、格段に浸出率が向上する。なお、
以上の酸化処理を併用したアンモニア浸出は加熱下で行
う必要はなく、常温下で良い。By ammonia leaching with oxidation treatment,
Nickel and vanadium in the incineration ash, which were not eluted by water leaching, elute, and the leaching effect is significantly improved. Specifically, the leaching rate of vanadium is 30 to 40% in the case of ammonia leaching without performing the oxidation treatment, but the leaching rate of vanadium is significantly improved to 90% or more in the case of ammonia leaching in combination with the oxidation treatment. . This is presumably because vanadium has a higher valence and is converted from neutral to easily ionized under alkaline conditions. The nickel leaching rate is
20 to 30 when the slurry is acidic (about pH 3 to 5)
%, But about 7 for neutral to alkaline (pH 7-9)
It reaches 0 to 100%, and the leaching rate is remarkably improved. In addition,
It is not necessary to perform the ammonia leaching in combination with the above oxidation treatment under heating, and may be performed at normal temperature.
【００２１】(Ｄ)溶媒抽出工程(D-1)ニッケル抽出 ニッケル抽出剤としてバーサチック酸を用い、アンモニ
ア浸出濾液に含まれるニッケルをこの浸出濾液から抽出
分離する。すなわち、上記アンモニア浸出濾液にバーサ
チック酸を混合して濾液中のニッケルイオンをバーサチ
ック酸に抽出する。このニッケル抽出は、アンモニア浸
出濾液のｐＨを弱アルカリ性、好ましくはｐＨ７.５〜
８.５に調整して行うのが好ましい。バーサチック酸に
抽出されたニッケルおよびマグネシウム等の濃度を浸出
濾液ｐＨに対応して図２に示す。このグラフに示すよう
に、ｐＨ７.５以上の範囲でニッケルの濃度は高くな
る。一方、マグネシウムの濃度はｐＨ８.５付近では未
だ低い。従ってｐＨ７.５〜８.５の範囲において、マグ
ネシウムを殆ど抽出せずにニッケルを選択的に抽出する
ことができる。(D) Solvent extraction step (D-1) Nickel extraction Nickel contained in the ammonia leached filtrate is extracted and separated from the leached filtrate using versatic acid as a nickel extracting agent. That is, versatic acid is mixed with the ammonia-leached filtrate to extract nickel ions in the filtrate into versatic acid. This nickel extraction reduces the pH of the ammonia leached filtrate to a slightly alkaline, preferably pH 7.5 to 7.5.
It is preferable to adjust to 8.5. FIG. 2 shows the concentrations of nickel, magnesium, and the like extracted into versatic acid, corresponding to the pH of the leaching filtrate. As shown in this graph, the concentration of nickel increases in the range of pH 7.5 or more. On the other hand, the concentration of magnesium is still low around pH 8.5. Therefore, nickel can be selectively extracted in the pH range of 7.5 to 8.5 with almost no extraction of magnesium.
【００２２】バーサチック酸の濃度は５％以上が適当で
あり、１０％以上が好ましい。バーサチック酸の濃度に
対するニッケル抽出率の一例を図３のグラフに示す。図
示するように、濾液のｐＨ９、混合時間３分のとき、バ
ーサチック酸の濃度１０％、１５％、２０％におけるニ
ッケルの抽出率は約８０％、約９０％、約９７％であ
り、高い抽出率が得られる。なお、従来のリン酸系抽出
剤は濃度１０％のとき、ニッケルの抽出率は４０〜５０
％程度であり、本発明のバーサチック酸に比べて大幅に
低い。The concentration of versatic acid is suitably 5% or more, preferably 10% or more. An example of the nickel extraction rate with respect to the concentration of versatic acid is shown in the graph of FIG. As shown in the figure, when the pH of the filtrate is 9 and the mixing time is 3 minutes, the extraction ratio of nickel at a versatic acid concentration of 10%, 15%, and 20% is about 80%, about 90%, and about 97%. Rate is obtained. When the concentration of the conventional phosphoric acid-based extractant is 10%, the extraction rate of nickel is 40 to 50.
%, Which is much lower than that of the versatic acid of the present invention.
【００２３】(D-2)抽出剤の洗浄 バーサチック酸をアンモニア浸出濾液から分離した後
に、このバーサチック酸に希硫酸を混合して洗浄する。
ニッケルに随伴して抽出されたマグネシウム(イオン)は
この洗浄によって希硫酸中に洗い出され、バーサチック
酸から除去される。この洗浄はｐＨ２〜４の酸性下で行
い、濃度０.０１〜５g/lの希硫酸を用いるのが良い。希
硫酸の濃度に対するニッケルおよびマグネシウムの濃度
(希硫酸に逆抽出される濃度)を図４に示す。このグラフ
に示すように、希硫酸の濃度が１g/l以下ではニッケル
は殆ど洗浄されず、２g/l以上になるとニッケルの濃度
が次第に高くなる。一方、マグネシウムの濃度は希硫酸
の濃度が０.１g/lでも比較的高く、３g/l以上ではほぼ
飽和する。従って、濃度０.０１〜５g/l、好ましくは
０.１〜２g/lの希硫酸を用いることにより、ニッケルを
バーサチック酸に残してマグネシウムを選択的に希硫酸
中に洗い出すことができる。このマグネシウムは石膏の
回収工程に導き、水酸化物として回収することができ
る。 (D-2) Washing of Extractant After separating versatic acid from the ammonia leached filtrate, the versatic acid is mixed with diluted sulfuric acid for washing.
Magnesium (ion) extracted along with nickel is washed out in dilute sulfuric acid by this washing and removed from versatic acid. This washing is performed under acidic condition of pH 2 to 4, and it is preferable to use diluted sulfuric acid having a concentration of 0.01 to 5 g / l. Nickel and magnesium concentrations relative to dilute sulfuric acid concentration
(Concentration back-extracted with dilute sulfuric acid) is shown in FIG. As shown in this graph, nickel is hardly washed when the concentration of dilute sulfuric acid is 1 g / l or less, and the concentration of nickel gradually increases when the concentration becomes 2 g / l or more. On the other hand, the concentration of magnesium is relatively high even when the concentration of dilute sulfuric acid is 0.1 g / l, and is substantially saturated when the concentration is 3 g / l or more. Therefore, by using dilute sulfuric acid at a concentration of 0.01 to 5 g / l, preferably 0.1 to 2 g / l, magnesium can be selectively washed out into the diluted sulfuric acid while leaving nickel in the versatic acid. This magnesium is led to a gypsum recovery step and can be recovered as hydroxide.
【００２４】(D-3)逆抽出 希硫酸で洗浄したバーサチック酸に濃硫酸を混合し、こ
の濃硫酸にバーサチック酸中のニッケル(イオン)を逆抽
出する。この逆抽出はｐＨ１以下の酸性下で行い、濃度
１００〜３００g/lの濃硫酸を用いるのが良い。混合
後、濃硫酸とバーサチック酸を分離する。このバーサチ
ック酸はニッケル抽出工程に循環して再度使用すること
ができる。一方、分離した濃硫酸には逆抽出したニッケ
ルが硫酸ニッケルの状態で含まれている。この濃硫酸液
を４０〜８０℃程度に加熱して水分を蒸発させ、濃縮し
て硫酸ニッケルを回収することができる。または、この
濃硫酸液を硫酸ニッケルの溶解度以下に冷却して析出さ
せても良い。この硫酸ニッケルを濾過して回収し、乾燥
すれば硫酸ニッケルの粉末を得ることができる。この濾
液(濃硫酸)は逆抽出工程に循環して再利用することがで
きる。 (D-3) Back Extraction Versatic acid washed with diluted sulfuric acid is mixed with concentrated sulfuric acid, and nickel (ion) in the versatic acid is back-extracted into the concentrated sulfuric acid. This back-extraction is performed under acidic condition of pH 1 or less, and it is preferable to use concentrated sulfuric acid having a concentration of 100 to 300 g / l. After mixing, concentrated sulfuric acid and versatic acid are separated. This versatic acid can be recycled to the nickel extraction step and reused. On the other hand, the separated concentrated sulfuric acid contains nickel back-extracted in the form of nickel sulfate. This concentrated sulfuric acid solution is heated to about 40 to 80 ° C. to evaporate water, and concentrated to recover nickel sulfate. Alternatively, the concentrated sulfuric acid solution may be cooled to a temperature lower than the solubility of nickel sulfate for precipitation. The nickel sulfate is collected by filtration and dried to obtain nickel sulfate powder. The filtrate (concentrated sulfuric acid) can be recycled to the back extraction step.
【００２５】[0025]
【実施例】以下、本発明を実施例によって具体的に示
す。実施例１ 重油質燃料の燃焼灰(V2O5:4.0wt％、Ni:0.4wt％、MgO:
4.2wt％、NH3:21.3wt％、SO3:53.9wt％)を固体濃度２０
％の水性スラリーとし、固液分離した固形分８kgにアン
モニア水を加えてｐＨ８にし、これに空気(２０リットル/mi
n)を導入して２時間攪拌した後に固液分離し、この固形
分にアンモニア水を加え、さらに過酸化水素水(濃度31v
ol％)を３０ml加えて攪拌混合した後に濾過し、濾液の
全量(14.6リットル)を空気酸化工程に循環して再度利用し
た。一方、上記空気酸化後の濾液２４００mlを抜き出
し、このアンモニア浸出濾液のｐＨを８に調整した後
に、８０mlずつにバーサチック酸(濃度30vol％)８０ml
を加える。３分間混合後、バーサチック酸を浸出濾液か
ら分離して希硫酸(濃度2g/l)８０mlを加えて３分間混合
した後に希硫酸を分離した。次に、このバーサチック酸
に濃硫酸(濃度200g/l)８０mlを加えて３分間混合した後
に、濃硫酸を分離した。この濃硫酸をさらに新しい抽出
液(上記成分)を用いて３０回抽出を繰り返して濃縮し
た。この硫酸液を蒸発して硫酸ニッケル２５.３４gを回
収した。この硫酸ニッケル中のマグネシウム量は検出限
界量以下であった。EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Combustion ash of heavy oil fuel (V 2 O 5 : 4.0 wt%, Ni: 0.4 wt%, MgO:
4.2wt%, NH 3: 21.3wt% , SO 3: 53.9wt%) solids concentration 20
% Aqueous slurry, ammonia water was added to 8 kg of solids separated into solid and liquid to adjust the pH to 8, and air (20 l / mi) was added thereto.
n) was introduced and stirred for 2 hours, followed by solid-liquid separation. To the solid content was added aqueous ammonia, and furthermore, aqueous hydrogen peroxide (concentration: 31 v
ol%) was added thereto, followed by stirring and mixing, followed by filtration. The entire amount of the filtrate (14.6 liters) was circulated to the air oxidation step and reused. On the other hand, 2,400 ml of the filtrate after the above air oxidation was withdrawn, and the pH of the ammonia-leached filtrate was adjusted to 8, and then 80 ml of versatic acid (concentration: 30 vol%) was added in 80 ml portions.
Add. After mixing for 3 minutes, versatic acid was separated from the leached filtrate, 80 ml of dilute sulfuric acid (concentration 2 g / l) was added, mixed for 3 minutes, and then dilute sulfuric acid was separated. Next, 80 ml of concentrated sulfuric acid (concentration: 200 g / l) was added to the versatic acid and mixed for 3 minutes, after which concentrated sulfuric acid was separated. The concentrated sulfuric acid was concentrated by repeating extraction 30 times using a fresh extract (the above-mentioned component). The sulfuric acid solution was evaporated to recover 25.34 g of nickel sulfate. The amount of magnesium in this nickel sulfate was below the detection limit.
【００２６】実施例２ バーサチック酸濃度を３０vol％、希硫酸の濃度を５g/
l、濃硫酸の濃度を２００g/lとした以外は実施例１と同
様にして硫酸ニッケル２５.１２ｇを回収した。この硫
酸ニッケル中のマグネシウム量は検出限界量以下であっ
た。 Example 2 The concentration of versatic acid was 30 vol% and the concentration of dilute sulfuric acid was 5 g /
1 and 25.12 g of nickel sulfate were recovered in the same manner as in Example 1 except that the concentration of concentrated sulfuric acid was changed to 200 g / l. The amount of magnesium in this nickel sulfate was below the detection limit.
【００２７】実施例３ 燃焼灰として、Ｎｉ量０.７７％、Ｍｇ量０.０８％およ
び未燃カーボン６３％を含有する灰を用い、バーサチッ
ク酸濃度を３０vo/％、希硫酸の濃度を０.５g/l、濃硫
酸の濃度を２００g/lとした以外は実施例１と同様にし
て硫酸ニッケル１０１.９ｇを回収した。なお、浸出条
件は、灰１kgに対してアンモニア水１０リットルを加え、こ
れを濾過した後に新しい灰を再度加えて浸出し、これを
３回繰り返した。この硫酸ニッケル中のマグネシウム量
は検出限界量以下であった。 Example 3 As combustion ash, ash containing 0.77% of Ni, 0.08% of Mg and 63% of unburned carbon was used, and the versatic acid concentration was 30 vo /% and the concentration of dilute sulfuric acid was 0. 101.9 g of nickel sulfate was recovered in the same manner as in Example 1 except that the concentration of concentrated sulfuric acid was changed to 0.5 g / l and the concentration of concentrated sulfuric acid was changed to 200 g / l. The leaching condition was such that 10 liters of ammonia water was added to 1 kg of ash, and after filtering this, fresh ash was added again for leaching, and this was repeated three times. The amount of magnesium in this nickel sulfate was below the detection limit.
【００２８】比較例１ バーサチック酸に代えてリン酸系ニッケル抽出剤(濃度
３０vol％)８０mlを用いた以外は実施例１と同様にして
ニッケルを回収し、２５.８ｇの硫酸ニッケルを得た。
この硫酸ニッケル中のマグネシウム含有量は０３８％で
あった。 Comparative Example 1 Nickel was recovered in the same manner as in Example 1 except that 80 ml of a phosphoric acid-based nickel extractant (concentration: 30 vol%) was used instead of versatic acid, to obtain 25.8 g of nickel sulfate.
The magnesium content in this nickel sulfate was 038%.
【００２９】[0029]
【発明の効果】本発明の処理方法によれば、石油系燃焼
灰からバナジウムやニッケルを回収する際に、ニッケル
とマグネシウムが共存する溶液から、ニッケルを容易に
かつ効率よくマグネシウムから分離して抽出することが
できる。従来のリン酸系抽出剤はマグネシウムの抽出ｐ
Ｈ域がニッケルよりも低ｐＨ域であるためニッケルを抽
出するとマグネシウムも抽出されるが、本発明で用いる
バーサチック酸の抽出ｐＨ域はリン酸系抽出液とは逆で
あり、そのニッケル抽出ｐＨ域はマグネシウムよりも低
ｐＨ域であるので、ニッケル抽出の際にマグネシウムは
殆ど抽出されず、従って、一段階の抽出処理でニッケル
をマグネシウムから分離して抽出することができる。According to the treatment method of the present invention, when recovering vanadium and nickel from petroleum-based combustion ash, nickel is easily and efficiently separated from magnesium and extracted from a solution in which nickel and magnesium coexist. can do. The conventional phosphate extractant is magnesium
Since the H range is a lower pH range than nickel, when nickel is extracted, magnesium is also extracted. However, the extraction pH range of the versatic acid used in the present invention is opposite to that of the phosphoric acid-based extract. Since is a lower pH range than magnesium, magnesium is hardly extracted during nickel extraction, and therefore, nickel can be separated and extracted from magnesium in a single-stage extraction process.
【図１】本発明の処理方法の概略を示す工程図FIG. 1 is a process diagram showing an outline of a processing method of the present invention.
【図２】浸出濾液のｐＨに対する抽出液中のニッケル濃
度等のグラフFIG. 2 is a graph of the pH of the leaching filtrate versus the nickel concentration in the extract.
【図３】抽出液の濃度に対するニッケル抽出率のグラフFIG. 3 is a graph of the nickel extraction ratio with respect to the concentration of the extract.
【図４】洗浄用の希硫酸濃度に対する希硫酸中のニッケ
ルとマグネシウムの濃度を示すグラフFIG. 4 is a graph showing the concentration of nickel and magnesium in diluted sulfuric acid with respect to the concentration of diluted sulfuric acid for cleaning.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｂ 7/02 Ｃ２２Ｂ 3/00 Ｑ (72)発明者 三浦 啓一 千葉県佐倉市大作二丁目４番２号 太平洋 セメント株式会社佐倉研究所内 Ｆターム(参考） 4D004 AA36 BA05 CA13 CA34 CA35 CA36 CA41 CB02 CC12 CC20 4K001 AA19 BA14 CA06 CA07 DB03 DB07 DB09 DB23 DB30 DB34──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22B 7/02 C22B 3/00 Q (72) Inventor Keiichi Miura 2-4-2 Daisaku, Sakura City, Chiba Prefecture Taiheiyo Cement Co., Ltd. Sakura Laboratory F-term (reference) 4D004 AA36 BA05 CA13 CA34 CA35 CA36 CA41 CB02 CC12 CC20 4K001 AA19 BA14 CA06 CA07 DB03 DB07 DB09 DB23 DB30 DB34
Claims (6)
ら溶媒抽出によってニッケルを抽出する処理方法におい
て、バーサチック酸を抽出液として用い、濾液を弱アル
カリ性として、濾液に含まれるニッケルをバーサチック
酸に抽出することを特徴とする石油系燃焼灰の処理方
法。1. A method for extracting nickel from a filtrate of petroleum-based combustion ash or a processed product thereof by solvent extraction, wherein versatic acid is used as an extract, the filtrate is weakly alkaline, and nickel contained in the filtrate is converted to versatic acid. A method for treating petroleum-based combustion ash, characterized by extracting.
出したバーサチック酸を希硫酸で洗浄することにより、
ニッケルに随伴して抽出されたマグネシウムを希硫酸中
に洗い出し、次に濃硫酸で洗浄することにより濃硫酸中
にニッケルを逆抽出する処理方法。2. The method according to claim 1, wherein the versatic acid from which nickel has been extracted is washed with dilute sulfuric acid.
A method of back-extracting nickel into concentrated sulfuric acid by washing out magnesium extracted with nickel in dilute sulfuric acid and then washing with concentrated sulfuric acid.
７.５〜８.５とし、濃度１０g/l以上のバーサチック酸
を用いて抽出を行う処理方法。3. The method according to claim 1, wherein the pH of the filtrate is 7.5 to 8.5 and extraction is performed using versatic acid having a concentration of 10 g / l or more.
ック酸の洗浄を濃度０.０１〜５g/lの希硫酸を用いてｐ
Ｈ２〜４の酸性下で行い、逆抽出を濃度１００〜３００
g/lの濃硫酸を用いてｐＨ１以下での強酸性下で行う処
理方法。4. The method according to claim 2, wherein the washing of the versatic acid is carried out by using diluted sulfuric acid having a concentration of 0.01 to 5 g / l.
H2-4 under acidic conditions, back-extraction at a concentration of 100-300
A treatment method using strong sulfuric acid at a pH of 1 or less using concentrated sulfuric acid at a concentration of 1 g / l.
スラリーにする水浸出工程、(ロ)水性スラリーの濾液を
酸性下で加熱してバナジウム化合物を析出させ、これを
濾別回収するバナジウム回収工程、(ハ)上記水性スラリ
ーの固形分にアンモニア水を加えて中性ないしアルカリ
性下で酸化処理して含有金属を液中に浸出させるアンモ
ニア浸出工程、(ニ)アンモニア浸出濾液にニッケル抽出
溶媒を加えてニッケルを抽出する工程を有する処理方法
において、ニッケル抽出溶媒としてバーサチック酸を用
い、アンモニア浸出濾液を弱アルカリ性として、濾液に
含まれるニッケルをバーサチック酸に抽出することを特
徴とする石油系燃焼灰の処理方法。(A) a water leaching step of converting petroleum-based combustion ash or a treated product thereof into an aqueous slurry; and (b) heating a filtrate of the aqueous slurry under acidic conditions to precipitate a vanadium compound, which is separated by filtration. Vanadium recovery step, (c) ammonia leaching step of adding ammonia water to the solid content of the aqueous slurry and oxidizing under neutral or alkaline conditions to leaching the contained metal into the liquid, (d) nickel in the ammonia leaching filtrate A processing method comprising a step of extracting nickel by adding an extraction solvent, wherein petroleum characterized by using versatic acid as a nickel extraction solvent, making the ammonia-leached filtrate weakly alkaline, and extracting nickel contained in the filtrate into versatic acid. Treatment method of system combustion ash.
水性スラリーの濾液を水浸出工程に循環して再使用し、
アンモニア浸出の際に、空気導入して固液分離した後に
過酸化水素を添加する二段階の酸化処理を行い、過酸化
水素添加後の濾液を空気酸化工程に循環して再使用し、
その空気酸化後の濾液を溶媒抽出工程に導く処理方法。6. The method according to claim 5, wherein during the water leaching, the filtrate of the aqueous slurry is recycled to the water leaching step and reused.
At the time of ammonia leaching, a two-stage oxidation treatment of adding hydrogen peroxide after introducing air and solid-liquid separation is performed, and the filtrate after the addition of hydrogen peroxide is circulated to the air oxidation step and reused,
A treatment method for guiding the filtrate after the air oxidation to a solvent extraction step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2469113C2 (en) * | 2010-01-21 | 2012-12-10 | Интевеп, С.А. | Regeneration method of metals from heavy hydrotreatment products |
| JP2013112530A (en) * | 2011-11-24 | 2013-06-10 | Sumitomo Metal Mining Co Ltd | Method for producing high-purity nickel sulfate |
| JP7408365B2 (en) | 2019-12-05 | 2024-01-05 | Ｄｏｗａメタルマイン株式会社 | How to dispose of smoke ash |
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1999
- 1999-12-28 JP JP37327499A patent/JP3796646B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2469113C2 (en) * | 2010-01-21 | 2012-12-10 | Интевеп, С.А. | Regeneration method of metals from heavy hydrotreatment products |
| JP2013112530A (en) * | 2011-11-24 | 2013-06-10 | Sumitomo Metal Mining Co Ltd | Method for producing high-purity nickel sulfate |
| JP7408365B2 (en) | 2019-12-05 | 2024-01-05 | Ｄｏｗａメタルマイン株式会社 | How to dispose of smoke ash |
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