JP2002166241A - Method for treating petroleum combustion ash - Google Patents
Method for treating petroleum combustion ashInfo
- Publication number
- JP2002166241A JP2002166241A JP2000363372A JP2000363372A JP2002166241A JP 2002166241 A JP2002166241 A JP 2002166241A JP 2000363372 A JP2000363372 A JP 2000363372A JP 2000363372 A JP2000363372 A JP 2000363372A JP 2002166241 A JP2002166241 A JP 2002166241A
- Authority
- JP
- Japan
- Prior art keywords
- vanadium
- leaching
- liquid
- solid
- solution
- 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
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 24
- 239000003208 petroleum Substances 0.000 title claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 84
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 238000002386 leaching Methods 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 18
- 238000000638 solvent extraction Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000003672 processing method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 8
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100033007 Carbonic anhydrase 14 Human genes 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867862 Homo sapiens Carbonic anhydrase 14 Proteins 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- -1 vanadium Chemical class 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Extraction Or Liquid Replacement (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
バナジウムを効果的に分離回収する処理方法に関する。
より詳しくは、石油系燃焼灰の浸出液からレッドケーキ
の沈澱を経ずに連続溶媒抽出によってバナジウムを効率
よく分離回収する方法に関する。The present invention relates to a method for effectively separating and recovering vanadium from petroleum-based combustion ash.
More specifically, the present invention relates to a method for efficiently separating and recovering vanadium from a leachate of petroleum-based combustion ash by continuous solvent extraction without precipitation of a red cake.
【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石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 of thermal power plants and various industrial plants use petroleum 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】このような重油灰から有価金属を回収する
方法が従来知られている。例えば、特開昭60−469
30号には、石油系燃料の燃焼灰スラリーに硫酸を加え
て灰中の有価金属を浸出させた後に、液性をアルカリ性
に転化して酸化剤を加え、鉄分を沈殿させた後に、液性
を再び強酸性として液中のバナジウムを五酸化バナジウ
ムとして沈殿させ、これを分離回収する方法が記載され
ている。また、特公平4−61709号には、上記方法
において鉄分を除去した後の濾液を冷却してバナジウム
のアンモニウム化合物を沈殿させて分離し、その濾液に
硫酸を添加して硫酸ニッケルアンモニウムを析出させる
方法が提案されている。さらに、特公平5−13718
号にはバナジウムのアンモニウム化合物を沈殿分離した
後に、残渣からアンモニアを分離し、残留するニッケル
スラッジと石膏とをおのおの分離する方法が記載されて
いる。[0003] Methods of recovering valuable metals from such heavy oil ash have been conventionally known. For example, JP-A-60-469
In No. 30, after adding sulfuric acid to the combustion ash slurry of petroleum-based fuel and leaching valuable metals in the ash, the liquid was converted to alkaline, an oxidizing agent was added, and iron was precipitated. Is again made strongly acidic, and vanadium in the liquid is precipitated as vanadium pentoxide, which is separated and recovered. Further, Japanese Patent Publication No. 4-61709 discloses that the filtrate after removing iron in the above method is cooled to precipitate and separate an ammonium compound of vanadium, and sulfuric acid is added to the filtrate to precipitate nickel ammonium sulfate. A method has been proposed. Furthermore, Japanese Patent Publication No. 5-13718
The publication describes a method in which ammonium compounds of vanadium are separated by precipitation, ammonia is separated from the residue, and the remaining nickel sludge and gypsum are each separated.
【0004】また、重油灰浸出スラリーの溶液にアンモ
ニアを添加してpH2.5〜3に調整すると共に塩素酸
ナトリウムを加えて酸性下で液中のバナジウムを酸化
し、液温85℃前後で酸化バナジウムを沈澱(レッドケ
ーキ)させ、固液分離後に、この固形分に温水と炭酸ナ
トリウムおよび塩素酸ナトリウムを加え、弱酸性(pH
6.5〜7.5)下で再溶解し、これを固液分離して固形
分に残留する鉄およびシリカを分離した後にアンモニア
水を加えて弱アルカリ(pH8.5〜9.5)に調整し、液
温75℃前後でバナジン酸アンモニウムを沈澱させ、こ
れを固液分離してバナジウムを回収する方法も知られて
いる。Further, ammonia is added to the solution of the heavy oil ash leaching slurry to adjust the pH to 2.5 to 3, and vanadium in the solution is oxidized under acidic conditions by adding sodium chlorate. After vanadium is precipitated (red cake) and solid-liquid separated, warm water, sodium carbonate and sodium chlorate are added to the solid, and the mixture is weakly acidic (pH
The solution was redissolved under 6.5-7.5) and separated into solid and liquid to separate iron and silica remaining in the solid, and then added with aqueous ammonia to weak alkali (pH 8.5-9.5). It is also known to adjust the temperature, precipitate ammonium vanadate at a liquid temperature of about 75 ° C., and separate the solid into a liquid to recover vanadium.
【0005】[0005]
【発明が解決しようとする課題】従来の処理方法のよう
に、重油灰スラリーに硫酸を添加して液性をpH3以下
に調整し、液温を30〜80℃に加温して、灰中に含ま
れるバナジウムやニッケルなどの有価金属を酸性浸出さ
せる方法では浸出槽などの腐蝕が激しい問題がある。ま
た、硫酸浸出後の酸化処理の際に液性をアルカリ性に転
化しており、その後に再び酸性に戻すなど液性の調整が
煩雑である。さらに、レッドケーキを沈澱させた後に再
溶解と再沈澱を行う方法は鉄分やシリカ分の少ないバナ
ジウム沈殿物を得ることができるが、処理プロセスが複
雑であり、液温も高く、反応時間が長いと云う問題があ
る。As in the conventional treatment method, sulfuric acid is added to heavy oil ash slurry to adjust the liquid property to pH 3 or less, and the liquid temperature is raised to 30 to 80 ° C. In the method of acidic leaching of valuable metals such as vanadium and nickel contained in water, there is a problem that corrosion of a leaching tank or the like is severe. In addition, during the oxidation treatment after sulfuric acid leaching, the liquid property is converted to alkaline, and thereafter the liquid property is adjusted again, for example, by returning to acidic again. In addition, the method of redissolving and reprecipitating the red cake after precipitation can obtain a vanadium precipitate having a small amount of iron and silica, but the treatment process is complicated, the liquid temperature is high, and the reaction time is long. There is a problem.
【0006】本発明は、従来の処理方法における上記問
題を解決したものであり、石油系燃焼灰の浸出スラリー
溶液を連続溶媒抽出に適するように希釈し、これを常温
下で中性ないし弱アルカリ性に調整し、この液性下でバ
ナジウムを酸化した後に連続溶媒抽出を利用してバナジ
ウムを回収する方法を提供するものであり、バナジウム
を比較的に簡単な処理プロセスで効率よく回収でき、常
温で処理するので設備の腐食も少なく、経済的に処理す
ることができる方法を提供する。The present invention solves the above-mentioned problems in the conventional treatment method, and dilutes a leaching slurry solution of petroleum-based combustion ash so as to be suitable for continuous solvent extraction, and neutralizes the solution at room temperature with neutral to weak alkaline. It is intended to provide a method of recovering vanadium using continuous solvent extraction after oxidizing vanadium under this liquidity, vanadium can be efficiently recovered by a relatively simple treatment process, and at room temperature. The present invention provides a method capable of economically treating because the treatment is less likely to corrode equipment.
【0007】[0007]
【課題を解決する手段】本発明は、(1)石油系燃焼灰
の浸出スラリーを固液分離した溶液のバナジウム濃度を
3000ppm以下、およびpHを中性ないし弱アルカリ
性に調整し、この液性下で液中のバナジウムを酸化し、
次いで、この浸出溶液にバナジウム抽出溶媒を導入して
バナジウムを抽出し、回収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 solution obtained by solid-liquid separation of a leaching slurry of petroleum-based combustion ash, wherein the vanadium concentration is adjusted to 3000 ppm or less, and the pH is adjusted to neutral or weakly alkaline. Oxidizes vanadium in the liquid with
Next, the present invention relates to a method for treating petroleum-based combustion ash, which comprises introducing a vanadium extraction solvent into the leaching solution to extract and recover vanadium.
【0008】本発明の上記処理方法は、(2)石油系燃
焼灰の浸出スラリーを固液分離した溶液を希釈してバナ
ジウム濃度を3000ppm以下に調整すると共に、アン
モニアを導入してpH8〜10に調整し、さらに空気お
よび/または過酸化水素を導入して液中のバナジウムを
酸化し、次いで、この浸出溶液にバナジウム抽出溶媒を
導入してバナジウムを抽出し、回収する処理方法、
(3)ミキサセトラーを用いてバナジウムの溶媒抽出を
連続して行う処理方法、(4)石油系燃焼灰を水ないし
硫酸で浸出し、その浸出スラリーを固液分離する工程、
その濾液のバナジウム濃度を3000ppm以下とし、p
H8〜10に調整すると共に空気および/または過酸化
水素を導入して液中のバナジウムを酸化する工程、この
浸出溶液にバナジウム抽出溶媒を導入してバナジウムを
抽出する工程、一方、上記浸出スラリーの固形分にアン
モニア水を加えてpH7〜10に調整し、酸化剤を加え
て酸化浸出し、固液分離する工程、この濾液をバナジウ
ム抽出工程に導く工程を有する処理方法、(5)酸化浸
出工程で固液分離した濾液をニッケル溶媒抽出工程に導
いて処理する工程を有する処理方法を含む。According to the above-mentioned treatment method of the present invention, (2) a solution obtained by solid-liquid separation of a leaching slurry of petroleum-based combustion ash is diluted to adjust the vanadium concentration to 3000 ppm or less, and ammonia is introduced to adjust the pH to 8 to 10. Adjusting, further oxidizing the vanadium in the liquid by introducing air and / or hydrogen peroxide, and then extracting vanadium by introducing a vanadium extraction solvent to the leaching solution, a processing method of recovering,
(3) a treatment method for continuously extracting the solvent of vanadium using a mixer settler, (4) a step of leaching petroleum-based combustion ash with water or sulfuric acid, and a solid-liquid separation of the leached slurry.
The vanadium concentration of the filtrate was adjusted to 3000 ppm or less, and p
Adjusting the H8 to 10 and introducing air and / or hydrogen peroxide to oxidize vanadium in the liquid; introducing a vanadium extraction solvent to the leaching solution to extract vanadium; A treatment method having a step of adding ammonia water to the solid content to adjust the pH to 7 to 10, adding an oxidizing agent, oxidizing and leaching, and solid-liquid separation, and a step of leading the filtrate to a vanadium extraction step; And a treatment method having a step of treating the filtrate separated by solid-liquid separation in the step of extracting with a nickel solvent.
【0009】[0009]
【発明の実施の形態】以下、本発明を実施形態に基づい
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。図示する本発明の処理方法の一例は、石油系燃焼灰
を水浸出または硫酸浸出し、この浸出スラリーを固液分
離する工程、固液分離した溶液のバナジウム濃度を30
00ppm以下に希釈する工程、およびpHを中性ないし
弱アルカリ性に調整すると共にこの液性下で液中のバナ
ジウムを酸化する工程、この浸出溶液にバナジウム抽出
溶媒を導入してバナジウムを抽出し回収する工程を有す
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. One example of the treatment method of the present invention shown in the drawings is a step of leaching petroleum-based combustion ash with water or sulfuric acid, separating the leached slurry into solid and liquid, and setting the vanadium concentration of the solid-liquid separated solution to 30.
A step of diluting the solution to 00 ppm or less, and a step of adjusting the pH to neutral to weakly alkaline and oxidizing vanadium in the solution under the liquidity, and extracting and recovering vanadium by introducing a vanadium extraction solvent into the leaching solution. Having a process.
【0010】本発明において石油系燃焼灰とは、タール
質燃料、重油、石油コークス、石油ピッチ、アスファル
ト等の石油系燃料を燃焼した際に生じる塵灰を云う。こ
れらは発電所や各種工業プラントのボイラー等から排出
される集塵灰等を処理対象にすることができる。この燃
焼灰には多量の硫黄分が含まれているので水を加えてス
ラリー(水浸出スラリー)にすると硫黄分が溶出して液性
はpH1前後の強酸性になる。また硫酸浸出しても同様
に強酸性になり、この浸出処理によって燃焼灰に含まれ
るバナジウムがスラリー中に溶出する。なお、ニッケル
やマグネシウムの一部も溶出するが大部分は固形分に残
留する。In the present invention, the petroleum-based combustion ash refers to dust ash generated when a petroleum-based fuel such as tar fuel, heavy oil, petroleum coke, petroleum pitch, and asphalt is burned. These can treat dust ash discharged from boilers and the like of power plants and various industrial plants. Since this combustion ash contains a large amount of sulfur, when water is added to form a slurry (water leached slurry), the sulfur is eluted and the liquid property becomes strongly acidic at around pH 1. Also, sulfuric acid leaching becomes strongly acidic, and vanadium contained in the combustion ash is eluted into the slurry by this leaching treatment. Note that a part of nickel or magnesium is also eluted, but most of the nickel or magnesium remains in the solid content.
【0011】本発明の溶媒抽出を利用する処理方法は、
この浸出スラリーを固液分離した濾液を水で希釈し、あ
るいは多量の水で浸出することによって、液中のバナジ
ウム濃度が3000ppm以下となるように調整する。次
工程でバナジウムの溶媒抽出を行う場合、高濃度の硫酸
アンモニウムが溶存する液中でバナジウム濃度が300
0ppmより高いと抽出溶媒の種類によってはバナジウム
の分離が遅くなるので好ましくない。The processing method using solvent extraction according to the present invention comprises:
The filtrate obtained by solid-liquid separation of the leached slurry is diluted with water or leached with a large amount of water so that the concentration of vanadium in the liquid is adjusted to 3000 ppm or less. When performing vanadium solvent extraction in the next step, the vanadium concentration is set to 300 in a solution in which a high concentration of ammonium sulfate is dissolved.
If it is higher than 0 ppm, the separation of vanadium will be slow depending on the kind of the extraction solvent, which is not preferable.
【0012】次に、この溶液にアンモニアを加えて液性
を中性ないし弱アルカリ性(pH8〜10)に調整する。
アンモニアの添加は常温下でよく、加熱する必要はな
い。この液性下で、さらに酸化剤、例えば、空気や過酸
化水素などを導入して液中の4価のバナジウムを5価に
酸化する。通常のバナジウム抽出溶媒では4価のバナジ
ウムイオンは抽出されないので、液中のバナジウムを酸
化して5価のバナジウムイオンにする。このとき、溶液
のpHが8より低い(酸性側)と酸化剤の量が多く必要に
なり、一方pHが10より高い(アルカリ側)とバナジウ
ムの抽出率が低下するので好ましくない。なお、空気酸
化の場合、その導入量は0.02m3N/秒以上が適当で
あり、過酸化水素の場合には2g/l以上が好ましい。Next, ammonia is added to the solution to adjust the solution to neutral to weakly alkaline (pH 8 to 10).
The addition of ammonia may be performed at room temperature and does not require heating. Under this liquidity, an oxidizing agent such as air or hydrogen peroxide is further introduced to oxidize tetravalent vanadium in the liquid to pentavalent. Since tetravalent vanadium ions are not extracted by a normal vanadium extraction solvent, vanadium in the liquid is oxidized to pentavalent vanadium ions. At this time, if the pH of the solution is lower than 8 (acid side), a large amount of the oxidizing agent is required, while if the pH is higher than 10 (alkaline side), the extraction rate of vanadium decreases, which is not preferable. In the case of air oxidation, the introduction amount is suitably 0.02 m 3 N / sec or more, and in the case of hydrogen peroxide, it is preferably 2 g / l or more.
【0013】以上のように液性を調整した浸出溶液をバ
ナジウム抽出溶媒と混合して溶液中のバナジウムを抽出
する。このバナジウム抽出液は中性ないし弱アルカリ性
で作用するもの、例えば、キレート剤(Tricaprylyl Met
hyl Ammonium Chloride)をケロシンで5vol%に希釈し
たメチルアンモニウム系キレート液などを用いることが
できる。抽出処理後、バナジウムを含む抽出溶媒に塩化
アンモニウムとアンモニア水の混合液(NH4Cl:75%、NH4
OH:25%)を水で希釈したものなどを混合して逆抽出を行
う。次いで、この逆抽出液にアンモニア水を加えてpH
10前後、液温75℃前後に調整してメタバナジン酸ア
ンモニウムを沈澱させ、この沈澱を濾過分離して回収す
る。分離した濾液は逆抽出工程に循環して再利用するこ
とができる。回収したメタバナジン酸アンモニウムは乾
燥し、あるいは加熱分解してバナジン酸の粉末を得る。[0013] The leaching solution whose liquid properties have been adjusted as described above is mixed with a vanadium extraction solvent to extract vanadium in the solution. This vanadium extract is neutral or weakly alkaline, for example, a chelating agent (Tricaprylyl Met
hyl Ammonium Chloride) diluted with kerosene to 5 vol% can be used. After the extraction treatment, a mixed solution of ammonium chloride and ammonia water (NH 4 Cl: 75%, NH 4 Cl) was added to an extraction solvent containing vanadium.
(OH: 25%) diluted with water and the like are mixed and back-extracted. Next, aqueous ammonia was added to the back extract to adjust the pH.
The solution is adjusted to about 10 and the liquid temperature to about 75 ° C. to precipitate ammonium metavanadate, and the precipitate is separated by filtration and collected. The separated filtrate can be recycled and recycled to the back extraction step. The recovered ammonium metavanadate is dried or thermally decomposed to obtain a vanadic acid powder.
【0014】上記バナジウムの抽出処理は、好ましく
は、条件を整えて連続抽出を行う。連続抽出装置はミキ
サセトラー等を用いることができ、抽出装置の種類は限
定されない。ミキサセトラーの場合、有機相(O)と水相
(A)の比(O/A)を、抽出工程では0.2〜5、逆抽出工
程では0.5〜2に調整し、セトラーで分離した水相を
ミキサーに一部戻して濃縮させると良い。In the above-mentioned vanadium extraction treatment, preferably, continuous extraction is performed under conditions. As the continuous extraction device, a mixer settler or the like can be used, and the type of the extraction device is not limited. In the case of mixer settler, organic phase (O) and aqueous phase
When the ratio (O / A) of (A) is adjusted to 0.2 to 5 in the extraction step and to 0.5 to 2 in the back extraction step, the aqueous phase separated by the settler is partially returned to the mixer and concentrated. good.
【0015】バナジウム抽出溶媒と分離した溶液には硫
酸イオンが含まれているので、これにカルシウム化合物
を加え、石膏(CaSO4・2H2O)を沈澱させて溶液から分離す
ることにより液中の硫酸濃度を低減することができる。
また、回収した石膏を再利用することができる。カルシ
ウム化合物としては生石灰(CaO)、消石灰[Ca(OH)2]、炭
酸カルシウム(CaCO3)などを用いることができる。さら
にこの溶液にはアンモニアが多量に含まれているので、
石膏を分離した溶液を蒸留塔に導き、アンモニアを蒸留
させて回収することができる。Since the solution separated from the vanadium extraction solvent contains sulfate ions, a calcium compound is added to the solution and gypsum (CaSO 4 .2H 2 O) is precipitated to separate the solution from the solution. The sulfuric acid concentration can be reduced.
Further, the collected gypsum can be reused. As the calcium compound, quick lime (CaO), slaked lime [Ca (OH) 2 ], calcium carbonate (CaCO 3 ) and the like can be used. In addition, this solution contains a large amount of ammonia,
The solution from which the gypsum has been separated is guided to a distillation column, and ammonia can be distilled and recovered.
【0016】以上の処理方法は、石油系燃焼灰の浸出ス
ラリーを固液分離して得た溶液についてのものである
が、この固液分離によって残留した固形分からもバナジ
ウムやニッケル、マグネシウムを回収することができ
る。先ず、上記浸出スラリーの固形分にアンモニア水を
加えてpH7〜10の中性ないし弱アルカリ性に調整
し、この液性下で酸化処理する。酸化処理は溶液に空気
を導入して攪拌する第一段処理と、さらに過酸化水素あ
るいは硫酸を溶液に加えて酸化する第二段処理とを行う
と良い。この中性ないし弱アルカリ性下の酸化浸出によ
って固形分に含まれるバナジウムおよびニッケルの浸出
効果が向上する。The above treatment method is for a solution obtained by solid-liquid separation of a leaching slurry of petroleum-based combustion ash, and vanadium, nickel and magnesium are also recovered from the solid content remaining by this solid-liquid separation. be able to. First, ammonia water is added to the solid content of the leached slurry to adjust the pH to a neutral to weakly alkaline pH of 7 to 10, and an oxidation treatment is performed under this liquidity. In the oxidation treatment, it is preferable to perform a first stage treatment in which air is introduced into the solution and agitating the solution, and a second stage treatment in which hydrogen peroxide or sulfuric acid is added to the solution to oxidize the solution. Oxidizing leaching under neutral or weak alkaline conditions improves the leaching effect of vanadium and nickel contained in the solid content.
【0017】このような中性ないし弱アルカリ性下での
酸化浸出後に、この浸出スラリーを固液分離し、この溶
液を溶媒抽出工程に導いてバナジウムおよびニッケルを
回収する。残渣は最初の浸出工程に戻して再処理すると
良い。このバナジウムの溶媒抽出は先の希釈工程で得た
溶液のバナジウム溶媒抽出と同様に行えば良い。あるい
は、この浸出溶液と先の希釈工程で得た溶液とを混合し
てバナジウムの溶媒抽出をまとめて行っても良い。After such oxidative leaching under neutral or weak alkaline conditions, the leached slurry is subjected to solid-liquid separation, and the solution is led to a solvent extraction step to recover vanadium and nickel. The residue may be returned to the first leaching step and reprocessed. This vanadium solvent extraction may be performed in the same manner as the vanadium solvent extraction of the solution obtained in the previous dilution step. Alternatively, the leaching solution and the solution obtained in the previous dilution step may be mixed, and the solvent extraction of vanadium may be performed collectively.
【0018】ニッケルを回収するには、バナジウム抽出
前あるいは抽出後の溶液をニッケル抽出工程に導き、中
性ないし弱アルカリ性で作用するアセトフェノン系キレ
ート液やバーサチック酸などの溶媒を用いてニッケルを
抽出し、次いでこれを濃硫酸で洗浄してニッケルを逆抽
出し、硫酸ニッケルとして回収することができる。これ
らバナジウムの抽出とニッケルの抽出は液中の含有量が
少ないほうから行えば抽出処理の負担が少なくて済む。To recover nickel, the solution before or after vanadium extraction is led to a nickel extraction step, and nickel is extracted using a solvent such as an acetophenone-based chelate solution or a versatic acid which acts in a neutral or weak alkaline state. It can then be washed with concentrated sulfuric acid to back-extract nickel and recover as nickel sulfate. If the extraction of vanadium and the extraction of nickel are performed from the side with the smaller content in the liquid, the burden of the extraction process can be reduced.
【0019】溶媒抽出後の溶液には硫酸イオンとマグネ
シウムイオンが溶存しているので、これを石膏および水
酸化マグネシウムとして回収することができる。石膏の
回収は先の希釈工程後の処理と同様にして行っても良い
が、この溶液に消石灰スラリーなどを混合して石膏と水
酸化マグネシウムを同時に沈澱させ、これを液体サイク
ロンに導いて分離する方法でも良い。ここで生じる水酸
化マグネシウムの沈澱粒子は概ね石膏の沈澱粒子よりも
微細であるので、これらの沈澱を含む懸濁液を液体サイ
クロンに導いて分離することができる。Since the sulfate ion and the magnesium ion are dissolved in the solution after the solvent extraction, it can be recovered as gypsum and magnesium hydroxide. The gypsum may be collected in the same manner as in the treatment after the previous dilution step.However, this solution is mixed with slaked lime slurry to precipitate gypsum and magnesium hydroxide at the same time, and then led to a liquid cyclone for separation. A method is also acceptable. Since the precipitated particles of magnesium hydroxide formed here are generally finer than the precipitated particles of gypsum, the suspension containing these precipitates can be introduced into a hydrocyclone for separation.
【0020】[0020]
【実施例】以下、本発明を実施例によって具体的に示
す。なお、%は特に示さない限り重量%である。EXAMPLES The present invention will be specifically described below with reference to examples. The percentages are by weight unless otherwise indicated.
【0021】〔実施例1〕燃焼灰(V:2.0wt%、N
i:0.44wt%、Mg:2.3wt%、S:22wt%)10
0kgに水100リットルを加え、pHが2.5以上の場合に
はさらに硫酸を加えて10分間浸出し、この浸出スラリ
ーをフィルタープレスで固液分離した。この濾液113
リットルにアンモニア水(20%濃度)11kgと水775kgを加
えて液中のバナジウム濃度を1700ppm、pH9.0に
調整し、これに空気0.03m3N/secを吹き込んで均一
に攪拌した。この溶液にバナジウム抽出溶媒を加えてバ
ナジウムを抽出した。バナジウムの抽出溶媒としては、
キレート剤(Tricaprylyl Methyl Ammonium Chloride)
をケロシンで5vol%に希釈したもの用い、浸出溶液に
対して抽出溶媒を1:1の液量で3分間混合した。この
抽出溶媒300mlに逆抽出液(NH4Cl8%とNH4OH3%の
混合液)300mlを混合し、溶液のpHを10.7に調
整し、3分間混合してバナジウムを逆抽出した。この逆
抽出液をバナジウム抽出溶媒と分離した後に再び新しい
抽出溶媒と混合して逆抽出を繰り返し、バナジウムを濃
縮した。このとき逆抽出液で生じた析出物は沈降させて
分離し、その上澄み液(285ml)に新しい逆抽出液(1
5ml)を補給して混合槽に戻し、抽出溶媒と混合して逆
抽出を繰り返した。沈降物は濾過分離して回収し、乾燥
してメタバナジン酸アンモニウム粉末3.4kgを得た。Example 1 Combustion ash (V: 2.0 wt%, N
i: 0.44 wt%, Mg: 2.3 wt%, S: 22 wt%) 10
100 kg of water was added to 0 kg, and when the pH was 2.5 or more, sulfuric acid was further added and leached for 10 minutes, and the leached slurry was solid-liquid separated by a filter press. This filtrate 113
11 kg of aqueous ammonia (20% concentration) and 775 kg of water were added to the liter to adjust the vanadium concentration in the liquid to 1700 ppm and pH 9.0, and air was blown into the liquid to give 0.03 m 3 N / sec, followed by uniform stirring. A vanadium extraction solvent was added to this solution to extract vanadium. As the extraction solvent for vanadium,
Chelating agent (Tricaprylyl Methyl Ammonium Chloride)
Was diluted to 5 vol% with kerosene, and the extraction solvent was mixed with the leaching solution at a 1: 1 volume for 3 minutes. The extraction solvent back extraction solution 300ml (NH 4 Cl8% and NH 4 OH3% of the mixture) were mixed 300 ml, the pH of the solution was adjusted to 10.7, were back extracted vanadium and mixed for 3 minutes. This back-extract was separated from the vanadium extraction solvent, mixed with a new extraction solvent again, and back-extraction was repeated to concentrate the vanadium. At this time, the precipitate formed in the back extract was settled and separated, and the supernatant (285 ml) was added to the fresh back extract (1).
(5 ml) was added back to the mixing tank, mixed with the extraction solvent, and the back extraction was repeated. The precipitate was collected by filtration and dried to obtain 3.4 kg of ammonium metavanadate powder.
【0022】〔実施例2〕実施例1の水浸出スラリーを
固液分離して得た固形分58kg(含水量34%)にアンモニ
ア水(20%濃度)3.7kgと水226kgを加えてpH約8.
0に調整し、これに空気0.03m3N/secを吹き込んで
酸化処理を行った。この浸出スラリーをフィルタープレ
スで固液分離し、濾液240リットルを得た。この濾液のバ
ナジウム濃度は2g/l、ニッケル濃度は1.9g/lであっ
た。この溶液にバーサチック酸を加え、溶液とバーサチ
ック酸の液量を1:1の割合で3分間混合してニッケル
を抽出した。次に、このバーサチック酸を溶液から分離
し、バーサチック酸300mlに対して硫酸(濃度20%)3
00mlを加えて3分間混合し、ニッケルを硫酸に逆抽出
した。バーサチック酸と分離した硫酸は新しくニッケル
を抽出したバーサチック酸と再び混合し、逆抽出を繰り
返してニッケルを濃縮した。これを40回繰り返した後
に逆抽出液を30〜80℃に加熱して水分を蒸発させ、
硫酸ニッケル粉末19kgを得た。一方、ニッケル抽出溶
媒と分離した浸出溶液240リットルを実施例1と同様のバ
ナジウム抽出工程に導き、メタバナジン酸アンモニウム
粉末1.1kgを得た。Example 2 3.7 kg of aqueous ammonia (20% concentration) and 226 kg of water were added to 58 kg of solid content (water content 34%) obtained by solid-liquid separation of the water leached slurry of Example 1 to obtain a pH. About 8.
Was adjusted to 0, it was performed Thereto blown by oxidizing the air 0.03m 3 N / sec. This leached slurry was subjected to solid-liquid separation with a filter press to obtain 240 liters of a filtrate. The filtrate had a vanadium concentration of 2 g / l and a nickel concentration of 1.9 g / l. Versatic acid was added to the solution, and nickel was extracted by mixing the solution and the versatic acid at a 1: 1 ratio for 3 minutes. Next, this versatic acid was separated from the solution, and sulfuric acid (concentration: 20%) was added to 300 ml of versatic acid.
00 ml was added and mixed for 3 minutes, and nickel was back-extracted into sulfuric acid. The sulfuric acid separated from versatic acid was mixed again with versatic acid from which nickel was newly extracted, and nickel was concentrated by repeating back-extraction. After repeating this 40 times, the back extract is heated to 30 to 80 ° C. to evaporate water,
19 kg of nickel sulfate powder was obtained. On the other hand, 240 l of the leach solution separated from the nickel extraction solvent was led to the same vanadium extraction step as in Example 1 to obtain 1.1 kg of ammonium metavanadate powder.
【0023】[0023]
【発明の効果】本発明の処理方法によれば、石油系燃焼
灰の浸出スラリー溶液からバナジウムを比較的に簡単な
処理プロセスで効率よく回収できる。また本処理方法は
常温で実施するので設備の腐食やエネルギー費用が少な
く、経済的である。According to the treatment method of the present invention, vanadium can be efficiently recovered from a leach slurry solution of petroleum-based combustion ash by a relatively simple treatment process. In addition, since the present treatment method is carried out at normal temperature, equipment corrosion and energy costs are small and economical.
【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.
───────────────────────────────────────────────────── フロントページの続き (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 セメント株式会社中央研究所内 Fターム(参考) 4D004 AA36 AB03 BA05 CA13 CA34 CA35 CA36 CC02 CC03 CC04 CC06 CC11 CC12 DA03 DA10 DA20 4D056 AB03 AC02 AC25 BA03 CA06 CA14 CA27 CA31 CA33 CA39 DA05 DA10 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Keiichi Miura 2-4-2, Osaku, Sakura City, Chiba Prefecture Pacific Cement Co., Ltd. Central Research Laboratory F-term (reference) 4D004 AA36 AB03 BA05 CA13 CA34 CA35 CA36 CC02 CC03 CC04 CC06 CC11 CC12 DA03 DA10 DA20 4D056 AB03 AC02 AC25 BA03 CA06 CA14 CA27 CA31 CA33 CA39 DA05 DA10
Claims (5)
した溶液のバナジウム濃度を3000ppm以下、および
pHを中性ないし弱アルカリ性に調整し、この液性下で
液中のバナジウムを酸化し、次いで、この浸出溶液にバ
ナジウム抽出溶媒を導入してバナジウムを抽出し、回収
することを特徴とする石油系燃焼灰の処理方法。1. A vanadium concentration of a solution obtained by solid-liquid separation of a leaching slurry of petroleum-based combustion ash is adjusted to 3000 ppm or less, and a pH is adjusted to neutral or weakly alkaline, and vanadium in the liquid is oxidized under the liquidity. Next, a vanadium extraction solvent is introduced into the leaching solution to extract and recover vanadium, and a method for treating petroleum-based combustion ash, comprising:
した溶液を希釈してバナジウム濃度を3000ppm以下
に調整すると共に、アンモニアを導入してpH8〜10
に調整し、さらに空気および/または過酸化水素を導入
して液中のバナジウムを酸化し、次いで、この浸出溶液
にバナジウム抽出溶媒を導入してバナジウムを抽出し、
回収する請求項1の処理方法。2. A solution obtained by solid-liquid separation of a leaching slurry of petroleum-based combustion ash is diluted to adjust the vanadium concentration to 3000 ppm or less, and ammonia is introduced to adjust the pH to 8 to 10.
And further introduce air and / or hydrogen peroxide to oxidize vanadium in the liquid, and then introduce vanadium extraction solvent into the leaching solution to extract vanadium,
The processing method according to claim 1, wherein the processing is performed.
媒抽出を連続して行う請求項1または2の処理方法。3. The treatment method according to claim 1, wherein the solvent extraction of vanadium is continuously performed using a mixer settler.
し、その浸出スラリーを固液分離する工程、その濾液の
バナジウム濃度を3000ppm以下とし、pH8〜10
に調整すると共に空気および/または過酸化水素を導入
して液中のバナジウムを酸化する工程、この浸出溶液に
バナジウム抽出溶媒を導入してバナジウムを抽出する工
程、一方、上記浸出スラリーの固形分にアンモニア水を
加えてpH7〜10に調整し、酸化剤を加えて酸化浸出
し、固液分離する工程、この濾液をバナジウム抽出工程
に導く工程を有する請求項1、2または3の処理方法。4. A step of leaching petroleum-based combustion ash with water or sulfuric acid, separating the leached slurry into a solid and a liquid, and setting the vanadium concentration of the filtrate to 3000 ppm or less and the pH of 8 to 10
Adjusting the air and / or introducing hydrogen peroxide to oxidize the vanadium in the liquid, introducing a vanadium extraction solvent to the leaching solution to extract vanadium, while the solid content of the leaching slurry 4. The method according to claim 1, further comprising the steps of adding ammonia water to adjust the pH to 7 to 10, adding an oxidizing agent, oxidizing and leaching, and solid-liquid separation, and introducing the filtrate to a vanadium extraction step.
ケル溶媒抽出工程に導いて処理する工程を有する請求項
4の処理方法。5. The processing method according to claim 4, further comprising the step of conducting the filtrate which has been subjected to the solid-liquid separation in the oxidative leaching step to a nickel solvent extraction step.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000363372A JP3780358B2 (en) | 2000-11-29 | 2000-11-29 | Treatment method for petroleum combustion ash |
Applications Claiming Priority (1)
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Cited By (2)
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WO2011074948A1 (en) * | 2009-10-06 | 2011-06-23 | Elemetal Holding B.V. | Hydrometalurgical process and apparatus for recovering metals from waste material |
JP2013133233A (en) * | 2011-12-26 | 2013-07-08 | Sumitomo Metal Mining Co Ltd | Method for treating leachate |
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Cited By (4)
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WO2011074948A1 (en) * | 2009-10-06 | 2011-06-23 | Elemetal Holding B.V. | Hydrometalurgical process and apparatus for recovering metals from waste material |
US20120234137A1 (en) * | 2009-10-06 | 2012-09-20 | Elemetal Holding B.V. | Hydrometalurgical process and apparatus for recovering metals from waste material |
US9023129B2 (en) * | 2009-10-06 | 2015-05-05 | Elemetal Holding B.V. | Hydrometalurgical process and apparatus for recovering metals from waste material |
JP2013133233A (en) * | 2011-12-26 | 2013-07-08 | Sumitomo Metal Mining Co Ltd | Method for treating leachate |
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