JP2010508440A - Recovery of non-ferrous metals from zinc and lead industry byproducts using electrothermal smelting in submerged plasma - Google Patents
Recovery of non-ferrous metals from zinc and lead industry byproducts using electrothermal smelting in submerged plasma Download PDFInfo
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- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 238000003723 Smelting Methods 0.000 title claims abstract description 8
- 239000011701 zinc Substances 0.000 title abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 26
- 238000011084 recovery Methods 0.000 title abstract description 5
- 239000006227 byproduct Substances 0.000 title abstract description 3
- -1 ferrous metals Chemical class 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000002893 slag Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 6
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims 1
- 229910052935 jarosite Inorganic materials 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000571 coke Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 208000024780 Urticaria Diseases 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010792 electronic scrap Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/28—Obtaining zinc or zinc oxide from muffle furnace residues
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/005—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys using plasma jets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/226—Remelting metals with heating by wave energy or particle radiation by electric discharge, e.g. plasma
-
- 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
Abstract
本発明は、亜鉛含有残留物からの、特に亜鉛及び鉛産業の副産物、例えば針鉄鉱及びジャロサイトからの、非鉄金属の回収のための単工程の乾式製錬法に関する。Ｚｎ、Ｆｅ及びＳを含有する産業Ｚｎ残留物からの金属の回収のための方法は、Ｚｎはヒューミングされ、Ｆｅはスラグにされ、かつＳはＳＯ2に酸化される場合において、Ｚｎのヒューミング、Ｆｅのスラグ形成及びＳの酸化が、酸化性ガス混合物を生じる少なくとも１つの液中プラズマトーチを含有する炉中で前記残留物を溶錬することによって、及び固体還元剤をその溶融物に供給することによって、単工程法で実施されることを特徴とすることを定義する。その方法は、Ｓの酸化及びＦｅのスラグ化を達成する一方で、同時に金属、例えばＳの還元及びヒューミングを達成する。The present invention relates to a single-step dry smelting process for the recovery of non-ferrous metals from zinc-containing residues, in particular from zinc and lead industry by-products such as goethite and jarosite. A method for the recovery of metals from industrial Zn residues containing Zn, Fe and S is that Zn is fumed, Fe is slag, and S is oxidized to SO 2. By smelting the residue in a furnace containing at least one submerged plasma torch, wherein ming, Fe slag formation and S oxidation produce an oxidizing gas mixture, and a solid reducing agent into the melt. By defining, it is characterized by being performed in a single step process. The method achieves S oxidation and Fe slagging, while at the same time achieving reduction and fuming of metals such as S.
Description
本発明は、亜鉛含有残留物からの、特に亜鉛及び鉛産業の副産物、例えば針鉄鉱及びジャロサイトからの、非鉄金属の回収のための単工程の乾式製錬法に関する。 The present invention relates to a single-step dry smelting process for the recovery of non-ferrous metals from zinc-containing residues, in particular from zinc and lead industry by-products such as goethite and jarosite.
廃棄物を含有する重金属、例えば浸出残留物及びＥＡＦ−ダストの埋め立てによる環境影響の高められた理解、並びにますます厳しくなる環境法に関して、冶金学界は、経済及び環境に優しい方法でそれら材料を加工することができる技術の開発のために励んでいる。過去に、いくつかの電熱製錬法が、開発され、かつそれら材料を加工するために操作されている。それらは、高温製錬における重金属の還元及び揮発に基づく。現存の方法の概要を簡単に次に示す。 With an increased understanding of the environmental impacts of waste-containing heavy metals such as leachable residues and EAF-dust landfills, and increasingly stringent environmental laws, the metallurgical community is processing these materials in an economical and environmentally friendly manner Encouraging for the development of technology that can be. In the past, several electrothermal smelting methods have been developed and operated to process the materials. They are based on the reduction and volatilization of heavy metals in high temperature smelting. A brief overview of existing methods follows.
ウェルツ（Ｗａｅｌｚ）法は、ＥＡＦ−ダスト及び亜鉛の浸出残留物の処理のためのおそらく最も広く使用される方法である。残留物、コークス、及びフラックスの乾燥混合物は、大きい回転炉に供給され、かつ１２００〜１３００℃まで加熱される。亜鉛フェライトが分解され、かつ揮発性種、例えばＺｎ及びＰｂＳがヒューミングされる。前記のヒューミングは、浴の上で再酸化されて、排ガスから濾過されうる固体粒子を形成する。回収されたＺｎＯ粒子は、例えば、湿式製錬のＺｎ流れ図における焼成のための代用として使用されうる。しかしながら、ウェルツ法において使用される回転炉は、高い出資及び操作費用を有する大きい装置である。さらに、そのエネルギー効率は、むしろ低く、かつコークス消費は、高い。 The Weelz method is probably the most widely used method for the treatment of leaching residues of EAF-dust and zinc. The dry mixture of residue, coke, and flux is fed to a large rotary furnace and heated to 1200-1300 ° C. Zinc ferrite is decomposed and volatile species such as Zn and PbS are fumed. The fuming is reoxidized on the bath to form solid particles that can be filtered from the exhaust gas. The recovered ZnO particles can be used, for example, as a substitute for firing in a hydrometallurgical Zn flow diagram. However, the rotary furnace used in the Wertz process is a large device with high capital and operating costs. Furthermore, its energy efficiency is rather low and coke consumption is high.
残留物を含有する重金属を加工するための他のアプローチは、高炉技術である。現在では滅多に使用されないが、日本において未だ広く適用されている。ウェルツ法として、その残留物が、フラックスで乾燥及び混合されるべきであり、追加のブリケッティング操作が、さらに要求される。大量の塊コークスが、還元剤及び熱源として添加される。他の亜鉛ヒューミング法と同様に、重金属は、ヒューミングされ、かつ後燃焼される。分離マット及びスラグ相が生じるが、しかしマット相は、鉄で強く希薄され、高価な金属、例えばＣｕ及び貴金属の比較的低い濃度を有する大量のマットを導く。ＺｎＯヒューミングは、ウェルツ法におけるように処理されうる。 Another approach for processing heavy metals containing residues is blast furnace technology. Although rarely used today, it is still widely applied in Japan. As the Welts method, the residue should be dried and mixed with the flux, further requiring additional briquetting operations. Large quantities of coke are added as a reducing agent and heat source. Similar to other zinc fuming methods, heavy metals are fumed and post-combusted. Separation mats and slag phases occur, but the mat phases are strongly diluted with iron, leading to large amounts of mats with relatively low concentrations of expensive metals such as Cu and noble metals. ZnO fuming can be processed as in the Welts process.
例えばＳＫＦ Ｐｌａｓｍａｄｕｓｔ（登録商標）法におけるコークス充填層反応器は、粒子における亜鉛含有残留物及びＥＡＦダストを処理するための第三の装置である。この方法において、酸化物の廃棄物は、前記の炉の底部における羽口を介して、微粉炭及びスラグ形成体と共に、粉体で注入される。エネルギーは、該羽口に連結されたプラズマトーチによって提供される。亜鉛ヒューミングを含有する上昇ガスは、さらに、充填コークス床中で還元及び冷却され、かつ該亜鉛は、スプラッシュコンデンサー中で回収される。高いエネルギー要求は、安価な電気での領域における経済的に実行可能な方法のみをもたらす。他の主な欠点は、供給材料が、前記羽口を介して、粉体で注入されるべきであることである。 For example, a coke packed bed reactor in the SKF Plasmamadst® process is a third device for treating zinc-containing residues and EAF dust in particles. In this method, oxide waste is injected in powder together with pulverized coal and slag formers through the tuyeres at the bottom of the furnace. Energy is provided by a plasma torch connected to the tuyere. The rising gas containing zinc fuming is further reduced and cooled in a packed coke bed, and the zinc is recovered in a splash condenser. High energy requirements only result in economically viable methods in the area of cheap electricity. Another major drawback is that the feed material should be injected in powder via the tuyere.
鉛溶鉱炉スラグは、通常、従来のバッチスラグヒューミング操作において処理される。その方法は、水冷却ジャケット中で実施され、かつ羽口を介して溶融スラグ中へ微粉炭及び空気の注入を含む。亜鉛、鉛及びいくつかの他の元素は、該スラグからヒューミングされ、かつ前記の浴を再酸化させて、濾過装置において得られた酸化粒子を生じる。 Lead blast furnace slag is typically processed in a conventional batch slag fuming operation. The method is carried out in a water cooling jacket and involves the injection of pulverized coal and air through the tuyere into the molten slag. Zinc, lead and some other elements are fumed from the slag and reoxidize the bath to produce oxidized particles obtained in the filtration device.
ランス炉（Ｉｓａｓｍｅｌｔ（登録商標）又はＡｕｓｍｅｌｔ（登録商標））を浸水させた上部の吹込成形は、廃棄物を含有する亜鉛を処理するためにも使用されうる。乾燥させた残留物、炭及びフラックスは、最初の浸水ランス炉の溶錬炉中へ供給されて、亜鉛及び鉛の部分をスラグから取り除き、かつ硫黄を取り除く。溶融スラグは、二番目の浸水ランス炉のヒューミング炉中へ連続的に溢流させて、該スラグから亜鉛及び鉛を、３％までのレベルまで十分に取り除く。該スラグにおける少量の亜鉛でさえ、適しているが、しかし著しく増加された操作費用と関連する。要求される炭の量は、非常に多い。２つの炉のための要求は、著しく投資費用をさらに増加する。 The upper blow molding submerged in a lance furnace (Issmelt (R) or Ausmelt (R)) can also be used to treat zinc containing waste. The dried residue, charcoal and flux are fed into the smelting furnace of the first submerged lance furnace to remove zinc and lead parts from the slag and to remove sulfur. The molten slag continuously overflows into the second submerged lance furnace's fuming furnace to sufficiently remove zinc and lead from the slag to a level of up to 3%. Even small amounts of zinc in the slag are suitable, but are associated with significantly increased operating costs. The amount of charcoal required is very large. The requirement for two furnaces significantly increases the investment costs.
電力を使用する種々の方法は、残留物を含有する亜鉛を加工するためにも開発されている。スラグ抵抗炉において、その供給物は、上部から溶融浴中で注入される。該スラグ自体が、電気伝導によって加熱される。電磁気撹拌は、該浴を均一に保つ。還元剤の添加は、該スラグから亜鉛ヒューミングを生じ、その際その亜鉛は、凝縮後にその金属の形で回収される。 Various methods using electric power have also been developed for processing zinc containing residues. In a slag resistance furnace, the feed is injected into the molten bath from the top. The slag itself is heated by electrical conduction. Electromagnetic stirring keeps the bath uniform. The addition of a reducing agent results in zinc fuming from the slag, where the zinc is recovered in the form of its metal after condensation.
残留物を含有する亜鉛を処理する最後の方法は、ＤＣアーク炉を使用することであり、その際その熱は、前記浴に電極から電気アークを移動することによって生じさせる。Ｅｎｖｉｒｏｐｌａｓ（登録商標）法は、例えば、鉛溶鉱炉スラグ、ＥＡＦダスト、及び中性浸出残留物を処理する。還元剤、例えば原料炭、木炭又は他の炭質材料は、湿分が低く、かつ揮発物は、亜鉛及び鉛を還元並びに揮発するために再度使用される。約１４５０℃の高いタッピング温度は、該スラグにおける低い残留亜鉛濃度を確実にするが、しかし耐火物ライニングが急速に劣化することももたらす。 The last method of treating the zinc containing residue is to use a DC arc furnace, where the heat is generated by transferring an electric arc from the electrode to the bath. The Enviroplas® process treats, for example, lead blast furnace slag, EAF dust, and neutral leaching residues. Reducing agents, such as raw coal, charcoal or other carbonaceous material, are low in moisture and volatiles are used again to reduce and volatilize zinc and lead. A high tapping temperature of about 1450 ° C. ensures a low residual zinc concentration in the slag, but also leads to a rapid deterioration of the refractory lining.
前記の方法は、全て、１つ以上の以下の欠点をこうむる：
− 特定の供給物準備、例えば乾燥、研摩、ハロゲン除去、ブリケッティングの必要性、
− 比較的低い温度で操作される場合の低いヒューミング率、
− 高温で操作される場合の速い耐火物ライニングの劣化、
− 低いマットの程度、
− 複数の単位操作の必要性、
− 高いエネルギー消費、
− 多量のＣＯ2の発生、
− 高い投資及び／又は操作費用。
All of the above methods suffer from one or more of the following drawbacks:
-The need for specific feed preparations, such as drying, polishing, halogen removal, briquetting,
-Low huming rate when operated at relatively low temperatures,
-Fast refractory lining degradation when operated at high temperatures,
-Low mat degree,
-The need for multiple unit operations,
-High energy consumption,
- of a large amount of CO 2 generation,
-High investment and / or operating costs.
大部分の前記の欠点を克服する新しい方法が提案される。その方法は、液中プラズマ火炎の酸化と、固体還元剤のスラグの上部への添加とを組合せた、単工程のみを要求する。 A new method is proposed that overcomes most of the above disadvantages. The method requires only a single step that combines the oxidation of a submerged plasma flame and the addition of a solid reducing agent to the top of the slag.
Ｚｎがヒューミングされ、Ｆｅがスラグにされ、かつＳがＳＯ2に酸化される、Ｚｎ、Ｆｅ及びＳを含有する産業Ｚｎ残留物からの金属の回収のための本発明の方法は、Ｚｎのヒューミング、Ｆｅのスラグ形成、及びＳの酸化が、酸化性ガス混合物を生じる少なくとも１つの液中プラズマトーチを含有する炉中で前記残留物を溶錬することによって、及び固体還元剤をその溶融物に供給することによって、単工程法で実施されることを特徴とする。 The method of the present invention for recovery of metals from industrial Zn residues containing Zn, Fe and S, wherein Zn is fumed, Fe is slag, and S is oxidized to SO 2 Humming, Fe slag formation, and S oxidation, by melting the residue in a furnace containing at least one submerged plasma torch resulting in an oxidizing gas mixture, and melting the solid reducing agent It is characterized in that it is carried out in a single-step method by supplying it to an object.
少なくとも１つの液中プラズマトーチは、有利には、酸化性ガス混合物が、スラグ相中へ注入されるために、無移送タイプである。 The at least one submerged plasma torch is advantageously of the non-transfer type because the oxidizing gas mixture is injected into the slag phase.
酸化性ガス混合物における遊離酸素量を、少なくとも大部分のＳ及びＦｅの酸化のための化学量論的要求に、及び固形還元剤量を、少なくとも大部分のＺｎの還元のための化学量論的要求に適応するために有用である。 The amount of free oxygen in the oxidizing gas mixture is at least stoichiometrically required for the oxidation of most S and Fe, and the amount of solid reducing agent is at least stoichiometrically for the reduction of most Zn. Useful to adapt to requirements.
好ましい一実施態様において、前記の酸化性ガス混合物は、空気とガス状炭化水素との混合物を前記のプラズマトーチに供給することによって生じる。 In a preferred embodiment, the oxidizing gas mixture is produced by supplying a mixture of air and gaseous hydrocarbons to the plasma torch.
前記の方法は、Ｉｎ及び／又はＧｅを含有する産業Ｚｎ残留物を処理するために特に有用であり、それら金属のヒューミングによって揮発（ｖａｌｏｒｉｚａｔｉｏｎ）をもたらす。それは、特に針鉄鉱を処理するためにも適応される。 The method described above is particularly useful for treating industrial Zn residues containing In and / or Ge, resulting in volatilization by the fuming of these metals. It is especially adapted for treating goethite.
該方法は、Ｃｕが、産業Ｚｎ残留物で及び／又は固体還元剤で存在する場合に最も有用である。当業者に公知の方法で酸化性ガス混合物を適用することは、有利には、４０質量％より多い、又はより有利には５０質量％より多いＣｕを含むＣｕマット相の形成を導く。 The method is most useful when Cu is present in an industrial Zn residue and / or in a solid reducing agent. Applying the oxidizing gas mixture in a manner known to the person skilled in the art advantageously leads to the formation of a Cu mat phase comprising more than 40% by weight or more advantageously more than 50% by weight of Cu.
液中プラズマ技術を使用する方法は、既にＥＰ１６７０９６０号において挙げられており、参照をもって本明細書に組み込まれたものとする。 The method of using the in-liquid plasma technique has already been mentioned in EP 1670960 and is incorporated herein by reference.
液中プラズマ反応器において、１つ以上の無移送ＤＣプラズマトーチを、高輝度熱源として使用する。始動中に、該反応器を、それらが浸漬されるまで、プラズマ羽口によって溶融される、スラグで満たす。その方法の間、該プラズマを、スラグ層中で連続して生じさせる。プラズマガス注入によって生じた気泡は、より高い乱流槽をもたらす。その供給物は、上部から入れられ、かつ全く準備を必要としない。湿った供給材料は、有利には許容できる。さらに炉は、凍結型のライニングのコンセプトを使用する。炉壁は、水冷され、かつ飛沫スラグは、熱の損失を低減する分離外被をもたらす該壁上で凝固する。該スラグ組成物は、該スラグの液相線温度が該スラグの過度の過熱を防ぐための高さであるべきであることを意味する、その加工を高温で、密な凍結型のライニングで実施することができる方法で選択される。その高い操作温度は、耐火れんがの劣化の問題なしに速いヒューミング速度を可能にする。 In a submerged plasma reactor, one or more no-transfer DC plasma torches are used as a high intensity heat source. During startup, the reactors are filled with slag that is melted by the plasma tuyere until they are immersed. During the process, the plasma is generated continuously in the slag layer. Bubbles generated by plasma gas injection result in a higher turbulence tank. The feed is entered from the top and requires no preparation. A wet feed is advantageously acceptable. In addition, the furnace uses the concept of a freezing lining. The furnace wall is water cooled and the splash slag solidifies on the wall resulting in a separation envelope that reduces heat loss. The slag composition is processed at high temperature and in a dense freeze-type lining, meaning that the liquidus temperature of the slag should be high to prevent excessive overheating of the slag Selected in a way that can be. Its high operating temperature allows a fast fume speed without the problem of refractory brick degradation.
固体還元剤、例えば炭、コークス、電子スクラップ、もしくは自動車の破砕機の残留物は、供給物に添加され、又は還元剤、例えば天然ガス、ＬＰＧＴもしくは油は、羽口を介して供給される。全ての前記の他の方法に関する限りでは、還元環境のみが、亜鉛ヒューミングの高い収率を得るために使用されうることが、一般に認められ、及びさらに熱力学によって必然的に決められる。しかしながら、公知の方法は、Ｆｅ及び硫黄の過剰量を含有する、劣った質のＣｕマットをもたらす。 Solid reductant, such as charcoal, coke, electronic scrap, or automobile crusher residue is added to the feed, or reductant, such as natural gas, LPGT or oil, is fed through the tuyere. As far as all the other methods are concerned, it is generally accepted and further inevitably determined by thermodynamics that only a reducing environment can be used to obtain a high yield of zinc fuming. However, known methods result in poor quality Cu mats containing excess Fe and sulfur.
現在、液中プラズマトーチを介して供給された酸化性ガスが、亜鉛ヒューミング率をわずかに作用することが判明している。予期せず、通常還元雰囲気を要求する高いヒューミング率に影響することなく、殆どの硫黄を除去し、かつ従って高いマットの程度を生じることが、十分に酸化しているプラズマガスの使用を可能にする。これは熱力学的予想に矛盾しているが、この操作の方法が、固体還元剤の近くでは還元しているが、しかし気泡の近くでは酸化している、種々の局所的な熱力学的領域をもたらすとみなされる。それらの明らかに区別される領域は、１つの単炉中で共存しうる。結果として、該方法は、高いヒューミング率を達成し、高い程度のマット及び綺麗な廃棄することができるスラグを生じることに成功する。その発見は、その工程の操作における追加の自由度を表す：プラズマ火炎における過剰酸素量は、自由に調整されることができ、目的の相の組成物に達するために要求される必須の過剰酸素量のみを提供する。これは、空気の混合物及び還元剤、例えばメタン又はあらゆる他の炭化水素化合物の制限量を使用することによって実現されうる。 Currently, it has been found that the oxidizing gas supplied via the submerged plasma torch has a slight effect on the zinc fuming rate. Unexpectedly, removing most sulfur without affecting the high fuming rate that normally requires a reducing atmosphere, and thus producing a high matte level, allows the use of a fully oxidized plasma gas To. This is inconsistent with thermodynamic predictions, but the various methods of local thermodynamics where the method of operation is reducing near the solid reducing agent but oxidizing near the bubbles. Is considered to bring Those distinct areas can coexist in a single furnace. As a result, the method achieves a high fuming rate and succeeds in producing a high degree of mat and clean slag that can be discarded. The discovery represents an additional degree of freedom in the operation of the process: the amount of excess oxygen in the plasma flame can be adjusted freely and the required excess oxygen required to reach the desired phase composition Provide quantity only. This can be achieved by using a mixture of air and a reducing agent such as methane or any other hydrocarbon compound.
典型的に、所望の相組成物は、供給材料の組成物に依存する。多量の銅が供給物中に存在する場合に、高い程度のマットが、通常所望される。従って、マットを過酸化し、その結果転化しないように処理しなければならない。メタンの前記のプラズマガスへの添加は、それらの条件において、遊離酸素の量を制限するために有用である。前記供給物が、例えば金属鉄を含有する場合に、前記の方法で金属鉄を酸化することが好ましくてよく、その際要求される酸素は、その時プラズマ火炎によって主に提供される。メタンは、この場合添加されない。 Typically, the desired phase composition will depend on the composition of the feedstock. A high degree of mat is usually desired when large amounts of copper are present in the feed. Therefore, the mat must be treated so as to be oxidized and not converted as a result. Addition of methane to the plasma gas is useful in these conditions to limit the amount of free oxygen. If the feed contains, for example, metallic iron, it may be preferred to oxidize metallic iron in the manner described above, the oxygen required being then provided mainly by the plasma flame. Methane is not added in this case.
この技術で針鉄鉱又は他の亜鉛残留物を加工することからの他の有益な結果は、さらにＺｎ、Ｉｎ及びＧｅのような元素をヒューミングすることである。それらは、後の加工工程において揮発されうる。典型的に亜鉛残留物において少量で存在する貴金属は、マット及びヒューミング中で回収されてよい。他の生成物、例えばパラゲータイト、ジャロサイト及び抽出残留物は、好適な方法であってもよい。 Another beneficial result from processing goethite or other zinc residues with this technique is to further fuming elements such as Zn, In and Ge. They can be volatilized in later processing steps. Precious metals that are typically present in small amounts in the zinc residue may be recovered in mats and fuming. Other products, such as paragite, jarosite and extraction residue may be suitable methods.
該方法を、次の実施例でさらに説明する。 The method is further illustrated in the following example.
比較例
出発溶融物を、鉛溶鉱炉（ＬＢＦ）スラグと以前の試験から再利用されたスラグとの混合物を溶融することによって製造する。そして針鉄鉱を、固体還元剤としてプラスチックスクラップと共にその浴へ供給する。中性プラズマガスを使用し、渦巻きガスとして空気１００ｍ3／ｈ、メタン１０ｍ3／ｈ、及び窒素１６ｍ3／ｈを提供する。その方法を、上記のように実施する。第１表は、供給物及び生産材料の組成物並びに量を示す。その試験は、製造されたスラグにおいて非常に低い亜鉛濃度をもたらしたが、マットの程度は低かった。
Comparative Example A starting melt is produced by melting a mixture of lead blast furnace (LBF) slag and slag recycled from previous tests. The goethite is then fed to the bath along with plastic scrap as a solid reducing agent. Use neutral plasma gas is provided as a vortex gas air 100 m 3 / h, methane 10 m 3 / h, and the nitrogen 16m 3 / h. The method is performed as described above. Table 1 shows the composition and amount of feed and production materials. The test resulted in a very low zinc concentration in the produced slag, but the degree of matte was low.
本発明による実施例
同様の試験を、今度は酸化プラズマガスで実施し、渦巻きガスとして空気１００ｍ3／ｈ、及び窒素１６ｍ3／ｈを提供した。メタンは注入されなかった。第２表は、供給物及び生産材料の組成物並びに量を示す。この場合において、得られたスラグは、より多くのＺｎをわずかに含有するのみであるが、一方で非常に高いマットの程度を達成することが明らかである。これは、さらに、供給物の量と比較して、より低い製造されたマットの量で示される。
A test similar to the example according to the invention was then carried out with oxidizing plasma gas, providing 100 m 3 / h of air and 16 m 3 / h of nitrogen as the swirl gas. Methane was not injected. Table 2 shows the composition and amount of feed and production materials. In this case, it is clear that the resulting slag contains only a little more Zn, while achieving a very high matte degree. This is further indicated by the lower amount of mat produced compared to the amount of feed.
そのヒューミングにおけるＩｎの富化の説明も、明らかにする。第２表は、Ｉｎ富化された煙塵をもたらす、インジウムのヒューミングを示す。ヒューミングドＩｎは、他の加工工程において経済的に回収されうる。同様の揮発を、場合によりＧｅのために実施する。Ａｇと共に他の貴金属を、マット中で、及び煙塵中で回収する。それは、公知の方法を使用して揮発されうる。 The explanation of In enrichment in the humming will also be clarified. Table 2 shows the indium fuming resulting in In-enriched dust. Fumed In can be recovered economically in other processing steps. Similar volatilization is optionally performed for Ge. Other precious metals with Ag are recovered in the mat and in the dust. It can be volatilized using known methods.
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| US60/856,821 | 2006-11-06 | ||
| PCT/EP2007/009023 WO2008052661A1 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
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| JP2015535883A (en) * | 2012-09-21 | 2015-12-17 | ヴァル’イース・リサイクリング・ソリューションズ・アクチボラグ | Plasma induced transpiration |
| JP2017526820A (en) * | 2014-08-14 | 2017-09-14 | ユミコア | Process for melting lithium ion batteries |
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| CN101906542B (en) * | 2010-08-11 | 2011-11-02 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
| ITRM20130205A1 (en) * | 2013-04-05 | 2014-10-06 | Ecotec Gestione Impianti S R L | PROCEDURE FOR THE EXTRACTION OF SULFUR AND METALS, IN THE FORM OF OXIDES, USABLE IN THE WAELTZ PROCESS, BY SLUDGE CONTAINING COMPOUNDS OF SULFUR AND OF THESE METALS |
| CN104232944B (en) * | 2014-09-05 | 2015-06-24 | 韶关凯鸿纳米材料有限公司 | Process for comprehensively recycling indium from ammonia leaching residues and co-producing zinc oxide |
| PT3277852T (en) | 2015-04-03 | 2021-06-21 | Metallo Belgium | Improved slag from non-ferrous metal production |
| ITUB20154943A1 (en) * | 2015-10-28 | 2017-04-28 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
| ES2887206T3 (en) * | 2015-10-14 | 2021-12-22 | Ecotec Gestione Impianti S R L | Method for producing a concentrate containing metals, rare metals and rare earth metals from waste generated in the zinc production chain and concentrate obtained by said method |
| ITUB20154661A1 (en) * | 2015-10-14 | 2017-04-14 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
| BE1027793B1 (en) | 2019-11-22 | 2021-06-23 | Metallo Belgium | Improved Fumigation Furnace with Plasma Induction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS57158336A (en) * | 1981-03-10 | 1982-09-30 | Skf Steel Eng Ab | Heavy metal selective reduction |
| JPH04507265A (en) * | 1989-08-24 | 1992-12-17 | オースメルト ピーティーワイ．リミテッド | Smelting of metallurgical waste containing iron compounds and toxic elements |
| WO2005031014A1 (en) * | 2003-09-29 | 2005-04-07 | Umicore | Process and apparatus for recovery of non-ferrous metals from zinc residues |
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| JPS57158336A (en) * | 1981-03-10 | 1982-09-30 | Skf Steel Eng Ab | Heavy metal selective reduction |
| JPH04507265A (en) * | 1989-08-24 | 1992-12-17 | オースメルト ピーティーワイ．リミテッド | Smelting of metallurgical waste containing iron compounds and toxic elements |
| WO2005031014A1 (en) * | 2003-09-29 | 2005-04-07 | Umicore | Process and apparatus for recovery of non-ferrous metals from zinc residues |
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| JP2015535883A (en) * | 2012-09-21 | 2015-12-17 | ヴァル’イース・リサイクリング・ソリューションズ・アクチボラグ | Plasma induced transpiration |
| JP2017526820A (en) * | 2014-08-14 | 2017-09-14 | ユミコア | Process for melting lithium ion batteries |
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