JP2004285473A - Method for recovering valuable metals from waste containing V, Mo and Ni - Google Patents
Method for recovering valuable metals from waste containing V, Mo and Ni Download PDFInfo
- Publication number
- JP2004285473A JP2004285473A JP2003409513A JP2003409513A JP2004285473A JP 2004285473 A JP2004285473 A JP 2004285473A JP 2003409513 A JP2003409513 A JP 2003409513A JP 2003409513 A JP2003409513 A JP 2003409513A JP 2004285473 A JP2004285473 A JP 2004285473A
- Authority
- JP
- Japan
- Prior art keywords
- slag
- waste
- based alloy
- valuable metals
- alloy
- 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
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 150000002739 metals Chemical class 0.000 title claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 59
- 239000000956 alloy Substances 0.000 claims abstract description 59
- 229910017318 Mo—Ni Inorganic materials 0.000 claims abstract description 50
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 230000004907 flux Effects 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 229910000756 V alloy Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 238000006722 reduction reaction Methods 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 239000002994 raw material Substances 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 16
- 230000023556 desulfurization Effects 0.000 description 16
- 239000010802 sludge Substances 0.000 description 15
- 238000009847 ladle furnace Methods 0.000 description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 9
- 235000011941 Tilia x europaea Nutrition 0.000 description 9
- 239000004571 lime Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010079 rubber tapping Methods 0.000 description 4
- 239000004484 Briquette Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 and the like Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Images
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
- Manufacture And Refinement Of Metals (AREA)
Abstract
【課題】 Ｖ、Ｍｏ及びＮｉ含有廃棄物から、Ｆｅ−Ｍｏ−Ｎｉ系合金及びＦｅ−Ｖ系合金を安定して歩留りよく回収できる方法を提供する。
【解決手段】 本発明によるＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法は、Ｖ、Ｍｏ及びＮｉ含有廃棄物を乾燥する工程と、前記Ｖ、Ｍｏ及びＮｉ含有廃棄、還元剤としてのＦｅ、及びフラックスを加熱炉に装入し、これらを加熱還元することで、Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程と、前記Ｖ含有スラグにＡｌ還元剤を投入して、Ｆｅ−Ｖ系合金及びＣａＯ−Ａｌ2Ｏ3スラグを生成させる工程とを備える。
【選択図】 図２PROBLEM TO BE SOLVED: To provide a method capable of stably recovering a Fe-Mo-Ni-based alloy and an Fe-V-based alloy from V, Mo and Ni-containing wastes with good yield.
SOLUTION: The method for recovering valuable metals from V, Mo and Ni-containing wastes according to the present invention comprises a step of drying V, Mo and Ni-containing wastes, and a step of drying the V, Mo and Ni-containing wastes as a reducing agent. And a step of generating a V-containing slag and an Fe-Mo-Ni-based alloy by heating and reducing the Fe and flux into a heating furnace, and charging an Al reducing agent to the V-containing slag. , and a step of generating a Fe-V alloys and CaO-Al 2 O 3 slag.
[Selection] Fig. 2
Description
本発明は、使用済脱硫触媒、ボイラー灰、ボイラースラッジ、ニッケル系スラッジ、メタバナジン酸アンモニウム等の廃棄物から有価金属を回収する方法に関する。 The present invention relates to a method for recovering valuable metals from waste such as a used desulfurization catalyst, boiler ash, boiler sludge, nickel-based sludge, and ammonium metavanadate.
例えば発電所のように石油系燃料を燃料とするボイラーにおいては、ボイラーの底に沈着するボイラースラッジ、集塵装置に捕捉されるボイラー灰の中に、Ｎｉ、Ｖの重金属が酸化物の形態で凝縮されている。ボイラー灰を湿式アルカリ処理して得られるメタバナジン酸アンモニウムにも、Ｖの重金属が酸化物の形態で凝縮されている。 For example, in a boiler that uses petroleum-based fuel as a power plant, Ni and V heavy metals are in the form of oxides in boiler sludge deposited on the bottom of the boiler and boiler ash captured by a dust collector. Condensed. Ammonium metavanadate obtained by subjecting boiler ash to wet alkali treatment also condenses heavy metals of V in the form of oxides.
石油精製、ガス処理工業等の分野においては、精製過程で脱硫触媒が設けられている。この使用済脱硫触媒にも、Ｎｉ、Ｍｏ、Ｖの重金属が酸化物の形態で凝縮されている。これらＮｉ、Ｍｏ、Ｖの酸化物をメタルの形態で回収することが、廃棄物の有効活用として望まれている。 In the fields of petroleum refining, gas processing industry and the like, a desulfurization catalyst is provided in the refining process. Also in this used desulfurization catalyst, heavy metals of Ni, Mo and V are condensed in the form of oxides. It is desired to recover these oxides of Ni, Mo, and V in the form of metal as effective use of waste.
こうした回収技術の一つに、Ｖ含有廃棄物を４５０〜９５０℃に加熱して廃棄物中のＳ分、Ｎ分及びＣ分を除去した後、この廃棄物を鉄源及び還元剤と共に混合、粉砕してから粒状に成形し、次いで、１１５０〜１３５０℃に過熱して原料中のＦｅ分、Ｎｉ分、Ｍｏ分を固相還元した後、電気炉に装入し過熱してＦｅ、Ｎｉ、Ｍｏを主成分とするメタルとＶリッチなフラックスとを生成させ、このＦｅ、Ｎｉ、Ｍｏを主成分とするメタルには脱Ｐ処理を行なって低Ｐ合金を得る一方、Ｖリッチなフラックスには強攪拌機能を有する容器にて還元材を投入するとともに攪拌を行ってフラックス中のＶを還元しＦｅ−Ｖ系合金を得る方法が開示されている（特許文献１、請求項１参照）。
One of such recovery techniques is to heat V-containing waste to 450 to 950 ° C. to remove S, N, and C in the waste, and then mix the waste with an iron source and a reducing agent. After pulverizing and forming into granules, the mixture is heated to 1150 to 1350 ° C. to solid-phase reduce Fe, Ni, and Mo in the raw material, and then charged into an electric furnace and heated to obtain Fe, Ni, A metal containing Mo as a main component and a V-rich flux are generated. The metal containing Fe, Ni, and Mo as a main component is subjected to a de-P treatment to obtain a low-P alloy, while a V-rich flux is obtained. A method is disclosed in which a reducing agent is charged into a container having a strong stirring function and stirring is performed to reduce V in the flux to obtain an Fe-V-based alloy (see
他の回収技術として、Ｖ、Ｍｏ、Ｃｏ及びＮｉ含有廃棄物を焙焼する第１工程と、Ｍｏ、Ｎｉ及びＣｏ酸化物を金属にまで還元するのに必要な化学的当量の５０〜１２０％相当の金属Ｓｉ及び／又は金属Ａｌを添加し、加熱還元して溶解することにより、Ｍｏ−Ｎｉ系合金又はＭｏ−Ｃｏ系合金又はＭｏ−Ｎｉ−Ｃｏ系合金とＣａＯ−Ａｌ2Ｏ3系スラグとを分離してそれぞれを回収する第２工程と、前記ＣａＯ−Ａｌ2Ｏ3系スラグに対し、このスラグ中に含まれるＶの酸化物を金属にまで還元するのに必要な化学的当量以上の金属Ｓｉ及び／又は金属Ａｌを添加し、加熱還元して溶解することにより、Ｖ−Ｓｉ系合金又はＶ−Ａｌ系合金とＣａＯ−Ａｌ2Ｏ3系スラグとを分離してそれぞれを回収する第３工程とを備える方法が開示されている（特許文献２、請求項１参照）。
Other recovery techniques include a first step of roasting V, Mo, Co and Ni-containing waste and 50-120% of the chemical equivalent required to reduce Mo, Ni and Co oxides to metal. was added equivalent of the metal Si and / or a metal Al, by dissolving heat reduced to, Mo-Ni alloy or Mo-Co alloy or Mo-Ni-Co alloy and CaO-Al 2 O 3 slag And a second step of recovering each of the slags, and a chemical equivalent or more to the CaO—Al 2 O 3 -based slag which is necessary to reduce oxides of V contained in the slag to metal. added a metallic Si and / or a metal Al, by dissolving heat reduced to, to recover each separating the V-Si alloy or V-Al alloys and CaO-Al 2 O 3 slag And a third step is disclosed. That (see
しかしながら特許文献１に記載の回収方法にあっては、原料中のＦｅ、Ｎｉ、及びＭｏ成分を固相還元する還元剤として、微粉炭又はコークスを用いている（特許文献１、段落００２２参照）。このため、生成されるＦｅ、Ｎｉ、Ｍｏを主成分とするメタル中にカーボンが残ってしまう。カーボンはメタル中のＦｅ−Ｍｏ、Ｆｅ−Ｎｉ等に結合し易いので、後の工程でカーボンを除去するのが困難になる。また固相還元する際にＭｏ成分がキルン内で昇華してしまい、Ｍｏ成分の回収歩留りが悪化してしまうという問題もある。さらに工程が長く設備費が増大してしまうという問題もある。
However, in the recovery method described in
特許文献２に記載の回収方法にあっては、第１工程において、廃棄物をペレットにしないで粉のまま焙焼する（特許文献２、段落００１０参照）。このため廃棄物がキルン内で焼結してしまい、流れなくなるという問題がある。
In the recovery method described in
また第２工程において、廃棄物を粉のまま溶解するので、炉況が悪化し、例えば溶解炉内で棚吊りや吹き上げが生じてしまう。炉況の悪化は電力原単位の悪化や操業の不安定を招く。さらに第２工程において、還元剤として金属Ｓｉ及び／又は金属Ａｌを用いているので、Ｖ成分とＭｏ、Ｎｉ成分との分離が困難になるという問題も生じる。すなわち金属Ｓｉ及び／又は金属Ａｌの量を少なくして弱還元したときには、Ｍｏ及びＮｉ成分の歩留りが悪くなり、Ｖ含有スラグにＭｏ及びＮｉ成分が入ってしまう。一方強還元したときには、還元されたＶ成分がＭｏ−Ｎｉ系合金に入ってしまうのみならず、Ｓｉ及び／又はＡｌ還元剤がＭｏ−Ｎｉ系合金に入ってしまう。特に還元剤としてＡｌを用いると、Ａｌが大気中の酸素と反応してしまい、酸化ロスも大きくなる。 Further, in the second step, the waste is melted as powder, so that the furnace condition is deteriorated, and for example, shelves are suspended or blown up in the melting furnace. Deteriorating reactor conditions lead to a deterioration in power consumption and operation instability. Further, in the second step, since metal Si and / or metal Al is used as the reducing agent, there is a problem that it becomes difficult to separate the V component from the Mo and Ni components. That is, when the amount of the metal Si and / or the metal Al is reduced and weakly reduced, the yield of the Mo and Ni components deteriorates, and the Mo and Ni components enter the V-containing slag. On the other hand, when strong reduction is performed, not only the reduced V component enters the Mo—Ni-based alloy, but also the Si and / or Al reducing agent enters the Mo—Ni-based alloy. In particular, when Al is used as the reducing agent, Al reacts with oxygen in the atmosphere, and the oxidation loss increases.
本発明は上記事情に鑑みなされたもので、その目的とするところは、Ｖ、Ｍｏ及びＮｉ含有廃棄物から、Ｆｅ−Ｍｏ−Ｎｉ系合金及びＦｅ−Ｖ系合金を安定して歩留りよく回収できる方法を提供することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to stably recover Fe-Mo-Ni-based alloys and Fe-V-based alloys from V, Mo, and Ni-containing wastes with good yield. It is to provide a method.
本発明者は、溶融還元温度１４００℃〜１８００℃におけるＮｉ、Ｍｏ、Ｖの酸素親和力に着目した。そして図１（酸化物の標準生成自由エネルギのグラフ）に示されるように、ＦｅがＮｉ及びＭｏよりも酸素親和力が強く、Ｖよりも弱いことに着目し、還元剤としてＦｅを用いればＶ含有スラグとＦｅ−Ｍｏ−Ｎｉ系合金とを歩留まり良く分離できることを知見した。 The present inventors focused on the oxygen affinity of Ni, Mo, and V at a smelting reduction temperature of 1400 ° C to 1800 ° C. As shown in FIG. 1 (graph of standard free energy of formation of oxide), attention is paid to the fact that Fe has a higher oxygen affinity than Ni and Mo and is weaker than V. It has been found that the slag and the Fe—Mo—Ni alloy can be separated with good yield.
すなわち本発明は、Ｖ、Ｍｏ及びＮｉ含有廃棄物をＦｅで還元して、Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程と、前記Ｖ含有スラグに還元剤を投入してＦｅ−Ｖ系合金を生成させる工程と、を備えることを特徴とする有価金属の回収方法により、上述した課題を解決する。 That is, the present invention provides a step of reducing V, Mo and Ni-containing waste with Fe to produce a V-containing slag and an Fe-Mo-Ni-based alloy, and adding a reducing agent to the V-containing slag to reduce the Fe- The above object is attained by a method for recovering valuable metals, which comprises a step of generating a V-based alloy.
また本発明は、Ｖ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法であって、以下の工程を備える：Ｖ、Ｍｏ及びＮｉ含有廃棄物を焙焼する工程；前記Ｖ、Ｍｏ及びＮｉ含有廃棄物、還元剤としてのＦｅ、及びフラックスを加熱炉に装入し、これらを加熱還元することで、Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程；前記Ｖ含有スラグにＡｌ還元剤を投入して、Ｆｅ−Ｖ系合金及びＣａＯ−Ａｌ2Ｏ3スラグを生成させる工程、としても構成することができる。 The present invention also provides a method for recovering valuable metals from V, Mo and Ni-containing waste, comprising the following steps: a step of roasting V, Mo and Ni-containing waste; A step of charging V-containing slag and an Fe-Mo-Ni-based alloy by charging the waste containing Fe, Fe as a reducing agent, and flux into a heating furnace and reducing them by heating; and the reducing agent were charged, can also be configured as a step, to produce a Fe-V alloys and CaO-Al 2 O 3 slag.
前記Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程において、前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を前記Ｆｅで還元した後、前記Ｆｅで還元することにより生じたＦｅ酸化物を、Ａｌ、Ｓｉ、及びＣの少なくとも一つで還元してもよい。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy, the V, Mo and Ni-containing waste is reduced with the Fe, and then the Fe oxide generated by the reduction with the Fe is converted into an Al oxide. , Si, and C may be reduced.
この発明によれば、還元反応により生じたＦｅ酸化物をＦｅ−Ｍｏ−Ｎｉ系合金の鉄源として用いることができる。またＶ含有スラグ中のＦｅ分を調整することができ、ひいては最終的に得られるＦｅ−Ｖ系合金の規格に合わせてＦｅ分を調整することができる。 According to the present invention, the Fe oxide generated by the reduction reaction can be used as the iron source of the Fe—Mo—Ni alloy. Further, the Fe content in the V-containing slag can be adjusted, and thus the Fe content can be adjusted according to the standard of the finally obtained Fe-V alloy.
前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を乾燥する工程において、前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を乾燥した後、粉砕し、団鉱に成形し、これを焙焼することが望ましい。 In the step of drying the V, Mo, and Ni-containing waste, it is preferable that the V, Mo, and Ni-containing waste be dried, crushed, formed into briquettes, and roasted.
この発明によれば、Ｖ、Ｍｏ及びＮｉ含有廃棄物を粉のまま加熱炉に装入することがないので、棚吊りや吹き上げが生ずることがなく、したがって安定した操業をすることがで
きる。
According to the present invention, waste containing V, Mo and Ni is not charged into the heating furnace as powder, so that shelving or blowing up does not occur, and thus stable operation can be performed.
また、前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を焙焼する工程において、前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を焙焼した後、団鉱に成形してもよい。 In the step of roasting the waste containing V, Mo and Ni, the waste containing V, Mo and Ni may be roasted and then formed into briquettes.
前記Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程において、あらかじめ鉄浴を生成しておき、該鉄浴に前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を装入して溶融還元反応を行うことが望ましい。 In the step of generating the V-containing slag and the Fe-Mo-Ni-based alloy, an iron bath is generated in advance, and the V, Mo, and Ni-containing waste is charged into the iron bath to perform a smelting reduction reaction. It is desirable.
この発明によれば、還元反応の反応効率を向上させることができ、しかも熱効率も向上させることができる。また加熱炉の連続した操業も可能になる。 According to the present invention, the reaction efficiency of the reduction reaction can be improved, and the thermal efficiency can be improved. In addition, continuous operation of the heating furnace becomes possible.
前記Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程において、前記Ｆｅ−Ｍｏ−Ｎｉ系合金を前記Ｖ含有スラグと分離した後、前記Ｆｅ−Ｍｏ−Ｎｉ系合金の脱Ｓ，脱Ｐ，脱Ｃを行うことが望ましい。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy, after the Fe-Mo-Ni-based alloy is separated from the V-containing slag, the removal of S and P from the Fe-Mo-Ni-based alloy is performed. , Desirably.
この発明によれば、Ｆｅ−Ｍｏ−Ｎｉ系合金の規格に合わせてＳ分，Ｐ分及びＣ分の不純物を除去することができる。また、団鉱に成形したＶ、Ｍｏ及びＮｉ含有廃棄物を焙焼する際に廃棄物中に含まれるＳ分をＳＯｘにし、Ｃ分をＣＯ2にして排出するが、Ｆｅ−
Ｍｏ−Ｎｉ系合金をＶ含有スラグと分離した後に脱Ｓ、脱Ｃすることで、焙焼する際の負担を軽減することができる。
According to the present invention, impurities for S, P, and C can be removed according to the standard of the Fe—Mo—Ni alloy. Also, V molded into briquettes, the S component contained in waste when roasting Mo and Ni-containing waste to SOx, but discharges to the C content in the CO 2, Fe-
By removing S and C after separating the Mo-Ni-based alloy from the V-containing slag, the burden of roasting can be reduced.
前記Ｆｅ−Ｍｏ−Ｎｉ系合金の脱Ｓ，脱Ｐ，脱Ｃを行うのに使用される加熱用容器と、前記Ｖ含有スラグに還元剤を投入してＦｅ−Ｖ系合金を生成させる工程において使用される加熱用容器とが、共用されることが望ましい。 In the heating vessel used to remove S, P and C from the Fe-Mo-Ni alloy, and in the step of adding a reducing agent to the V-containing slag to generate an Fe-V alloy. It is desirable that the heating container used be shared.
この発明によれば、最少の設備で回収方法を実施することができる。 According to the present invention, the collection method can be performed with the minimum equipment.
前記Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程において、前記Ｆｅ−Ｍｏ−Ｎｉ系合金が一回出湯される間に、前記Ｖ含有スラグが複数回出湯されるのが望ましい。 In the step of generating the V-containing slag and the Fe-Mo-Ni-based alloy, it is preferable that the V-containing slag is discharged a plurality of times while the Fe-Mo-Ni-based alloy is discharged once.
生成されるＦｅ−Ｍｏ−Ｎｉ系合金の量はＶ含有スラグに比較して非常に少ない。この発明によれば、Ｖ含有スラグを頻繁に出湯することにより、熱効率が向上する。またＶ含有スラグを出湯するバッチ毎にＦｅ−Ｍｏ−Ｎｉ系合金を出湯する場合に比較して、生産性も向上する。 The amount of the produced Fe-Mo-Ni-based alloy is much smaller than that of the V-containing slag. According to the present invention, the thermal efficiency is improved by frequently tapping the V-containing slag. In addition, productivity is also improved as compared with the case where the Fe-Mo-Ni-based alloy is tapped for each batch in which the V-containing slag is tapped.
以上説明したように本発明によれば、還元剤としてＦｅを用いるので、Ｖ、Ｍｏ及びＮｉ含有廃棄物から、Ｆｅ−Ｍｏ−Ｎｉ系合金及びＦｅ−Ｖ系合金を安定して歩留りよく回収できる。 As described above, according to the present invention, since Fe is used as the reducing agent, Fe-Mo-Ni-based alloys and Fe-V-based alloys can be recovered from V, Mo, and Ni-containing waste stably with good yield. .
以下、本発明の一実施形態について説明する。本実施形態では、Ｖ、Ｍｏ及びＮｉを含有する廃棄物を原料とする。具体的には使用済脱硫触媒（直接脱硫触媒、間接脱硫触媒）、ボイラー灰、ボイラースラッジ、ニッケル系スラッジ、メタバナジン酸アンモニウム等の少なくとも一つ又はこれらを混合した廃棄物を原料とする。表１は原料毎の成分の一例を示す。 Hereinafter, an embodiment of the present invention will be described. In this embodiment, a waste containing V, Mo, and Ni is used as a raw material. Specifically, at least one of a used desulfurization catalyst (direct desulfurization catalyst, indirect desulfurization catalyst), boiler ash, boiler sludge, nickel-based sludge, ammonium metavanadate, and the like, or a mixture thereof is used as a raw material. Table 1 shows an example of components for each raw material.
例えば脱硫触媒にはＮｉ、Ｍｏ、及びＶ成分が多く、Ｃ、Ｓ成分も多い。ボイラー灰にはＣ成分が例えば８０％程度含まれるが、Ｍｏ成分が含まれていない。カーボン系スラッジには水分が例えば５０％も含まれる。このように多種多様な成分を有する廃棄物を原料としている。原料は重油又は水分が付着した状態になっている。 For example, a desulfurization catalyst has many Ni, Mo, and V components, and also has many C and S components. Boiler ash contains, for example, about 80% of a C component, but does not contain a Mo component. The carbon-based sludge contains, for example, 50% of water. Thus, wastes having various components are used as raw materials. The raw material is in a state where heavy oil or moisture is attached.
表２は最終的に得られる製品規格の一例を示す。 Table 2 shows an example of a finally obtained product standard.
Ｆｅ−Ｖ系合金には例えばＪＩＳ２号規格品相当の規格が求められる。この規格では、Ｖ成分を４５〜５５ｍａｓｓ％に調整し、Ｃ、Ｓｉ、Ｐ、Ｓ成分等を低く抑える必要があり、Ｎｉ、Ｍｏ及びＡｌ成分も低く抑える必要がある。またＦｅ−Ｎｉ−Ｍｏ系合金には
、例えば鉄鋼関係で使用される際の規格があり、この規格によればＰ、Ｓ成分を低く抑える必要がある。
For example, a standard equivalent to JIS No. 2 standard product is required for the Fe-V alloy. In this standard, it is necessary to adjust the V component to 45 to 55 mass%, to keep the C, Si, P, S components and the like low, and to keep the Ni, Mo and Al components low. In addition, Fe-Ni-Mo alloys have, for example, a standard when used in relation to iron and steel. According to this standard, it is necessary to keep P and S components low.
図２は有価金属の回収方法のフローを示し、図３はこのフローを図式化したものである。まず脱硫触媒（直接脱硫触媒、間接脱硫触媒）、ボイラー灰、カーボン系スラッジ、ニッケル系スラッジ、重質油ガス化スラッジ等の原料を乾燥する（Ｓ１）。この乾燥工程では、ロータリードライヤで原料を例えば１２０℃程度の温度に加熱して乾燥する。原料中には水分が例えば３０〜４０％程度揮発分として存在する。水分がある状態でこのまま次工程に進むと、水分が多すぎて団鉱できないことがある。なお、脱硫触媒及びコークスボイラー灰はもともと水分が少ないので、乾燥工程の後に投入することもある。 FIG. 2 shows a flow of the method for recovering valuable metals, and FIG. 3 is a schematic diagram of this flow. First, raw materials such as a desulfurization catalyst (a direct desulfurization catalyst and an indirect desulfurization catalyst), boiler ash, carbon-based sludge, nickel-based sludge, and heavy oil gasification sludge are dried (S1). In this drying step, the raw material is heated to a temperature of, for example, about 120 ° C. by a rotary dryer and dried. In the raw material, for example, about 30 to 40% of water exists as a volatile matter. If the process proceeds to the next step in a state where there is water, the water may be too much to aggregate. Since the desulfurization catalyst and the coke boiler ash originally have a low moisture content, they may be added after the drying step.
次に、乾燥したＶ、Ｍｏ及びＮｉ含有廃棄物を粉砕する（Ｓ２）。例えば潤式ミルによりＶ、Ｍｏ及びＮｉ含有廃棄物を粉砕する。粉砕すると多種多様な原料が混合され、均一になる。 Next, the dried V, Mo and Ni-containing waste is crushed (S2). For example, V, Mo and Ni-containing waste is pulverized by a wet mill. When pulverized, various raw materials are mixed and become uniform.
次に粉砕した廃棄物を造粒して団鉱に成形する（Ｓ３）。例えばペレタイザー又はブリケットにより粉砕物をペレット状又はブリケット状の団鉱に成形する。原料を団鉱に成形することなく粉のまま次工程に進むと、焙焼するキルンで原料が焼結したり、溶融還元する加熱炉で棚吊りや吹き上げが生じて炉況が悪くなったりするおそれがある。 Next, the crushed waste is granulated and formed into briquettes (S3). For example, the pulverized material is formed into pellets or briquettes using a pelletizer or briquettes. If the raw material proceeds to the next process without being formed into briquettes, the raw material will sinter in the kiln to be roasted, and the furnace will deteriorate due to shelving and blowing up in the heating furnace for smelting and reducing. There is a risk.
次に団鉱した原料を焙焼する（Ｓ４）。この工程では、団鉱した原料をキルンで例えば８００〜９００℃に加熱する。この焙焼により廃棄物中のＳ分、Ｃ分が加熱分解され、ＳＯｘ、ＣＯ2等として除去される。８００℃以上にするのは、原料に付着した重油とかＣ
分を酸化物にして除去するのに適した温度であり、９５０℃以下にするのはＭｏが昇華して回収率が落ちてしまうのを防止するためである。
Next, the aggregated raw material is roasted (S4). In this step, the aggregated raw material is heated to, for example, 800 to 900 ° C. by a kiln. By this roasting, S and C components in the waste are thermally decomposed and removed as SOx, CO 2 and the like. The temperature of 800 ° C or higher is determined by heavy oil or C
The temperature is suitable for removing oxides into oxides, and the temperature is set to 950 ° C. or lower to prevent the sublimation of Mo from lowering the recovery rate.
なおこれら乾燥工程（Ｓ１）から焙焼工程（Ｓ４）までは、加熱炉での操業の状況によっては省略されることもあり得る。 Note that the steps from the drying step (S1) to the roasting step (S4) may be omitted depending on the operation in the heating furnace.
次に焙焼した原料、還元剤としてのＦｅ、及びフラックスとしての石灰を、加熱炉としての電気炉に装入する。そして、これらを約１７００℃で加熱還元することで、Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる（Ｓ５）。 Next, the roasted raw material, Fe as a reducing agent, and lime as a flux are charged into an electric furnace as a heating furnace. Then, by heating and reducing these at about 1700 ° C., V-containing slag and an Fe—Mo—Ni-based alloy are generated (S5).
この工程（Ｓ５）では、焙焼した原料、Ｆｅ、及びフラックスを同時に電気炉に装入してもよいし、またあらかじめ鉄浴を生成しておき、該鉄浴に原料及び石灰を装入することで溶融還元反応を行ってもよい。あらかじめ鉄浴を生成すると、還元反応の反応効率を向上させることができ、しかも熱効率も向上させることができる。 In this step (S5), the roasted raw material, Fe, and flux may be simultaneously charged into an electric furnace, or an iron bath is generated in advance, and the raw material and lime are charged into the iron bath. Thus, a smelting reduction reaction may be performed. If an iron bath is generated in advance, the reaction efficiency of the reduction reaction can be improved, and the thermal efficiency can be improved.
原料中のＭｏ酸化物及びＮｉ酸化物の還元は、Ｆｅで行なわれる。還元剤としてのＦｅの量は、Ｖ、Ｍｏ及びＮｉ含有廃棄物中のＭｏ酸化物及びＮｉ酸化物を金属にまで還元するのに必要な化学的当量に略等しく設定される。 Reduction of the Mo oxide and the Ni oxide in the raw material is performed with Fe. The amount of Fe as the reducing agent is set substantially equal to the chemical equivalent required to reduce Mo oxides and Ni oxides in V, Mo and Ni-containing wastes to metals.
原料をＦｅで還元した後、溶湯にＡｌ還元剤を添加して、Ｆｅ還元により生じたＦｅ酸化物及び原料中のＦｅ酸化物をＡｌ還元剤で還元する。Ａｌ還元剤で還元するのは、還元反応により生じたＦｅ酸化物をＦｅ−Ｍｏ−Ｎｉ系合金の鉄源としてメタル中に戻すためであり、またＶ含有スラグ中のＦｅ分を調整するためでもある。Ａｌ還元剤はあくまでＦｅ分の成分調整用に補助的に用いられる。Ｆｅ酸化物の還元剤としては、金属Ａｌ、金属Ｓｉ、フェロシリコン、コークス等のいずれか一つ、又はこれらの組み合わせを用いることができる。 After reducing the raw material with Fe, an Al reducing agent is added to the molten metal, and the Fe oxide generated by the Fe reduction and the Fe oxide in the raw material are reduced with the Al reducing agent. The reduction with the Al reducing agent is for returning the Fe oxide generated by the reduction reaction to the metal as an iron source of the Fe-Mo-Ni-based alloy, and also for adjusting the Fe content in the V-containing slag. is there. The Al reducing agent is used only for adjusting the component of Fe. As the reducing agent for Fe oxide, any one of metal Al, metal Si, ferrosilicon, coke, and the like, or a combination thereof can be used.
Ａｌ還元剤を添加することなく、全てＦｅ還元剤で還元することも、還元剤としてのＦｅの量にＦｅ−Ｍｏ−Ｎｉ系合金の鉄源としての分を加えることで可能である。しかしそうすると次工程でＶ含有スラグ中のＦｅ分が多くなりすぎて、Ｖ成分を還元するのが困難になってしまう。Ｖ含有スラグ中のＦｅ分が多い場合、Ｖ含有スラグにＶ成分調整用にＶ2Ｏ5又はメタバナジン酸アンモニウムを装入する必要がある。 It is also possible to perform all reduction with the Fe reducing agent without adding the Al reducing agent by adding the amount of Fe as the reducing agent to the amount of Fe as the iron source of the Fe—Mo—Ni alloy. However, in this case, the amount of Fe in the V-containing slag in the next step becomes too large, and it becomes difficult to reduce the V component. When the Fe content in the V-containing slag is large, it is necessary to charge the V-containing slag with V 2 O 5 or ammonium metavanadate for adjusting the V component.
次にＦｅ−Ｍｏ−Ｎｉ系合金をＶ含有スラグと分離した後、Ｆｅ−Ｍｏ−Ｎｉ系合金の脱Ｓ，脱Ｐ，脱Ｃを行う（Ｓ６，Ｓ７）。原料中のＰ成分はＦｅ−Ｍｏ−Ｎｉ系合金中に残る。Ｓ成分は規格が厳しいので脱Ｓする必要があり、Ｃ成分は電極からの加炭もあるので脱Ｃする必要がある。 Next, after separating the Fe-Mo-Ni-based alloy from the V-containing slag, the Fe-Mo-Ni-based alloy is subjected to de-S, de-P, and de-C (S6, S7). The P component in the raw material remains in the Fe-Mo-Ni-based alloy. Since the S component has a strict standard, it is necessary to remove S, and the C component needs to be removed from C because of carburization from the electrode.
この工程では、まずＦｅ−Ｍｏ−Ｎｉ系合金を加熱用容器としてのレードル・ファーネスに出湯する（Ｓ６）。次に、石灰、ＣａＯ−Ａｌ2Ｏ3系フラックス、及びＣａＯ−Ａｌ2Ｏ3−ＦｅＯ系フラックス等を装入し、脱Ｓ，Ｐ，Ｃを行う（Ｓ７）。ＣａＯ−Ａｌ2Ｏ3系フラックスには、後述するＶ含有スラグをＡｌ還元することで発生するスラグを利用してもよい。ＡｒガスやＯ2ガス吹き（バブリング利用）は効果がある。最後に脱Ｓ，脱Ｐ
，脱Ｃを行ったＦｅ−Ｍｏ−Ｎｉ系合金を鋳型に鋳込む。
In this step, first, the Fe-Mo-Ni alloy is poured into a ladle furnace as a heating vessel (S6). Next, lime was charged with CaO-Al 2 O 3 based flux, and CaO-Al 2 O 3 -FeO based flux or the like, and de-S, P, and C (S7). The CaO-Al 2 O 3 based flux, may be utilized slag generated by Al reducing the V-containing slag to be described later. Ar gas or O 2 gas blowing (using bubbling) is effective. Finally, de-S, de-P
Then, the Fe-Mo-Ni-based alloy de-C is cast into a mold.
一方Ｖ含有スラグも、加熱用容器としてのレードル・ファーネスに出湯される（Ｓ８）。このレードル・ファーネスには、Ａｌ還元剤、石灰及びＶ成分調整用のＶ2Ｏ5も投入され、これによりＶ含有スラグからＦｅ−Ｖ系合金及びＣａＯ−Ａｌ2Ｏ3スラグが生成する。ここで最少の設備にするために、Ｆｅ−Ｍｏ−Ｎｉ系合金を脱Ｓ，脱Ｐ，脱Ｃするのに使用されるレードル・ファーネスと、Ｖ含有スラグをＡｌ還元するのに使用されるレードル・ファーネスとが共用される。 On the other hand, the V-containing slag is also supplied to the ladle furnace as a heating vessel (S8). An Al reducing agent, lime, and V 2 O 5 for adjusting the V component are also supplied to the ladle furnace, whereby an Fe—V alloy and a CaO—Al 2 O 3 slag are generated from the V-containing slag. Here, in order to minimize the equipment, a ladle furnace used to remove S, P, and C from the Fe-Mo-Ni alloy and a ladle used to reduce V-containing slag to Al. -Shared with furnace.
図４は電気炉における溶湯量と、メタルＦｅ、Ｎｉ、Ｍｏ成分の経時的な変化を示す概念図である。Ｆｅ還元することにより、時間の経過に伴ってメタル中のＦｅ成分が少なくなり、Ｎｉ及びＭｏ成分が多くなり、その後安定させることができる。また、Ｖ含有スラグが所定の量になると、メタルをそのまま炉内に残し、Ｖ含有スラグだけレードル・ファーネスに出湯する。そしてレードル・ファーネスでＶ含有スラグの還元が行なわれる。一方Ｖ含有スラグがレードル・ファーネスに出湯される複数バッチに一回、Ｆｅ−Ｍｏ−Ｎｉ系合金が同じレードル・ファーネスに出湯される。そして同じレードル・ファーネスで脱Ｓ，脱Ｐ，脱Ｃの精錬が行われる。 FIG. 4 is a conceptual diagram showing the amount of molten metal in an electric furnace and changes over time of metal Fe, Ni, and Mo components. By reducing Fe, the Fe component in the metal decreases over time, the Ni and Mo components increase, and the metal can be stabilized thereafter. Further, when the V-containing slag reaches a predetermined amount, the metal is left as it is in the furnace, and only the V-containing slag flows into the ladle furnace. Then, the V-containing slag is reduced in the ladle furnace. On the other hand, once in a plurality of batches in which the V-containing slag is discharged to the ladle furnace, the Fe-Mo-Ni-based alloy is discharged to the same ladle furnace. Refining for removal of S, removal of P and removal of C is performed in the same ladle furnace.
生成されるＦｅ−Ｍｏ−Ｎｉ系合金の量はＶ含有スラグに比較して非常に少ない。Ｖ含有スラグを頻繁に出湯することにより、電気炉の熱効率が向上する。またＶ含有スラグを出湯するバッチ毎にＦｅ−Ｍｏ−Ｎｉ系合金を出湯する場合に比較して、生産性も向上する。 The amount of the produced Fe-Mo-Ni-based alloy is much smaller than that of the V-containing slag. By frequently tapping the V-containing slag, the thermal efficiency of the electric furnace is improved. In addition, productivity is also improved as compared with the case where the Fe-Mo-Ni-based alloy is tapped for each batch in which the V-containing slag is tapped.
図５は有価金属の回収方法のフローの他の例を示す。このフローでは、予備処理工程の乾燥工程と焙焼工程とを一緒にして、プロセスをシンプルにしている。まず脱硫触媒（直接脱硫触媒、間接脱硫触媒）、ボイラー灰、カーボン系スラッジ、ニッケル系スラッジ、重質油ガス化スラッジ等の原料を焙焼する（Ｓ１´）。この工程では、例えばロータリーキルンで例えば８００〜９００℃に加熱する。この焙焼により、廃棄物中の水分が蒸発し、また、Ｓ分、Ｃ分が除かれる。 FIG. 5 shows another example of the flow of the valuable metal recovery method. In this flow, the drying step and the roasting step of the pretreatment step are combined to simplify the process. First, raw materials such as a desulfurization catalyst (a direct desulfurization catalyst and an indirect desulfurization catalyst), boiler ash, carbon-based sludge, nickel-based sludge, and heavy oil gasification sludge are roasted (S1 '). In this step, for example, heating is performed to, for example, 800 to 900 ° C. by a rotary kiln. By this roasting, moisture in the waste evaporates, and S and C components are removed.
次に、粉々になっている原料を団鉱する（Ｓ３´）。例えばペレタイザー又はブリケットにより原料をペレット状又はブリケット状の団鉱に成形する。原料によっては、ブリケット状により団鉱しやすくするために、団鉱する前に粉砕工程を入れてもよい（Ｓ２´）。粉でないものは団鉱せずにそのまま装入してもよい。原料、還元剤としてのＦｅ、及び
フラックスとしての石灰を、加熱炉としての電気炉に装入する（Ｓ５）以降のプロセスは、上記図２に示される回収方法のフローと同一なので、同一の符号を附してその説明を省略する。
Next, the powdered raw material is aggregated (S3 '). For example, the raw material is formed into pellets or briquettes using a pelletizer or briquettes. Depending on the raw material, a pulverizing step may be performed before briquetting to facilitate briquetting in a briquette shape (S2 '). Non-powder may be charged as it is without bridging. The process after charging the raw material, Fe as the reducing agent, and lime as the flux into the electric furnace as the heating furnace (S5) and thereafter is the same as the flow of the recovery method shown in FIG. And the description is omitted.
図６は、有価金属の回収方法のフローのさらに他の例を示す。このフローでは、さらにプロセスをシンプルにし、原料をそのまま電気炉に装入している。油、水等の揮発分が含まれる原料を電気炉に装入すると、電気炉操業が困難になるおそれがあるが、原料によっては揮発分が少ないものもある。このフローは、揮発分が少ない原料の処理に適している。原料、還元剤としてのＦｅ、及びフラックスとしての石灰を、加熱炉としての電気炉に装入する（Ｓ５）以降のプロセスは、上記図２に示される回収方法のフローと同一なので、同一の符号を附してその説明を省略する。 FIG. 6 shows still another example of the flow of the valuable metal recovery method. In this flow, the process is further simplified, and the raw materials are directly charged into the electric furnace. If a raw material containing volatile components such as oil and water is charged into an electric furnace, the operation of the electric furnace may be difficult, but some raw materials have a small volatile component. This flow is suitable for processing a raw material having a low volatile content. The process after charging the raw material, Fe as the reducing agent, and lime as the flux into the electric furnace as the heating furnace (S5) and thereafter is the same as the flow of the recovery method shown in FIG. And the description is omitted.
脱硫触媒、ボイラー灰、ニッケル系スラッジの混合原料をドライヤで焙焼して表３の成分組成が得られた。 The raw material mixture of the desulfurization catalyst, boiler ash, and nickel-based sludge was roasted in a dryer to obtain the component compositions shown in Table 3.
次に５００ＫＶＡ電気炉に、乾燥原料１００ｋｇ、生石灰１４ｋｇ、Ｆｅ７ｋｇを装入し、これらを約１７００℃に加熱し、溶融還元反応を行った。表４に示される成分組成のＦｅ−Ｍｏ−Ｎｉ系合金１０ｋｇとＶリッチスラグを生成した。 Next, 100 kg of dry raw material, 14 kg of quicklime, and 7 kg of Fe were charged into a 500 KVA electric furnace, and these were heated to about 1700 ° C. to perform a smelting reduction reaction. 10 kg of an Fe-Mo-Ni-based alloy having the component composition shown in Table 4 and V-rich slag were produced.
分離回収したＶリッチスラグ５７ｋｇを高周波炉で１６００℃に保持し、還元剤として金属Ａｌを５ｋｇと石灰５ｋｇ、Ｖ2Ｏ5７ｋｇを添加して表５に示されるＦｅ−Ｖ系合金１０ｋｇを回収した。 57 kg of the separated and recovered V-rich slag is kept at 1600 ° C. in a high-frequency furnace, and 5 kg of metal Al, 5 kg of lime and 7 kg of V 2 O 5 are added as a reducing agent, and 10 kg of an Fe-V alloy shown in Table 5 is recovered. did.
脱硫触媒、ボイラースラッジ、ニッケル系スラッジ、ボイラー灰等の原料を乾燥後、バインダとしてベントナイトを２％添加してから潤式ボールミルにて２００ｍｅｓｈ以下に調湿・粉砕し、次いで団鉱機を用いて直径１０ｍｍ程度のペレットに成形した。その後、竪型キルンにて、８００℃、３時間焙焼し、表６に示される焙焼物を得た。 After drying raw materials such as a desulfurization catalyst, boiler sludge, nickel-based sludge, and boiler ash, 2% of bentonite is added as a binder, and then moisture-conditioned and pulverized to 200 mesh or less by a wet ball mill, and then using a briquette machine. It was formed into a pellet having a diameter of about 10 mm. Thereafter, the resultant was roasted in a vertical kiln at 800 ° C. for 3 hours to obtain a roasted product shown in Table 6.
マグネシアライニングされた５００ＫＶＡ電気炉に、あらかじめＦｅ１７ｋｇを溶融しておき、そこに上記焙焼物１００ｋｇと生石灰３２、Ａｌ４ｋｇを添加し、さらにＡｒガスを吹き込む攪拌を加えることにより、表７に示されるＦｅ−Ｍｏ−Ｎｉ系合金２４ｋｇを得た。 In a magnesia-lined 500 KVA electric furnace, 17 kg of Fe was previously melted, and 100 kg of the roasted material, 32 lime and 4 kg of Al were added thereto, and further, stirring was performed by blowing Ar gas to obtain Fe- 24 kg of a Mo—Ni alloy was obtained.
さらにＦｅ−Ｍｏ−Ｎｉ系合金を高周波炉で加熱保持し、脱Ｓ，Ｐ，Ｃを行った。表８に結果を示す。 Further, the Fe-Mo-Ni alloy was heated and held in a high-frequency furnace to remove S, P, and C. Table 8 shows the results.
分離回収したＶリッチスラグ１３８ｋｇを約１６００℃に保持し、Ａｒガスで攪拌した。還元剤として金属Ａｌ２５ｋｇと、Ｖ2Ｏ5を２１ｋｇと、石灰２５ｋｇとを添加することで、表９に示されるＦｅ−Ｖ系合金３９ｋｇを回収した。 138 kg of the V-rich slag separated and recovered was kept at about 1600 ° C., and stirred with Ar gas. Metal Al25kg as a reducing agent, and 21kg of V 2 O 5, by adding a lime 25 kg, was recovered Fe-V alloy 39kg shown in Table 9.
また、スラグ成分は、ＣａＯ３１％、Ａｌ2Ｏ3５２％、ＳｉＯ2２％、ＭｇＯ８％、Ｆ
ｅＯ０．８％であった。
The slag components are CaO 31%, Al 2 O 3 52%,
eO was 0.8%.
Ｓ１…Ｖ，Ｎｉ，Ｍｏ含有廃棄物を乾燥する工程
Ｓ２…乾燥したＶ、Ｍｏ及びＮｉ含有廃棄物を粉砕する工程
Ｓ３…粉砕した廃棄物を造粒して団鉱に成形する工程
Ｓ４…団鉱した原料を焙焼する工程
Ｓ５…Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程
Ｓ６…Ｆｅ−Ｍｏ−Ｎｉ系合金をレードルファーネルに出湯する工程
Ｓ７…脱Ｓ，脱Ｐ，脱Ｃを行う工程
Ｓ８…Ｖ含有スラグをレードル・ファーネスに出湯する工程
S1: Step of drying V, Ni, and Mo-containing waste S2: Step of pulverizing the dried V, Mo, and Ni-containing waste S3: Step of granulating the pulverized waste to form a briquette S4: Dang Step of roasting the ore raw material S5 ... Step of producing V-containing slag and Fe-Mo-Ni alloy S6 ... Step of tapping Fe-Mo-Ni alloy into ladle funnel S7 ... DeS, DeP, DeP Step of performing C S8: Step of tapping V-containing slag into ladle furnace
Claims (9)
前記Ｖ含有スラグに還元剤を投入してＦｅ−Ｖ系合金を生成させる工程と、を備えるＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 Reducing V, Mo and Ni-containing waste with Fe to produce a V-containing slag and a Fe-Mo-Ni-based alloy;
Supplying a reducing agent to the V-containing slag to generate an Fe-V-based alloy, and recovering valuable metals from V, Mo, and Ni-containing waste.
Ｖ、Ｍｏ及びＮｉ含有廃棄物を焙焼する工程；
前記Ｖ、Ｍｏ及びＮｉ含有廃棄物、還元剤としてのＦｅ、及びフラックスを加熱炉に装入し、これらを加熱還元することで、Ｖ含有スラグ及びＦｅ−Ｍｏ−Ｎｉ系合金を生成させる工程；
前記Ｖ含有スラグにＡｌ還元剤を投入して、Ｆｅ−Ｖ系合金及びＣａＯ−Ａｌ2Ｏ3スラグを生成させる工程。 A method for recovering valuable metals from waste containing V, Mo and Ni, comprising the following steps:
Roasting V, Mo and Ni containing waste;
A step of charging the V, Mo, and Ni-containing waste, Fe as a reducing agent, and a flux into a heating furnace and reducing them by heating to generate a V-containing slag and an Fe-Mo-Ni-based alloy;
The V-containing slag by introducing the Al reducing agent, Fe-V alloys and CaO-Al 2 O 3 process to produce the slag.
前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を前記Ｆｅで還元した後、前記Ｆｅで還元することにより生じたＦｅ酸化物をＡｌ、Ｓｉ、及びＣの少なくとも一つで還元することを特徴とする請求項１又は２に記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy,
The V, Mo and Ni-containing waste is reduced with the Fe, and then the Fe oxide generated by the reduction with the Fe is reduced with at least one of Al, Si, and C. 3. The method for recovering valuable metals from waste containing V, Mo and Ni according to 1 or 2.
前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を乾燥した後、粉砕し、団鉱に成形し、これを焙焼することを特徴とする請求項２又は３に記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of roasting the V, Mo and Ni-containing waste,
The V, Mo, and Ni-containing waste according to claim 2 or 3, wherein the V, Mo, and Ni-containing waste is dried, pulverized, formed into briquettes, and roasted. Recovery method of valuable metals.
前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を焙焼した後、団鉱に成形することを特徴とする請求項２又は３に記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of roasting the V, Mo and Ni-containing waste,
The method for recovering valuable metals from V, Mo, and Ni-containing waste according to claim 2 or 3, wherein the V, Mo, and Ni-containing waste is roasted and then formed into briquettes.
あらかじめ鉄浴を生成しておき、該鉄浴に前記Ｖ、Ｍｏ及びＮｉ含有廃棄物を装入して溶融還元反応を行うことを特徴とする請求項１ないし５いずれかに記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy,
The V, Mo according to any one of claims 1 to 5, wherein an iron bath is generated in advance, and the V, Mo, and Ni-containing waste is charged into the iron bath to perform a smelting reduction reaction. And a method of recovering valuable metals from Ni-containing waste.
前記Ｆｅ−Ｍｏ−Ｎｉ系合金を前記Ｖ含有スラグと分離した後、前記Ｆｅ−Ｍｏ−Ｎｉ系合金の脱Ｓ，脱Ｐ，脱Ｃを行うことを特徴とする請求項１ないし６いずれかに記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy,
The method according to any one of claims 1 to 6, wherein after the Fe-Mo-Ni-based alloy is separated from the V-containing slag, the Fe-Mo-Ni-based alloy is subjected to de-S, P, and C removal. The method for recovering valuable metals from waste containing V, Mo and Ni described in the above.
前記Ｆｅ−Ｍｏ−Ｎｉ系合金が一回出湯される間に、前記Ｖ含有スラグが複数回出湯されることを特徴とする請求項１ないし８いずれかに記載のＶ、Ｍｏ及びＮｉ含有廃棄物からの有価金属の回収方法。 In the step of producing the V-containing slag and the Fe-Mo-Ni-based alloy,
9. The V-, Mo-, and Ni-containing waste according to any one of claims 1 to 8, wherein the V-containing slag is tapped a plurality of times while the Fe-Mo-Ni-based alloy is tapped once. For recovering valuable metals from coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003409513A JP3705498B2 (en) | 2002-12-06 | 2003-12-08 | Method for recovering valuable metals from waste containing V, Mo and Ni |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002355729 | 2002-12-06 | ||
| JP2003059837 | 2003-03-06 | ||
| JP2003409513A JP3705498B2 (en) | 2002-12-06 | 2003-12-08 | Method for recovering valuable metals from waste containing V, Mo and Ni |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005119829A Division JP4485987B2 (en) | 2002-12-06 | 2005-04-18 | Method for recovering valuable metals from waste containing V, Mo and Ni |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2004285473A true JP2004285473A (en) | 2004-10-14 |
| JP2004285473A5 JP2004285473A5 (en) | 2005-06-23 |
| JP3705498B2 JP3705498B2 (en) | 2005-10-12 |
Family
ID=33303660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003409513A Expired - Lifetime JP3705498B2 (en) | 2002-12-06 | 2003-12-08 | Method for recovering valuable metals from waste containing V, Mo and Ni |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3705498B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008068810A1 (en) * | 2006-11-30 | 2008-06-12 | Kohsei Co., Ltd. | Process for recovering valuable metals from waste |
| JP2009287053A (en) * | 2008-05-27 | 2009-12-10 | Sumitomo Heavy Ind Ltd | Vanadium recovery device |
| US8137654B2 (en) | 2005-10-05 | 2012-03-20 | Jfe Material Co., Ltd. | Method of roasting material containing at least one of V, Mo and Ni and rotary kiln for roasting the same |
| KR101569911B1 (en) | 2014-05-09 | 2015-11-17 | 주식회사 미네월드 | Recovering method of ferro-molybdenum from ferro-molybdenum slag |
| CN110735080A (en) * | 2019-10-10 | 2020-01-31 | 南京钢铁股份有限公司 | Production method of steel multi-stage special container steel blank |
| JPWO2023084947A1 (en) * | 2021-11-12 | 2023-05-19 | ||
| WO2024225041A1 (en) * | 2023-04-28 | 2024-10-31 | Ｊｆｅスチール株式会社 | Method for recovering valuable element |
| JPWO2024225035A1 (en) * | 2023-04-28 | 2024-10-31 |
-
2003
- 2003-12-08 JP JP2003409513A patent/JP3705498B2/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8137654B2 (en) | 2005-10-05 | 2012-03-20 | Jfe Material Co., Ltd. | Method of roasting material containing at least one of V, Mo and Ni and rotary kiln for roasting the same |
| WO2008068810A1 (en) * | 2006-11-30 | 2008-06-12 | Kohsei Co., Ltd. | Process for recovering valuable metals from waste |
| US8317895B2 (en) | 2006-11-30 | 2012-11-27 | Kohsei Co., Ltd. | Method for recovering valuable metals from wastes |
| JP2009287053A (en) * | 2008-05-27 | 2009-12-10 | Sumitomo Heavy Ind Ltd | Vanadium recovery device |
| KR101569911B1 (en) | 2014-05-09 | 2015-11-17 | 주식회사 미네월드 | Recovering method of ferro-molybdenum from ferro-molybdenum slag |
| CN110735080A (en) * | 2019-10-10 | 2020-01-31 | 南京钢铁股份有限公司 | Production method of steel multi-stage special container steel blank |
| JP7609274B2 (en) | 2021-11-12 | 2025-01-07 | Ｊｆｅスチール株式会社 | Method for recovering valuable elements |
| WO2023084947A1 (en) * | 2021-11-12 | 2023-05-19 | Ｊｆｅスチール株式会社 | Valuable element recovery mehtod |
| JPWO2023084947A1 (en) * | 2021-11-12 | 2023-05-19 | ||
| EP4403658A4 (en) * | 2021-11-12 | 2025-06-04 | JFE Steel Corporation | Valuable element recovery mehtod |
| WO2024225041A1 (en) * | 2023-04-28 | 2024-10-31 | Ｊｆｅスチール株式会社 | Method for recovering valuable element |
| JPWO2024225035A1 (en) * | 2023-04-28 | 2024-10-31 | ||
| JPWO2024225041A1 (en) * | 2023-04-28 | 2024-10-31 | ||
| WO2024225035A1 (en) * | 2023-04-28 | 2024-10-31 | Ｊｆｅスチール株式会社 | Valuable element recovery method |
| JP7670248B2 (en) | 2023-04-28 | 2025-04-30 | Ｊｆｅスチール株式会社 | Method for recovering valuable elements |
| JP7670246B2 (en) | 2023-04-28 | 2025-04-30 | Ｊｆｅスチール株式会社 | Method for recovering valuable elements |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3705498B2 (en) | 2005-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA3056280C (en) | Carbothermic direct reduction of chromite using a catalyst for the production of ferrochrome alloy | |
| CN102337408B (en) | Two-step reduction method for recycling stainless steel scales | |
| JP2009079303A (en) | Manufacturing method of stainless steel by reutilizing waste in stainless steel manufacturing process | |
| KR100764259B1 (en) | METHOD FOR RECOVERING VALUABLE METAL FROM WASTE CONTAINING V, Mo AND Ni | |
| CA2607770C (en) | Method for recovering valuable metals from wastes | |
| JP3705498B2 (en) | Method for recovering valuable metals from waste containing V, Mo and Ni | |
| KR100291250B1 (en) | Process for reducing the electric steelworksdusts and facility for implementing it | |
| JP3705472B2 (en) | Method for recovering useful metals from vanadium-containing waste | |
| JP2011094207A (en) | Method for producing metal manganese | |
| WO2009145348A1 (en) | Method for manufacturing pig iron | |
| JP2002105550A (en) | Method for zinc recovery | |
| JP2011246760A (en) | Method of manufacturing ferromolybdenum, and ferromolybdenum | |
| JP6409811B2 (en) | Recycling method for chromium-containing dust | |
| JP4485987B2 (en) | Method for recovering valuable metals from waste containing V, Mo and Ni | |
| RU2612330C2 (en) | Method of direct reduction of materials containing metal oxides to produce melt metal and device for carrying out method | |
| JP2004270036A (en) | Recovering method of useful metal from useful metal-containing waste | |
| JP2004143492A (en) | Melting method of ultra low phosphorus stainless steel | |
| CN120359194A (en) | A slag treatment process and equipment | |
| CN100494423C (en) | Method for recovery of valuable metals from waste containing V, Mo and Ni | |
| KR100770059B1 (en) | Recovery of valuable metals from wastes containing Ｖ, MO, and Ni | |
| JPS59159945A (en) | Method for producing metallic magnesium and calcium ferrite from dolomite | |
| JP2001098339A (en) | Method of producing vanadium alloy iron and vanadium alloy steel | |
| JP2011094206A (en) | Method for recovering valuable metal from waste battery or the like | |
| JP2023168817A (en) | RECOVERY METHOD OF VALUABLE METALS FROM Mo, Ni, V-CONTAINING WASTE | |
| JP2004076152A (en) | Method for producing stainless steel reusing waste material in stainless steel producing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040126 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041208 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20041208 |
|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20041208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20041210 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20050207 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050304 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050629 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050629 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050721 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050721 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3705498 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041208 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080805 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090805 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100805 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110805 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120805 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130805 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |