Classifications

• • 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
  • C22B34/00—Obtaining refractory metals
  • C22B34/20—Obtaining niobium, tantalum or vanadium
  • C22B34/22—Obtaining vanadium
• • 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
• • 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
  • C22B34/00—Obtaining refractory metals
  • C22B34/30—Obtaining chromium, molybdenum or tungsten
  • C22B34/34—Obtaining molybdenum
• • 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
  • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
• • 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
  • 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
  • C22B7/02—Working-up flue dust
• • 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
  • C22B7/04—Working-up slag
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C33/00—Making ferrous alloys
  • C22C33/04—Making ferrous alloys by melting
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
  • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
• • 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

Definitions

• 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 metapanadinate.
• Ni and V heavy metals are in the form of oxides in boiler sludge deposited at the bottom of the boiler and boiler ash captured by the dust collector. Condensed. The heavy metal of V is also condensed in the form of oxides on ammonium metapananadate, which is obtained by subjecting boiler ash to wet alkali treatment.
• desulfurization catalysts are provided in the refining process. Also in this used desulfurization catalyst, Ni, Mo, and V heavy metals are condensed in the form of oxides. It is desired to recover these Ni, Mo and V oxidized substances in the form of metal as an effective use of waste.
• One of such recovery technologies is to heat V-containing waste to 450 to 950 ° C to remove S, N, and C in the waste, and then transfer the waste to an iron source and It is mixed with a reducing agent, pulverized, formed into granules, and then heated to 115-135 ° C to reduce the Fe, Ni, and Mo components in the raw material by solid-phase reduction. After that, it is charged into an electric furnace and heated to generate a metal mainly composed of Fe, Ni, and Mo and a V-rich flux, and mainly composed of Fe, Ni, and Mo.
• the metal is subjected to a de-P treatment to obtain a low-P alloy, while a V-rich flux is supplied with a reducing agent in a container having a strong stirring function, and is stirred to reduce V in the flux to reduce Fe.
• a method for obtaining a V-based alloy has been disclosed (see Patent Document 1, Claim 1).
• Another recovery technique is the first step of roasting waste containing V, Mo, Co and Ni. And 50 to 120% of the chemical equivalent of the metal equivalent necessary for reducing Mo, Ni and Co oxides to metal, and adding and reducing by heating and dissolving by it is Rukoto, Mo- N i alloy or Mo- Co alloy or Mo- N i-Co-based alloy and C a O- a 1 2 0 3 system second step of recovering each and slag separates When the CaO-a 1 2 0 3 based slag to, oxides metal above chemical equivalent necessary for reduction to a metallic S i and / or metal a 1 of V contained in the slag It was added pressure by dissolving heat reduced to a third step of recovering each by separating the V-S i based alloy or V- A1 alloy and C a O- a 1 2 ⁇ 3 slag (See Patent Document 2, Claim 1).
• Patent Document 2 Japanese Patent Application Laid-Open No. 2001-214423
• Patent Document 1 pulverized coal or coatas is used as a reducing agent for solid-phase reduction of Fe, Ni, and Mo components in a raw material (Patent Document 1, See paragraph 0022). For this reason, carbon remains in the generated metal mainly composed of Fe, Ni, and Mo. Since carbon is easily bonded to Fe—Mo, Fe—Ni, and the like in the metal, it becomes difficult to remove carbon in a later step. In addition, there is also a problem that the Mo component sublimates in the kiln during the solid-phase reduction, and the recovery yield of the Mo component is deteriorated. There is also the problem that the process is long and equipment costs increase.
• waste is melted as powder, which deteriorates the furnace condition, for example, causing shelves to be suspended or blown up in the melting furnace.
• Deteriorating reactor conditions lead to deterioration of power consumption and operation instability.
• metal Si and / or metal A1 is used as a 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 Z or the metal A1 is reduced and the amount of the metal A1 is weakly reduced, the yield of the Mo and Ni components deteriorates, and the Mo and Ni components enter the V-containing slag.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a Fe-Mo-Ni-based alloy and a Fe-V-based alloy from V, Mo, and Ni-containing waste. It is an object of the present invention to provide a method for recovering the yield in a stable manner.
• the present inventors focused on the oxygen affinity of Ni, Mo, and V at a smelting reduction temperature of 140 ° C. to 180 ° C. As shown in Fig. 1 (graph of the standard free energy of formation of oxides), focusing on the fact that Fe has a stronger oxygen affinity than Ni and Mo and is weaker than V, Fe is used as a reducing agent. It was found that if used, V-containing slag and Fe—Mo—Ni alloy can be separated with good yield.
• the present invention provides a step of reducing V, Mo, and Ni-containing waste with Fe to generate a V-containing slag and a Fe-Mo-Ni-based alloy, and reducing the V-containing slag to the V-containing slag.
• a method for recovering a valent metal which comprises the steps of:
• the present invention also relates to 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; , Mo and Ni-containing waste, Fe as a reducing agent, and flux are charged into a heating furnace, and these are heated and reduced to convert the V-containing slag and Fe-Mo-Ni-based alloy. step generate; by introducing the a 1 reducing agent to the V-containing slag, the step of generating a F e- V alloy ⁇ beauty C a O- a 1 2 0 3 slag can also be configured as.
• the V, Mo and Ni-containing waste is reduced by the Fe and then reduced by the F'e. And the resulting Fe oxide may be reduced with A 1 and Z or Si.
• the Fe oxide generated by the reduction reaction can be used as an iron source of the Fe—Mo—Ni based alloy.
• the Fe content in the V-containing slag can be adjusted, and thus the Fe content can be adjusted in accordance with the final Fe-V alloy specifications. Can be adjusted.
• the V, Mo, and Ni-containing waste be dried, crushed, formed into briquettes, and roasted. No.
• 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 therefore, stable operation can be performed. .
• the V, Mo and Ni-containing waste may be roasted and then formed into briquettes.
• an iron bath is generated in advance, and the V, Mo and Ni-containing waste is charged into the iron bath. It is desirable to carry out the smelting reduction reaction.
• the reaction efficiency of the reduction reaction can be improved, and the heat efficiency can be improved.
• continuous operation of the heating furnace becomes possible.
• impurities of S, P and C can be removed according to the standard of Fe—Mo—Ni alloy. Also, V molded into briquettes, the S component contained in waste when roasting Mo ⁇ Pi N i-containing waste to SO X, it is discharged to the C content in co 2, Fe-Mo By removing S and C after separating the Ni-based alloy from the V-containing slag, the burden of roasting can be reduced.
• the recovery method can be performed with a minimum number of facilities.
• the V-containing slag is discharged a plurality of times while the Fe-Mo-Ni-based alloy is once discharged. Is desirable.
• the amount of Fe—Mo—Ni alloy produced is very small compared to V-containing slag.
• the thermal efficiency is improved by frequently tapping the V-containing slag.
• productivity is improved as compared with the case where Fe-Mo-Ni alloy is tapped for each batch in which V-containing slag is tapped.
• Fig. 1 Graph of standard free energy of formation of oxide.
• FIG. 2 is a diagram showing a flow of a method for recovering valuable metals in one embodiment of the present invention.
• FIG. 3 is a diagram illustrating the flow of FIG.
• Fig. 4 Conceptual diagram showing changes over time in Fe, Ni, and Mo components in metal and changes in the amount of molten metal in the electric furnace.
• Fig. 5 Diagram showing another example of the flow of the method for recovering valuable metals.
• Fig. 6 is a diagram showing still another example of the flow of the method for recovering valuable metals.
• a waste containing V, Mo, and Ni is used as a raw material.
• the raw material shall be at least one of spent desulfurization catalyst (direct desulfurization catalyst, indirect desulfurization catalyst), boiler ash, boiler sludge, nickele sludge, ammonium metavanadate, or a mixture thereof.
• Table 1 shows an example of components for each raw material.
• desulfurization catalysts have many Ni, Mo, and V components, and many C and S components.
• Boiler ash contains, for example, about 80% of the C component, but does not contain the Mo component.
• Power-pond sludge contains, for example, 50% water. Waste materials with various components are used as raw materials. The original family is in a state where heavy oil or moisture is attached.
• Table 2 shows an example of the final product standard.
• Fe-V alloys for example, standards equivalent to JIS No. 2 standard products are required. 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 also to keep the Ni, Mo and A1 components low.
• Fe-Ni-Mo alloys for example, there is a standard for use in steel-related applications. According to this standard, it is necessary to keep the P and S components low.
• Fig. 2 shows the flow of the method for recovering valuable metals
• Fig. 3 illustrates this flow.
• raw materials such as a desulfurization catalyst (direct desulfurization catalyst and indirect desulfurization catalyst), boiler ash, carbon-based sludge, nickel-based sludge, and heavy oil gasification sludge are dried (S1).
• the raw material is dried by heating to a temperature of, for example, about 120 ° C. using a rotary dryer. Water is present in the raw materials as volatile matter, for example, at about 30 to 40%. If the process proceeds to the next step in a state where there is water, briquetting may not be possible due to too much water. Since the desulfurization catalyst and coke boiler ash originally have low water content, they may be added after the drying process.
• the dried V, Mo, and Ni-containing waste is ground (S2).
• the waste containing V, Mo and Ni is ground by a wet mill. When crushed, a wide variety of raw materials are mixed and become uniform.
• the crushed waste is granulated and formed into briquettes (S3).
• the crushed material is formed into pellets or briquettes using a pelletizer or briquettes. If the raw material proceeded to the next process without being formed into briquettes, the raw material sintered in the kiln to be roasted, and the condition of the furnace deteriorated due to shelving and blowing up in the heating furnace for smelting and reducing. May be lost.
• the aggregated raw material is roasted (S4).
• the aggregated raw material is heated in a kiln to, for example, 800 to 900 ° C.
• S and C components in the waste are pyrolyzed and removed as SOx, CO2, etc.
• the temperature of 800 ° C or higher is a temperature suitable for removing heavy oil and C attached to the raw material as oxides, and the temperature of 950 ° C or lower is sublimation of Mo and the recovery rate is lower than 950 ° C. This is to prevent it from falling.
• the steps from the drying step (S1) to the roasting step (S4) may be omitted depending on the situation of the operation in the heating furnace.
• the baked raw material, Fe as a reducing agent, and lime as a flux are charged into an electric furnace as a heating furnace. These are reduced by heating at about 1700 ° C to produce V-containing slag and Fe-Mo-Ni alloy (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 added to the iron bath.
• the smelting reduction reaction can be performed by charging. If an iron bath is generated in advance, the reaction efficiency of the reduction reaction can be improved, and the thermal efficiency can also be improved.
• Reduction of Mo oxide and Ni oxide in the raw material is performed by Fe.
• the amount of Fe as a reducing agent is set approximately equal to the chemical equivalent required to reduce Mo oxides and Ni oxides in V, Mo and Ni-containing wastes to metals. .
• an A 1 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 A 1 reducing agent.
• the reduction with the A1 reducing agent is to return the Fe oxide generated by the reduction reaction to the metal as an iron source of the Fe—Mo—Ni alloy, and to reduce the Fe in the V-containing slag. It is also to adjust the minute.
• the A 1 reducing agent is used only for adjusting the component of Fe.
• metal A1, metal Si, fue silicon, carbon, or the like, any one of them, or a combination thereof can be used.
• the Fe-Mo-Ni-based alloy is de-S, de-P, and de-C (S6, S7).
• the P component in the raw material remains in the Fe—Mo—Ni alloy.
• the S component must be de-S because of strict specifications, and the C component must be de-C because there is carburization from the electrode.
• Fe-Mo-Ni alloy is used as a heating vessel with a ladle Take water to the furnace (S6).
• lime, ⁇ & ⁇ over eight 1 2 ⁇ 3 based flux was charged with ⁇ beauty CaO- A l 2 0 3 -FeO based flux or the like, de S, P, and C performed (S 7).
• Ca_ ⁇ to one A 1 2 0 3 based flux it may be utilized slag generated by A 1 reducing the V-containing slag to be described later.
• Ar gas and 0 2 gas blowing (bubbling use) is effective.
• the Fe-Mo-Ni-based alloy, which has been de-S, de-P, and de-C-deposited is incorporated into the ⁇ type.
• V-containing slag is also supplied to the ladle and furnace as heating vessels (S8).
• the ladle 'furnace, A 1 reducing agent, also V 2 O g for lime and V components adjusted is turned on, thereby V-containing Fe- V alloy from the slag and CaO- A 12O3 slag is produced.
• the ladle furnace used to remove S, P, and C from Fe—Mo—Ni alloys and A 1 reduction of slag containing V The ladle used is shared with the furnace.
• Fig. 4 is a conceptual diagram showing the changes over time in the amount of molten metal and the Fe, Ni, and Mo components in an electric furnace.
• the Fe reduction the Fe component in the metal decreases with time, the Ni and M0 components increase, and the metal can be stabilized thereafter. Also, when the V-containing slag reaches a predetermined amount, the metal is left in the furnace as it is, and only the V-containing slag flows out to the ladle furnace. Then, the V-containing slag is reduced in the Ladle's furnace. On the other hand, once every batch containing V-containing slag into the ladle furnace, the Fe-Mo-Ni-based alloy is tapped into the same ladle-furnace. Then, scouring for removal of S, removal of P, and removal of the same material is performed in the same furnace.
• the amount of Fe-Mo-Ni-based alloy produced is very small compared to V-containing slag. Frequent tapping of V-containing slag improves the thermal efficiency of the electric furnace. Also, productivity is improved compared to the case where Fe-Mo-Ni alloy is tapped for each batch in which V-containing slag is tapped.
• Fig. 5 shows another example of the flow of the valuable metal recovery method. This flow simplifies the process by combining the drying and roasting steps of the pretreatment step.
• First desulfurization catalyst direct desulfurization catalyst, indirect desulfurization catalyst
• boiler ash carbon-based sludge, nickel sludge, roasting raw materials such as heavy oil gasification sludge (S 1 ') 0
• S 1 ' heavy oil gasification sludge
• the raw material that has been shattered is aggregated (S 3 ′).
• the raw material is formed into pellet-like or pricket-like briquettes using a pelletizer or a pricket.
• a grinding process may be performed before briquetting to reduce briquettes by briquetting (S 2 ′).
• 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) is the same as the flow of the recovery method shown in Fig. 2 above.
• the same reference numerals are given and the description is omitted.
• FIG. 6 shows still another example of the flow of the method for recovering valuable metals.
• the process is further simplified, and the raw materials are charged directly 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 become difficult, but some raw materials have low volatile components.
• This flow is suitable for processing raw materials with low volatile content.
• the raw material, Fe as a reducing agent, and lime as a flux are charged into an electric furnace as a heating furnace (S 5).
• the process after that is the same as the flow of the recovery method shown in FIG. The description is omitted by attaching the sign.
• the raw material mixture of the desulfurization catalyst, boiler ash, and nickel-based sludge was roasted with a dryer to obtain the component compositions shown in Table 3.
• 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.
• Fe-Mo-Ni-based alloys and Fe-V-based alloys can be stably produced with high yield from V, M0, and Ni-containing wastes. Can be collected.

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• 2003
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