EP0530893B1 - Procédé pour la fusion de plomb métallique en continu - Google Patents

Procédé pour la fusion de plomb métallique en continu Download PDF

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Publication number
EP0530893B1
EP0530893B1 EP92202548A EP92202548A EP0530893B1 EP 0530893 B1 EP0530893 B1 EP 0530893B1 EP 92202548 A EP92202548 A EP 92202548A EP 92202548 A EP92202548 A EP 92202548A EP 0530893 B1 EP0530893 B1 EP 0530893B1
Authority
EP
European Patent Office
Prior art keywords
lead
slag
phase
primary
zone
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.)
Expired - Lifetime
Application number
EP92202548A
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German (de)
English (en)
Other versions
EP0530893A1 (fr
Inventor
Lutz Dr. Deininger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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Filing date
Publication date
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0530893A1 publication Critical patent/EP0530893A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes

Definitions

  • the invention relates to a process for the continuous melting of metallic lead from noble metal-containing and lead-containing precursors.
  • Lead ores practically always contain silver and in many cases gold and platinum. Precious metals can also be contained in lead-containing intermediates or waste. In the pyrometallurgical extraction of lead, the precious metals go into the lead. After refining to remove copper, nickel, cobalt, tin, arsenic and antimony, the removal and extraction of the noble metals from the pre-refined lead lead is generally carried out using the Parkes process. Excess zinc is introduced into the liquid lead and silver-zinc-lead mixed crystals are precipitated by cooling, which are skimmed off as so-called foams or crusts from the lead bath. These foams also contain the other precious metals.
  • the excess zinc present in the desilvered lead is removed either by the Harris method by adding NaOH, by the Betterton method by chlorination or by vacuum dezincification.
  • the zinc is mechanically adhered to the foams by pressing or segregation and the zinc is removed by distillation and the so-called rich lead is produced, which contains the precious metals in high concentration.
  • the rich lead which can contain up to about 50% silver
  • the lead is oxidized to PbO in the so-called propellant process by selective oxidation with air and drawn off as a liquid smoothness, leaving behind the silver or guildish silver.
  • the Güldisch silver is then subjected to refining electrolysis.
  • a method for lead extraction in which a mixture of oxidic and sulfidic lead compounds in a first stage in a moving furnace, e.g. a rotary kiln is melted down, whereby in addition to primary lead, a high-lead-containing slag is formed, which contains the lead partly as an oxide and partly as a silicate. Lead and slag are withdrawn from the first stage, the slag being extracted in pieces. In a second stage, the slag is melted in a shaft furnace to reduce it, resulting in a low-lead slag and secondary lead. Precious metals in the feed go into the primary lead almost quantitatively.
  • Part of the primary lead obtained in the first stage can be oxidized again and form the feed for the first stage as an oxidic component with fresh amounts of sulfidic ore.
  • the silver contained in the primary lead is enriched in a small amount of lead so that it can be directly subjected to the driving process.
  • This process relates to a batch process in which the slag tapped from the first stage has to be melted down again in the second stage.
  • the lead tapped from the first stage must be oxidized in order to produce a lead worthy of driving.
  • a method for processing lead, copper and sulfur-containing materials in two separate stages is known, a copper stone phase and a lead-containing primary lead phase being formed in the first stage.
  • the separated slag phase is reduced in a second stage, with low-lead slag and secondary lead as well as possibly a cobalt-containing arsenic alloy.
  • Both stages can be carried out in shaft furnaces, flame furnaces, short drum furnaces, head-blown rotary converters or bottom-blown tilting converters.
  • Arc resistance furnaces are specified as advantageous units.
  • Most of the leading silver is accumulated in the first stage in the primary lead and in the copper stone.
  • the lead content of the slag in the first stage is set at 20 to 40%.
  • the silver content of the lead is largely in the copper stone and the primary lead.
  • the silver content of the primary lead is less than 1%, so that the primary lead has to be subjected to the usual refining in order to obtain the silver.
  • this method is only intended for copper-rich lead materials.
  • the precursors can be in any form, for example as oxides, sulfides, sulfates, silicates. It is also possible to add or use metallic raw materials such as computer scrap, in which case additives for the formation of slag may then have to be added. If the precursors do not contain any fuel, for example in sulfidic form, or if their fuel content is insufficient to cover the heat requirement in the oxidation zone, the required fuel is added to the oxidation zone in solid, gaseous or liquid form. The fuel can be added by means of nozzles from below or laterally into the melt and / or into the gas space or with the feed mixture.
  • the metal phases in the oxidation zone and the reduction zone are separated from one another by a partition arranged on the bottom of the reactor.
  • the slag flows from the oxidation zone through this partition or through an opening in the partition into the reduction zone.
  • the gas spaces of the oxidation and reduction zones can be separated from one another or the gas from the reduction zone flows into the oxidation zone and is used there for after-combustion to cover the heat.
  • oxygen-containing gases are blown into the lead phase from below or from the side.
  • the oxygen partial pressure in the oxidation zone is set so that only the desired amount of primary lead is obtained from the leading amount of lead and the remaining lead content is driven into the slag as oxide.
  • an appropriate rich lead with the desired silver content can be presented, then the oxygen partial pressure required for continuous operation can be set directly. If lead is presented when starting, an oxygen partial pressure must first be used, in which the lead is enriched with silver to the desired value and little or no primary lead is obtained. To When the desired concentration is reached, the oxygen partial pressure is then set to the value for continuous operation. The oxygen partial pressure is adjusted by regulating the ratio of the amount of oxygen blown in to the amount of the oxidizable constituents contained in the primary substances. If fuels are blown into the melt, these must be taken into account. Oxygen, oxygen-enriched air or air can be used as the oxygen-containing gases.
  • the silver content in the primary lead can be increased to such an extent that, for example, Güldischsilver is obtained with a high silver content in the primary materials.
  • the secondary lead phase is located under the slag phase in the reduction zone.
  • the reducing agent is blown into the lead phase from below or from the side and flows from there into the slag phase and then into the free reactor space.
  • Carbon-containing solid, liquid or gaseous materials are used as reducing agents. They are blown in with oxygen-containing gases and at least partially converted to CO and possibly H2 in the lead phase, so that a reducing gas from the lead phase enters the slag phase.
  • the combustible components can be post-burned in the escaping gas. If necessary, fuel is burned in the gas space of the reduction zone to cover the heat requirement.
  • the advantage of the method of operation according to the invention is that no classical enrichment by adding zinc, Seigers and distillation is required to remove the precious metals from the lead, but the primary lead can be used directly in the driving work. in addition, there is only a very small amount of precious metal in the cycle and / or intermediate products.
  • the secondary lead produced in the reduction zone is largely free of precious metals and does not require desilvering.
  • a preferred embodiment consists in that according to c) the oxygen partial pressure in the oxidation zone is controlled so that the melted primary lead has a silver content of at least 50% and the amount of primary lead is less than 5% of the leading lead content. This makes the extraction of the precious metals from the primary lead particularly economical.
  • the starting materials used contain sulfidic lead materials.
  • Sulfidic lead materials are primarily lead ore concentrates. They are processed in accordance with the QSL procedure, e.g. in U.S. Patent 4,266,971 and U.S. Patent 4,895,595. Other materials containing precious metals can be added to the lead ore.
  • the fuel required in the form of sulfide sulfur is already contained in the feedstock in a very uniform distribution, so that very good operating conditions result.
  • a preferred embodiment consists in that in the reduction zone carbon-containing reducing agents and oxygen-containing gases are blown into the secondary lead phase by means of nozzles and a level of the lead phase is set which converts the reducing agent to CO and, if appropriate, H2 of at least 50% in the lead phase before Entry into the slag phase causes.
  • the amount of oxygen introduced in the oxygen-containing gases is such that the reducing agent in the lead phase is converted to CO and possibly H2 in the desired percentage.
  • the education of H2 occurs when using hydrocarbons or through the implementation of volatile components that are contained in the coal.
  • the height of the lead phase required for the desired implementation of the reducing agent in the lead phase depends on the type of reducing agent and the oxygen-containing gas, the temperature of the lead phase and the strength and speed of the blowing jets.
  • the required height can, however, be determined relatively easily empirically for each operating case.
  • a protective gas can be blown in as a jacket gas in multi-component nozzles to protect the nozzle mouthpieces against severe erosion.
  • the CO and H2-containing reducing gas produced by the reaction is simultaneously heated up strongly in the metal layer and accordingly enters the slag at high temperature, creating very good reduction conditions. In addition, in the event of an incomplete implementation, this favors a further conversion to CO and H2 in the slag layer.
  • the height of the lead phase above floor-blowing nozzles is at least 4 cm and is preferably above 20 cm.
  • the QSL reactor has a length of 33 m, an inner diameter of 3 m in the oxidation zone and 2.5 m in the reduction zone.
  • a weir is arranged between the oxidation zone and the reduction zone, which mixes the lead phases of the oxidation and reduction zones prevents, but allows the high lead-containing slag to flow out of the oxidation zone into the reduction zone.
  • the reactor is equipped with six bottom-blowing nozzles in the oxidation zone and five in the reduction zone.
  • Technically pure oxygen is blown into the oxidation zone. Fine-grained coal, technically pure oxygen and nitrogen or natural gas or mixtures as a protective gas for the nozzles are blown into the reduction zone.
  • Secondary lead and slag are alternately tapped from the reduction zone, while a lead bath of approx. 250 mm is maintained.
  • the primary lead or rich lead is continuously withdrawn from the oxidation zone.
  • the exhaust gas from the oxidation zone and the reduction zone is drawn off together on the side of the lead of the oxidation zone.
  • Approx. 25 t / h of a feed mixture with 10% Ag, 40% Pb and the rest of the slag components are charged onto the slag layer in the oxidation zone.
  • the oxygen potential in the oxidation zone is adjusted by adjusting the amount of oxygen blown in so that 10% of the lead flow is obtained as primary lead and about 99% of the silver lead is collected in this primary lead.
  • a rich lead or raw silver with about 70% Ag is generated in the oxidation zone and drawn off from it.
  • the low-silver secondary lead with a silver content of approximately 0.01 to 0.02% and the slag are drawn off from the reduction zone.
  • the feed mixture corresponds to Example 1.
  • the oxygen potential in the oxidation zone is set so that 5% of the lead flow as primary lead accumulate and about 99% of the silver lead is collected in the primary lead. A rich lead or raw silver with about 83% Ag is produced.
  • Approx. 25 t / h of a feed mixture with 1% Ag, 40% Pb and the rest of the slag components are fed into the oxidation zone.
  • the oxygen potential is adjusted in such a way that about 10% of the lead lead is obtained as primary lead and about 99% of the silver lead is collected in this primary lead.
  • a rich lead with about 20% Ag is generated in the oxidation zone and drawn off from it.
  • the low-silver secondary lead with a silver content of approximately 0.01% and the slag are drawn off from the reduction zone.
  • the feed mixture corresponds to Example 3.
  • the oxygen potential in the oxidation zone is set so that 5% of the lead lead is obtained as the primary lead and about 99% of the silver lead is collected in the primary lead. A rich lead with about 32% Ag is produced.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (4)

  1. Procédé de fusion en continu de plomb métallique constitué de précurseurs contenant des métaux précieux et du plomb, caractérisé en ce qu'il consiste,
    a) à effectuer la fusion de la charge dans un réacteur horizontal oblong ayant une masse fondue constituée d'une phase de crasse et de deux phases distinctes de plomb,
    b) à charger la charge d'un côté du réacteur dans une zone d'oxydation sur la phase de crasse et à insuffler des gaz contenant de l'oxygène dans la phase de plomb,
    c) à se rendre maître de la pression partielle de l'oxygène dans la zone d'oxydation de façon que le plomb primaire fondu ait une teneur en argent d'au moins 20 %, que la quantité de plomb primaire représente moins de 10 % de la teneur précédente en plomb et qu'il se forme une crasse contenant de l'oxyde de plomb,
    d) à retirer le plomb primaire de la zone d'oxydation et à faire s'écouler la crasse contenant de l'oxyde de plomb dans une zone de réduction de l'autre côté du réacteur,
    e) à introduire dans la zone de réduction des substances réductrices dans la phase de crasse,
    f) à soutirer de la zone de réduction une crasse pauvre en plomb et du plomb secondaire de leurs phases.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il consiste à se rendre maître suivant c) de la pression partielle dans la zone d'oxydation de façon que le plomb primaire fondu ait une teneur en argent d'au moins 50 % et que la quantité de plomb primaire représente moins de 5 % de la teneur précédente en plomb.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les précurseurs engagés contiennent des matériaux sulfurés contenant du plomb.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'il consiste à insuffler dans la phase de plomb secondaire dans la zone de réduction des agents réducteurs carbonacés et des gaz contenant de l'oxygène au moyen de buses et à régler le niveau de la phase de plomb de manière à provoquer une conversion de l'agent réducteur en CO et le cas échéant en H₂ d'au moins 50 % dans la phase de plomb avant l'entrée dans la phase de crasse.
EP92202548A 1991-09-05 1992-08-20 Procédé pour la fusion de plomb métallique en continu Expired - Lifetime EP0530893B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4129475A DE4129475A1 (de) 1991-09-05 1991-09-05 Verfahren zum kontinuierlichen erschmelzen von metallischem blei
DE4129475 1991-09-05

Publications (2)

Publication Number Publication Date
EP0530893A1 EP0530893A1 (fr) 1993-03-10
EP0530893B1 true EP0530893B1 (fr) 1995-11-08

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EP92202548A Expired - Lifetime EP0530893B1 (fr) 1991-09-05 1992-08-20 Procédé pour la fusion de plomb métallique en continu

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EP (1) EP0530893B1 (fr)
DE (2) DE4129475A1 (fr)
ES (1) ES2081034T3 (fr)
GR (1) GR3018515T3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101200777B (zh) * 2007-09-24 2010-06-16 云南锡业集团（控股）有限责任公司 硫化铅精矿连续冶炼的方法及设备
CN110804701A (zh) * 2019-12-06 2020-02-18 湖北大江环保科技股份有限公司 侧吹转炉过饱和富氧熔炼工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU75732A1 (fr) * 1976-09-06 1978-04-27
DE3029682A1 (de) * 1980-08-06 1982-03-11 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum kontinuierlichen direkten schmelzen von metallischem blei aus sulfidischen bleikonzentraten
US4741770A (en) * 1985-04-03 1988-05-03 Cra Services Limited Zinc smelting process using oxidation zone and reduction zone
DE3539164C1 (en) * 1985-11-05 1987-04-23 Kloeckner Humboldt Deutz Ag Process and smelting furnace for producing non-ferrous metals

Also Published As

Publication number Publication date
EP0530893A1 (fr) 1993-03-10
ES2081034T3 (es) 1996-02-16
GR3018515T3 (en) 1996-03-31
DE4129475A1 (de) 1993-03-11
DE59204246D1 (de) 1995-12-14

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