EP0438622A1 - Method and apparatus for removing arsenic, tin and antimony from crude lead. - Google Patents

Method and apparatus for removing arsenic, tin and antimony from crude lead. Download PDF

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Publication number
EP0438622A1
EP0438622A1 EP90101459A EP90101459A EP0438622A1 EP 0438622 A1 EP0438622 A1 EP 0438622A1 EP 90101459 A EP90101459 A EP 90101459A EP 90101459 A EP90101459 A EP 90101459A EP 0438622 A1 EP0438622 A1 EP 0438622A1
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Prior art keywords
lead
oxygen
cylinder
antimony
volume
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German (de)
French (fr)
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EP0438622B1 (en
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Peter Dipl.-Ing. Burany
Juan Jorge Dipl.-Ing. Von Lücken
Bernhard Hendriks
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Metaleurop Weser Blei GmbH
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Metaleurop Weser Blei GmbH
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Priority to DE59006768T priority Critical patent/DE59006768D1/en
Priority to AT90101459T priority patent/ATE109839T1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/06—Refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ

Definitions

  • the invention relates to a method for removing arsenic, tin, antimony from silver-containing lead by means of technical oxygen in a lead smelting boiler and an apparatus for carrying out the method.
  • Tin, arsenic and antimony are removed from lead containing silver in lead metallurgy using either the Harris or flame furnace method.
  • Harris process In addition to the separation of tin, arsenic and antimony, the Harris process (Ullmann, 3rd edition, volume 4, pages 498 - 501) is primarily used to process lead-rich and / or tellurium-rich lead, resulting in valuable, sometimes highly concentrated end products .
  • the above-mentioned contamination is separated from the lead with caustic soda and a strong oxidizing agent, preferably saltpetre, to form Na 3 Sb0 4 , Na 3 AS0 4 . and Na 2 SnO 3 , which are obtained in the form of a liquid salt slag.
  • a strong oxidizing agent preferably saltpetre
  • Salt slag processing as the actual core of the Harris process requires extensive equipment and correspondingly high investment costs. The process is considered costly and requires careful monitoring. For the reasons mentioned, the Harris process has not become established on most lead smelters.
  • the antimony is oxidized in addition to arsenic and tin at 700-750 C by means of atmospheric oxygen.
  • rectangular flame or refining furnaces are used, the exhaust gas of which is fed to a dedusting filter in a cooler after the temperature has been reduced.
  • the air blown into the lead bath via lances oxidizes tin, arsenic and antimony in the order mentioned to form double oxides, which are drawn off from the furnace as a liquid smear.
  • smears 8 - 25% Sb, 1 - 5% As and 30 - 50 ppm Ag are produced.
  • the continuous flame furnace process which is characterized by high sales, results in smears with only 8 - 13% Sb.
  • the low antimony contents lead to correspondingly high smear quantities and therefore to increased processing costs.
  • the smears are further processed by reducing melting into an alloy containing antimony and arsenic, called raw hard lead, from which subsequent hard lead quality results from subsequent refining.
  • the silver contained in it passes into the hard lead, from which it cannot be removed, so that there is a corresponding loss of valuable metal.
  • the silver-containing hard lead cannot be marketed due to the exceeding of the silver limit values in the commercial hard lead.
  • This method can only be used for primary lead smelters that process silver-containing lead, if, as in the example above, the smear is broken down into a low-Ag smear and Ag-rich lead before the reduction to raw lead in a separate process step .
  • the Seiger process is carried out, for example, in a short drum oven or in a Herdseiger oven. The additional effort for segregation considerably reduces the advantage of boiler refining.
  • the invention is therefore based on the object of specifying an apparatus and a method which avoid the abovementioned disadvantages (such as, for example, silver-containing smears, additional reagent consumption, higher working temperature, etc.) during refining in the lead smelting boiler and tin, arsenic and antimony removal using technical oxygen is carried out in a conventional lead smelting boiler.
  • disadvantages such as, for example, silver-containing smears, additional reagent consumption, higher working temperature, etc.
  • oxygen is introduced into a turbulent stream of liquid lead which is restricted to a proportionate volume, based on the melting tank, whereupon the lead intimately mixed with oxygen enters a larger volume for calming purposes, in which the elements to be separated float and are smeared in the form of the oxides.
  • the method is carried out in a device which consists of two cylinders of different volumes, which are arranged vertically to one another and mutually adjustable and protrude above the surface of the melt. They are suspended from a crossbar and the entire melting tank is covered by a hood.
  • the turbulent flow of lead is generated by a lead pump, the outlet opening of which is located on the pressure side of the pump above the lead level.
  • the turbulence in the small cylinder can also be generated by a nozzle-like configuration of the outlet opening of the pump below the lead level.
  • Reaction tube 4 in the manner of a small cylinder, pumped.
  • the reaction tube is vertically and adjustably attached to the wall of the cylinder 1 and is immersed in the lead bath located in the cylinder 1 with approximately two thirds of its total length.
  • the lead entering the reaction tube vertically from above then flows through the cylinder 1 at a reduced speed and flows back at the bottom of the cylinder through the opening 3 located there into the lead melting tank.
  • Technical oxygen is blown into the reaction tube through a lance 5.
  • the strong turbulent flow mixes the oxygen and lead intimately.
  • the oxygen is entrained in the lead bath of cylinder 1 so that the good dispersion results in rapid oxidation, primarily of the secondary metals.
  • the flow is slowed down to such an extent that the liquid smear 15 separates from the lead due to the density differences, collects on the bath surface 16 of the cylinder 1 and can run through the puncture opening 6 in the cylinder wall via a channel 7 into a crucible 8.
  • the boiler remains constantly covered with a hood 9, which is connected to a dedusting device via a suction pipe 10.
  • the process can be carried out batchwise, semi-continuously or continuously.
  • the Sn-As-Sb removal was set using the flame furnace method and replaced by the proposed method and apparatus, which now refines the entire silver-containing lead flow without problems.
  • the melting kettles available for the furnace refining were sufficient for the kettle refining, so that, apart from the simple refining apparatus according to the invention, no additional outlay on equipment was required.
  • the amount of smear reduced compared to the flame furnace method from 45 kg smear per ton of lead to 26 kg smear / t of lead, which means that the smear on hard lead 15 is further processed kWh / t of lead reduction energy and 6 kWh / t of lead lead heating energy were saved.
  • This method eliminates the need for refinery furnaces, including exhaust gas dedusting, which significantly reduces operating costs, which in turn significantly reduces the harmful effects on the atmosphere.

Abstract

A method and apparatus for removing arsenic, tin and antimony from lead bullion by means of industrial oxygen are described, the oxygen being introduced into a turbulent molten stream of lead, restricted to a limited volume and entering, mixed with lead, a larger volume of molten lead, in which the compounds, which are to be separated off, float in the form of the oxides and run out as dross into a crucible. The apparatus for carrying out the method comprises two cylinders, arranged one within the other, of different volume, which dip to different depths into the molten lead in the melting vessel, the lead stream in the smaller cylinder being generated by means of a lead pump and the industrial oxygen being introduced into this lead stream. <IMAGE>

Description

Die Erfindung betrifft ein Verfahren zur Entfernung von Arsen, Zinn, Antimon aus silberhaltigem Werkblei mittels technischem Sauerstoff in einem Bleischmelzkessel sowie eine Vorrichtung zur Durchführung des Verfahrens.The invention relates to a method for removing arsenic, tin, antimony from silver-containing lead by means of technical oxygen in a lead smelting boiler and an apparatus for carrying out the method.

Die Entfernung von Zinn, Arsen und Antimon aus silberhaltigem Werkblei erfolgt in der Bleimetallurgie entweder nach dem Harris- oder Flammofen-Verfahren.Tin, arsenic and antimony are removed from lead containing silver in lead metallurgy using either the Harris or flame furnace method.

Das Harris-Verfahren (Ullmann, 3. Auflage, Band 4, Seite 498 - 501) wird neben der Abtrennung von Zinn, Arsen und Antimon vor allem zur Aufarbeitung von zinnreichem und/oder tellurreichen Blei eingesetzt, wobei wertvolle, zum Teil hochkonzentrierte Enderzeugnisse anfallen.In addition to the separation of tin, arsenic and antimony, the Harris process (Ullmann, 3rd edition, volume 4, pages 498 - 501) is primarily used to process lead-rich and / or tellurium-rich lead, resulting in valuable, sometimes highly concentrated end products .

Die Abtrennung der vorgenannten Verunreinigung aus dem Werkblei geschieht mit Ätznatron und einem starken Oxidationsmittel, vorzugsweise Salpeter, unter Bildung von Na3Sb04, Na3AS04. und Na2SnO3, die in Form einer flüssigen Salzschlacke anfallen.The above-mentioned contamination is separated from the lead with caustic soda and a strong oxidizing agent, preferably saltpetre, to form Na 3 Sb0 4 , Na 3 AS0 4 . and Na 2 SnO 3 , which are obtained in the form of a liquid salt slag.

Anschließend müssen aus der Salzschlacke durch naßmetallurgische Aufarbeitung die aus dem Werkblei entfernten Verunreinigungen in Form konzentrierter und bleifreier Produkte abgetrennt werden. Die Salzschlackenaufarbeitung als eigentliches Kernstück des Harris-Verfahrens benötigt umfangreiche apparative Einrichtungen und entsprechend hohe Anlagekosten. Der Prozeß gilt als kostspielig und erfordert sorgfältige Überwachung. Aus den genannten Gründen hat sich das Harris-Verfahren auf den meisten Bleihütten nicht durchgesetzt.The contaminants removed from the lead in the form of concentrated and lead-free products must then be separated from the salt slag by wet metallurgical processing. Salt slag processing as the actual core of the Harris process requires extensive equipment and correspondingly high investment costs. The process is considered costly and requires careful monitoring. For the reasons mentioned, the Harris process has not become established on most lead smelters.

Bei dem bevorzugt angewendeten Flammofen-Verfahren (Ullmann, 3. Auflage, Band 4, Seite 498 - 501) wird das Antimon neben Arsen und Zinn bei 700 - 750 C mittels Luftsauerstoff oxidiert. Dazu verwendet man rechteckige Flamm- bzw. Raffinieröfen, deren Abgas nach Senken der Temperatur in einem Kühler einem Entstaubungsfilter zugeführt wird. Die über Lanzen in das Bleibad eingeblasene Luft oxidiert Zinn, Arsen und Antimon in der genannten Reihenfolge unter Bildung von Doppeloxiden, die als flüssiger Abstrich aus dem Ofen abgezogen werden. In Abhängigkeit von einer kontinuierlichen bzw. diskontinuierlichen Arbeitsweise werden Abstriche von 8 - 25 % Sb, 1 - 5 % As und 30 - 50 ppm Ag erzeugt. Bei dem durch hohen Umsatz gekennzeichneten kontinuierlichen Flammofen-Verfahren entstehen Abstriche mit nur 8 - 13 % Sb. Die niedrigen Antimongehalte führen zu entsprechend hohen Abstrichmengen und daher zu erhöhten Aufarbeitungskosten.In the preferred flame furnace method (Ullmann, 3rd edition, volume 4, pages 498-501), the antimony is oxidized in addition to arsenic and tin at 700-750 C by means of atmospheric oxygen. For this purpose, rectangular flame or refining furnaces are used, the exhaust gas of which is fed to a dedusting filter in a cooler after the temperature has been reduced. The air blown into the lead bath via lances oxidizes tin, arsenic and antimony in the order mentioned to form double oxides, which are drawn off from the furnace as a liquid smear. Depending on a continuous or discontinuous procedure, smears of 8 - 25% Sb, 1 - 5% As and 30 - 50 ppm Ag are produced. The continuous flame furnace process, which is characterized by high sales, results in smears with only 8 - 13% Sb. The low antimony contents lead to correspondingly high smear quantities and therefore to increased processing costs.

Die Abstriche werden durch reduzierendes Schmelzen zu einer antimon- und arsenhaltigen Legierung, Rohhartblei genannt, weiterverarbeitet, aus dem durch anschließende Raffination handelsübliche Hartbleiqualitäten entstehen.The smears are further processed by reducing melting into an alloy containing antimony and arsenic, called raw hard lead, from which subsequent hard lead quality results from subsequent refining.

Die vorgenannten Verfahren sind gekennzeichnet durch großen apparativen Aufwand (wie z.B. Salzschlackenaufbereitung beim Harris-Prozeß bzw. Kühler, Entstaubungs-Filter, Reserve-Öfen usw. beim Flammofen-Verfahren), durch einen hohen Energieverbrauch für die Aufarbeitung großer Zwischenprodukt-Mengen (Salzschlacken, Abstriche) sowie letztlich durch hohe Betriebskosten.The above-mentioned processes are characterized by a large outlay on equipment (such as salt slag processing in the Harris process or cooler, dedusting filter, reserve furnaces, etc. in the flame furnace process), by a high energy consumption for processing large quantities of intermediate products (salt slags, Cutbacks) and ultimately due to high operating costs.

Moderne Verfahren zur Abtrennung von Zinn, Arsen und Antimon aus Werkblei, die sowohl in Primär- als auch Sekundär-Bleihütten zum Einsatz kommen, arbeiten unter Verwendung von Sauerstoff/Luftgemischen in einem herkömmlichen Bleischmelzkessel. Dabei entstehen in Sekundär-Bleihütten vorzugsweise Abstriche, die problemlos aufgearbeitet werden können, weil das Werkblei der Sekundär-Bleihütten nur sehr geringe Silbergehalte aufweist ( < 30 g Ag/t). Änlichen Verfahren wird in einer Primär-Bleihütte, in der aus der vorzugsweisen Verarbeitung silberhaltiger Konzentrate und edelmetallhaltiger Vorstoffe ein silberhaltiges Werkblei mit Silbergehalten bis zu mehreren Tausend g Ag/t anfällt, ein abstrich mit 3,85 % Arsen, 3,25 % Antimon und 1 098 g/t Silber erzeugt. (Proceedings CIM Symposium on "Quality in Nonferrous Pyrometallurgical Processes" Vancouver (1985), Seite 137 - 140)Modern processes for the separation of tin, arsenic and antimony from lead, which are used in both primary and secondary lead smelters, work using oxygen / air mixtures in a conventional lead smelting boiler. Smears are preferably produced in secondary lead smelters, which can be worked up without any problems, because the lead of the secondary lead smelters has only very low silver contents (<30 g Ag / t). Similar processes are carried out in a primary lead smelter, in which a silver-containing lead with silver contents of up to several thousand g Ag / t is obtained from the preferred processing of silver-containing concentrates and precious metal-containing raw materials, a smear with 3.85% arsenic, 3.25% antimony and 1,098 g / t silver produced. (Proceedings CIM Symposium on "Quality in Nonferrous Pyrometallurgical Processes" Vancouver (1985), pages 137-140)

Das darin enthaltene Silber geht bei der anschließenden Reduktion des Abstrichs in das Hartblei über, aus dem es nicht entfernt werden kann, so daß ein entsprechender Wertmetallverlust eintritt. Außerdem läßt sich das silberhaltige Hartblei aufgrund der Überschreitung der Silbergrenzwerte im Handelshartblei nicht vermarkten. Diese Methode kann bei Primär-Bleihütten, die silberhaltiges Werkblei verarbeiten, nur dann durchgeführt werden wenn, wie im obigen Beispiel, der Abstrich vor der Reduktion zu Rohhartblei in einem seperaten Verfahrensschritt durch Seigerung in einen Ag-armen Abstrich und Ag-reiches Werkblei zerlegt wird. Der Seigerprozeß wird zum Beispiel in einem Kurztrommelofen oder in einem Herdseigerofen durchgeführt. Durch den zusätzlichen Aufwand für die Seigerung wird der Vorteil der Kesselraffination erheblich gemindert.When the smear is subsequently reduced, the silver contained in it passes into the hard lead, from which it cannot be removed, so that there is a corresponding loss of valuable metal. In addition, the silver-containing hard lead cannot be marketed due to the exceeding of the silver limit values in the commercial hard lead. This method can only be used for primary lead smelters that process silver-containing lead, if, as in the example above, the smear is broken down into a low-Ag smear and Ag-rich lead before the reduction to raw lead in a separate process step . The Seiger process is carried out, for example, in a short drum oven or in a Herdseiger oven. The additional effort for segregation considerably reduces the advantage of boiler refining.

Somit wird deutlich, daß die Kesselraffination mittels mit Sauerstoff angereicherte Luft nur dann wirtschaftlich durchgeführt werden kann, wenn die Silbergehalte im Werkblei sehr niedrig sind, wie zum Beispiel bei der Raffination von Altblei gemäß DE-PS 3 332 796, die bei Temperaturen von mindestens 630 ° C betrieben werden muß.It is thus clear that the boiler refining by means of oxygen-enriched air can only be carried out economically if the silver content in the lead is very low, such as in the refining of used lead according to DE-PS 3 332 796, which occurs at temperatures of min at least 630 ° C must be operated.

Der Erfindung liegt daher die Aufgabe zugrunde, eine Vorrichtung und ein Verfahren anzugeben, welche die vorgenannten Nachteile (wie z.B. silberhaltige Abstriche, zusätzlicher Reagenzienverbrauch, höhere Arbeitstemperatur, usw.) bei der Raffination im Bleischmelzkessel vermeiden und Zinn-, Arsen und Antimonentfernung unter Einsatz von technischem Sauerstoff in einem herkömmlichen Bleischmelzkessel durchgeführt wird.The invention is therefore based on the object of specifying an apparatus and a method which avoid the abovementioned disadvantages (such as, for example, silver-containing smears, additional reagent consumption, higher working temperature, etc.) during refining in the lead smelting boiler and tin, arsenic and antimony removal using technical oxygen is carried out in a conventional lead smelting boiler.

Gelöst wird diese Aufgabe dadurch, daß bei dem Verfahren der eingangs beschriebenen Art Sauerstoff in einen auf ein anteiliges Volumen, bezogen auf den Schmelzkessel, eingeengten turbulenten Strom flüssigen Bleies eingeleitet wird, worauf das mit Sauerstoff innig vermischte Blei in ein größeres Volumen zur Beruhigung eintritt, in welchem die abzutrennenden Elemente in Form der Oxide aufschwimmen und abgestrichen werden.This object is achieved in that, in the process of the type described at the outset, oxygen is introduced into a turbulent stream of liquid lead which is restricted to a proportionate volume, based on the melting tank, whereupon the lead intimately mixed with oxygen enters a larger volume for calming purposes, in which the elements to be separated float and are smeared in the form of the oxides.

Das Verfahren wird in einer Vorrichtung durchgeführt, die aus zwei Zylindern unterschiedlichen Volumens bestehen, die vertikal aneinander und gegeneinander verstellbar angeordnet sind und über die Oberfläche der Schmelze heraus-ragen. Sie sind an einer Traverse aufgehängt und der gesamte Schmelzkessel ist durch eine Haube abgedeckt. Der turbulente Strom des Bleies wird durch eine Bleipumpe erzeugt, deren Auslaßöffnung der Druckseite der Pumpe oberhalb des Bleispiegels liegt.The method is carried out in a device which consists of two cylinders of different volumes, which are arranged vertically to one another and mutually adjustable and protrude above the surface of the melt. They are suspended from a crossbar and the entire melting tank is covered by a hood. The turbulent flow of lead is generated by a lead pump, the outlet opening of which is located on the pressure side of the pump above the lead level.

Die Turbulenz in dem kleinen Zylinder kann auch durch eine düsenartige Ausgestaltung der Auslaßöffnung der Pumpe erzeugt werden unterhalb des Bleispiegels.The turbulence in the small cylinder can also be generated by a nozzle-like configuration of the outlet opening of the pump below the lead level.

Die erfindungsgemäße Vorrichtung wird nun anhand der Zeichnung, die einen schematischen Querschnitt zeigt, näher erläutert:

  • Die zur Durchführung des Verfahrens erfindungsgemäße erdachte und verwendete Vorrichtung ist im Prinzip von zylindrischer Gestalt und mit einer Bleipumpe verbunden. Sie besteht im wesentlichen aus einem Stahlblechzylinder 1, der mit seinem Unterteil in das Bleibad 12 des Bleischmelzkessels eintaucht. Der Zylinder 1 und die Bleipumpe 2 bilden eine transportable Einheit, die zusammen mit einer Traverse auf den Kesselrand aufgesetzt wird. Bei Einsetzen der Vorrichtung tritt das Blei aus dem Kessel durch eine Öffnung 3 im Unterteil des Zylinders 1 hindurch und füllt diesen nach dem Prinzip der kommunizierenden Systeme. Mit einer Bleipumpe 2 wird das Blei aus dem Kessel in das im Zylinder 1 befindliche
The device according to the invention will now be explained in more detail with reference to the drawing, which shows a schematic cross section:
  • The device invented and used to carry out the method is in principle cylindrical in shape and connected to a lead pump. It consists essentially of a sheet steel cylinder 1, which dips with its lower part into the lead bath 12 of the lead smelting boiler. The cylinder 1 and the lead pump 2 form a transportable unit which is placed on the edge of the boiler together with a crossbar. When the device is inserted, the lead leaves the boiler through an opening 3 in the lower part of the cylinder 1 and fills it according to the principle of the communicating systems. With a lead pump 2, the lead from the boiler into that in the cylinder 1

Reaktionsrohr 4, in der Art eines kleinen Zylinders, gepumpt. Das Reaktionsrohr ist senkrecht und einstellbar an der Wand des Zylinders 1 befestigt und wird etwa mit zweidrittel seiner Gesamtlänge in das im Zylinder 1 befindliche Bleibad eingetaucht.Reaction tube 4, in the manner of a small cylinder, pumped. The reaction tube is vertically and adjustably attached to the wall of the cylinder 1 and is immersed in the lead bath located in the cylinder 1 with approximately two thirds of its total length.

Das senkrecht von oben in das Reaktionsrohr einlaufende Blei durchströmt anschließend mit verringerter Geschwindigkeit den Zylinder 1 und fließt am Boden des Zylinders durch die dort befindliche Öffnung 3 in den Bleischmelzkessel zurück. In das Reaktionsrohr wird technischer Sauerstoff durch eine Lanze 5 eingeblasen. Durch die starke turbulente Strömung werden der Sauerstoff und das Blei innig vermischt. Der Sauerstoff wird in das Bleibad des Zylinder 1 mitgerissen so daß durch die gute Dispersion eine rasche Oxidation vornehmlich der Nebenmetalle stattfindet. Im Zylinder 1 wird die Strömung soweit verlangsamt, daß sich der flüssige Abstrich 15 vom Blei aufgrund der Dichteunterschiede trennt, auf der Badoberfläche 16 des Zylinders 1 sammelt und durch die Stichöffnung 6 in der Zylinderwand über eine Rinne 7 in einen Tiegel 8 ablaufen kann. Der Kessel bleibt mit einer Haube 9 ständig abgedeckt, die über eine Absaug-Rohrleitung 10 mit einer Entstaubungseinrichtung verbunden ist. Das Verfahren kann diskontinuierlich, halbkontinuierlich oder kontinuierlich durchgeführt werden.The lead entering the reaction tube vertically from above then flows through the cylinder 1 at a reduced speed and flows back at the bottom of the cylinder through the opening 3 located there into the lead melting tank. Technical oxygen is blown into the reaction tube through a lance 5. The strong turbulent flow mixes the oxygen and lead intimately. The oxygen is entrained in the lead bath of cylinder 1 so that the good dispersion results in rapid oxidation, primarily of the secondary metals. In the cylinder 1, the flow is slowed down to such an extent that the liquid smear 15 separates from the lead due to the density differences, collects on the bath surface 16 of the cylinder 1 and can run through the puncture opening 6 in the cylinder wall via a channel 7 into a crucible 8. The boiler remains constantly covered with a hood 9, which is connected to a dedusting device via a suction pipe 10. The process can be carried out batchwise, semi-continuously or continuously.

Die Erfindung wird an zwei Anwendungsbeispielen nachfolgend näher erläutert:The invention is explained in more detail below using two application examples:

Beispiel 1:Example 1:

150 000 kg entkupfertes Werkblei mit 0,8 % Sb, 0,05 % As und 1 500 g/t Ag wurden im Kessel bei 580 ° C Anfangstemperatur mittels technischem Sauerstoff nach der beschriebenen Erfindung raffiniert. Nach einer Stunde begann der Abstrich in einen Tiegel abzulaufen. Nach 300 Minuten zeigte eine Probe, daß das Antimon und Arsen entfernt worden war. Die Endtemperatur betrug 210 610 oe, der Sauerstoffverbrauch betrug 210 Nm3. Es wurden 3 400 kg Abstrich mit 30,2 Sb, 2,0 % As und 9 g/t Ag erzeugt.150,000 kg of decoupled lead with 0.8% Sb, 0.05% As and 1 500 g / t Ag were refined in the boiler at 580 ° C starting temperature using technical oxygen according to the invention described. After an hour the smear started to drain into a crucible. After 300 minutes a sample showed that the antimony and arsenic had been removed. The final temperature was 210 610 o e, the oxygen consumption was 210 Nm 3 . 3,400 kg smear with 30.2 Sb, 2.0% As and 9 g / t Ag were produced.

Beispiel 2:Example 2:

In einem Hüttenwerk wurde die Sn-As-Sb-Entfernung nach dem Flammofen-Verfahren eingestellt und durch die vorgeschlagene Methode und Apparatur ersetzt, mit der nun der gesamte silberhaltige Werkbleivorlauf problemlos raffiniert wird. Die für die Ofenraffination vorhandenen Schmelzkessel reichten für die Kesselraffination aus, so daß abgesehen von der einfachen erfindungsgemäßen Raffinationsapparatur kein zusätzlicher apparativer Aufwand erforderlich war.In a metallurgical plant, the Sn-As-Sb removal was set using the flame furnace method and replaced by the proposed method and apparatus, which now refines the entire silver-containing lead flow without problems. The melting kettles available for the furnace refining were sufficient for the kettle refining, so that, apart from the simple refining apparatus according to the invention, no additional outlay on equipment was required.

Folgende charakteristischen Verfahrensdaten wurden mit der erfindungsgemäßen Betriebsweise ermittelt:

  • Der Heizungsenergieverbrauch verminderte sich bei gleichbleibender Raffinationsleistung um 58 kWH/t Werkblei.
The following characteristic process data were determined using the operating mode according to the invention:
  • The heating energy consumption was reduced by 58 kWH / t of lead while the refining output remained the same.

Durch die im Vergleich zum Flammofen-Verfahren nicht benötigten Mengen an Kühlwasser und Druckluft sowie durch Fortfall der Abgaskühlung und durch die Verminderung des Abgasvolumens konnte der Stromverbrauch um 2,3 kWh/t Werkblei (einschließlich Strom zur Sauerstoffherstellung) reduziert werden. Ausgehend von einem Werkblei mit durchschnittlichen 0,8 % Antimon und 0,05 % Arsen verminderte sich der Abstrichanfall gegenüber dem Flammofen-Verfahren von 45 kg Abstrich je Tonne Werkblei auf 26 kg Abstrich/t Werkblei, wodurch bei der Weiterverarbeitung des Abstrichs auf Hartblei 15 kWh/t Werkblei Reduktionsenergie und 6 kWh/t Werkblei Heizenergie eingespart wurden.The amount of cooling water and compressed air that is not required in comparison to the flame furnace method, as well as the elimination of the exhaust gas cooling and the reduction in the exhaust gas volume, reduced the electricity consumption by 2.3 kWh / t of lead (including electricity for oxygen production). Starting from a lead with an average of 0.8% antimony and 0.05% arsenic, the amount of smear reduced compared to the flame furnace method from 45 kg smear per ton of lead to 26 kg smear / t of lead, which means that the smear on hard lead 15 is further processed kWh / t of lead reduction energy and 6 kWh / t of lead lead heating energy were saved.

Bei einem Werkblei-Vorlauf von zum Beispiel 120 000 t im Jahr ergibt sich eine Energieeinsparung von rund 9 760 000 kWh/Jahr. Durch diese Methode entfällt das Vorhalten von Raffinieröfen einschließlich der Abgasentstaubung, wodurch die Betriebskosten merklich reduziert werden, wodurch sich wiederum eine beträchtliche Verringerung schädlicher Einwirkung auf die Atmosphäre ergibt.With a lead production of, for example, 120,000 t per year, this results in energy savings of around 9,760,000 kWh / year. This method eliminates the need for refinery furnaces, including exhaust gas dedusting, which significantly reduces operating costs, which in turn significantly reduces the harmful effects on the atmosphere.

Da der bei dieser Methode entstehende Abstrich durch die fehlenden Anteile an Zuschlägen wie z . B. Kalk oder Ätznatron einen niedrigen Schmelzpunkt aufweist, wird die Weiterverarbeitung kostenmäßig begünstigt, darüber hinaus auch dadurch, daß geringe Schlackenmengen anfallen.Since the smear created with this method is due to the lack of shares in supplements such. B. lime or caustic soda has a low melting point, the processing is favored in terms of cost, moreover in that small amounts of slag are obtained.

Claims (5)

1. Verfahren zur Entfernung von As, Sn und Sb aus Werkblei aus schmelzflüssigem, im Schmelzkessel befindlichen Blei mittels technischen Sauerstoff, dadurch gekennzeichnet, daß der Sauerstoff in einen, auf ein anteiliges Volumen, bezogen auf den Schmelzkessel, eingeengten turbulenten Strom flüssigen Bleies eingeleitet wird, worauf das mit Sauerstoff innig vermischte Blei in ein größeres Volumen zur Beruhigung eintritt, in welchem die abzutrennenden Elemente in Form der Oxide aufschwimmen und abgestrichen werden.1. A process for the removal of As, Sn and Sb from lead from molten lead in the melting tank by means of technical oxygen, characterized in that the oxygen is introduced into a turbulent stream of liquid lead restricted to a proportionate volume, based on the melting tank , whereupon the lead intimately mixed with oxygen enters a larger volume for calming, in which the elements to be separated float and are wiped off in the form of the oxides. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Sauerstoff in der Nähe des Eintritts des flüssigen Bleies eingeleitet wird.2. The method according to claim 1, characterized in that the oxygen is introduced in the vicinity of the entry of the liquid lead. 3. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1 und 2, dadurch gekennzeichnet, daß sie aus zwei ineinander angeordneten Zylindern (1 und 4) unterschiedlichen Volumens besteht, wobei in dem kleineren Zylinder (4) die Reaktion zwischen Blei und Sauerstoff stattfindet und beide Zylinder (1 und 4) gegeneinander verstellbar sind und über die Oberfläche der Schmelze hinausragen.3. Device for carrying out the method according to claim 1 and 2, characterized in that it consists of two cylinders (1 and 4) of different volumes arranged one inside the other, the reaction between lead and oxygen taking place in the smaller cylinder (4) and both cylinders (1 and 4) are mutually adjustable and protrude above the surface of the melt. 4. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, daß der große Zylinder (1) an seinem unteren Ende bis auf eine Auslaßöffnung (3) verschlossen ist, daß die Zylinder an einer Traverse aufgehängt sind und daß der Schmelzkessel (11) mit einer Haube abgedeckt ist.4. The device according to claim 4, characterized in that the large cylinder (1) is closed at its lower end except for an outlet opening (3), that the cylinders are suspended on a crossmember and that the melting tank (11) is covered with a hood is. 5. Vorrichtung nach Anspruch 4 und 5, dadurch gekennzeichnet, daß eine Bleipumpe (2) den turbulenten Strom des flüssigen Bleies in dem kleinen Zylinder (4) erzeugt, wobei die Auslaßöffnung (17) der Bleipumpe (2) oberhalb des Bleispiegels (16) in dem Zylinder (4) kleineren Volumens angeordnet ist.5. Apparatus according to claim 4 and 5, characterized in that a lead pump (2) generates the turbulent flow of the liquid lead in the small cylinder (4), the outlet opening (17) of the lead pump (2) above the lead level (16) is arranged in the cylinder (4) of smaller volume.
EP90101459A 1988-09-20 1990-01-25 Method and apparatus for removing arsenic, tin and antimony from crude lead. Expired - Lifetime EP0438622B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59006768T DE59006768D1 (en) 1990-01-25 1990-01-25 Method and device for removing arsenic, tin and antimony from lead with oxygen.
AT90101459T ATE109839T1 (en) 1990-01-25 1990-01-25 PROCESS AND APPARATUS FOR REMOVING ARSENIC, TIN AND ANTIMONY FROM LEAD WITH OXYGEN.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3831898A DE3831898A1 (en) 1988-09-20 1988-09-20 METHOD AND DEVICE FOR REMOVING ARSEN, TIN AND ANTIMONE FROM WORK LEAD WITH OXYGEN
CA002012981A CA2012981C (en) 1988-09-20 1990-03-23 Removal of arsenic, tin and antimony from crude lead containing silver

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EP0438622B1 EP0438622B1 (en) 1994-08-10

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DE4322782A1 (en) * 1993-07-08 1995-01-12 Messer Griesheim Gmbh Process for removing tin, arsenic and antimony from molten lead
DE19500266C1 (en) * 1995-01-07 1996-02-22 Metallgesellschaft Ag Method of separating a heavy liquid phase from a light liquid phase

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE522976C (en) * 1930-03-19 1931-04-17 Blei Und Silberhuette Braubach Method and device for mixing gases or vapors with melts, in particular with metal or alloy melts
DE654528C (en) * 1932-11-25 1937-12-27 George Kenneth Williams Process for removing arsenic, antimony and / or tin from lead
DE3332796C1 (en) * 1983-07-25 1984-06-28 Josef Dr.-Ing. 8000 München Blanderer Process for refining antimony-containing lead melts with supply of oxygen-enriched air

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE522976C (en) * 1930-03-19 1931-04-17 Blei Und Silberhuette Braubach Method and device for mixing gases or vapors with melts, in particular with metal or alloy melts
DE654528C (en) * 1932-11-25 1937-12-27 George Kenneth Williams Process for removing arsenic, antimony and / or tin from lead
DE3332796C1 (en) * 1983-07-25 1984-06-28 Josef Dr.-Ing. 8000 München Blanderer Process for refining antimony-containing lead melts with supply of oxygen-enriched air

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ulmann 3. Auflage, Band 4, Seiten 494-501, 1943, Urban & Scharzenberg, München-Berlin *

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DE3831898A1 (en) 1990-03-29
ES2023624A4 (en) 1992-02-01
CA2012981A1 (en) 1991-09-23
DE3831898C2 (en) 1991-07-18
CA2012981C (en) 1996-01-16
EP0438622B1 (en) 1994-08-10
ES2023624T3 (en) 1994-10-16

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