EP0438622A1 - Procédé et dispositif pour l'élimination d'arsenic, d'étain et d'antimoine à partir de plomb d'oeuvre par oxygène - Google Patents

Procédé et dispositif pour l'élimination d'arsenic, d'étain et d'antimoine à partir de plomb d'oeuvre par oxygène 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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EP
European Patent Office
Prior art keywords
lead
oxygen
cylinder
antimony
volume
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
Application number
EP90101459A
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German (de)
English (en)
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EP0438622B1 (fr
Inventor
Peter Dipl.-Ing. Burany
Juan Jorge Dipl.-Ing. Von Lücken
Bernhard Hendriks
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.)
Metaleurop Weser Blei GmbH
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Metaleurop Weser Blei GmbH
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Metaleurop Weser Blei GmbH filed Critical Metaleurop Weser Blei GmbH
Priority to DE59006768T priority Critical patent/DE59006768D1/de
Priority to AT90101459T priority patent/ATE109839T1/de
Publication of EP0438622A1 publication Critical patent/EP0438622A1/fr
Application granted granted Critical
Publication of EP0438622B1 publication Critical patent/EP0438622B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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.
EP90101459A 1988-09-20 1990-01-25 Procédé et dispositif pour l'élimination d'arsenic, d'étain et d'antimoine à partir de plomb d'oeuvre par oxygène Expired - Lifetime EP0438622B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59006768T DE59006768D1 (de) 1990-01-25 1990-01-25 Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff.
AT90101459T ATE109839T1 (de) 1990-01-25 1990-01-25 Verfahren und vorrichtung zur entfernung von arsen, zinn und antimon aus werkblei mit sauerstoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3831898A DE3831898A1 (de) 1988-09-20 1988-09-20 Verfahren und vorrichtung zur entfernung von arsen, zinn und antimon aus werkblei mit sauerstoff
CA002012981A CA2012981C (fr) 1988-09-20 1990-03-23 Elimination de l'arsenic, de l'etain et de l'antimoine du plomb brut argentifere

Publications (2)

Publication Number Publication Date
EP0438622A1 true EP0438622A1 (fr) 1991-07-31
EP0438622B1 EP0438622B1 (fr) 1994-08-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90101459A Expired - Lifetime EP0438622B1 (fr) 1988-09-20 1990-01-25 Procédé et dispositif pour l'élimination d'arsenic, d'étain et d'antimoine à partir de plomb d'oeuvre par oxygène

Country Status (4)

Country Link
EP (1) EP0438622B1 (fr)
CA (1) CA2012981C (fr)
DE (1) DE3831898A1 (fr)
ES (1) ES2023624T3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4322782A1 (de) * 1993-07-08 1995-01-12 Messer Griesheim Gmbh Verfahren zum Entfernen von Zinn, Arsen und Antimon aus schmelzflüssigem Blei
DE19500266C1 (de) * 1995-01-07 1996-02-22 Metallgesellschaft Ag Verfahren und Vorrichtung zur Trennung einer spezifisch leichteren Phase von einer spezifisch schwereren flüssigen Phase

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE522976C (de) * 1930-03-19 1931-04-17 Blei Und Silberhuette Braubach Verfahren und Vorrichtung zur Durchmischung von Gasen oder Daempfen mit Schmelzen, insbesondere mit Metall- bzw. Legierungsschmelzen
DE654528C (de) * 1932-11-25 1937-12-27 George Kenneth Williams Verfahren zur Entfernung von Arsen, Antimon und/oder Zinn aus Blei
DE3332796C1 (de) * 1983-07-25 1984-06-28 Josef Dr.-Ing. 8000 München Blanderer Verfahren zur Raffination von antimonhaltigen Bleischmelzen unter Zufuhr von Luft, die mit Sauerstoff angereichert wird

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE522976C (de) * 1930-03-19 1931-04-17 Blei Und Silberhuette Braubach Verfahren und Vorrichtung zur Durchmischung von Gasen oder Daempfen mit Schmelzen, insbesondere mit Metall- bzw. Legierungsschmelzen
DE654528C (de) * 1932-11-25 1937-12-27 George Kenneth Williams Verfahren zur Entfernung von Arsen, Antimon und/oder Zinn aus Blei
DE3332796C1 (de) * 1983-07-25 1984-06-28 Josef Dr.-Ing. 8000 München Blanderer Verfahren zur Raffination von antimonhaltigen Bleischmelzen unter Zufuhr von Luft, die mit Sauerstoff angereichert wird

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 *

Also Published As

Publication number Publication date
DE3831898C2 (fr) 1991-07-18
DE3831898A1 (de) 1990-03-29
CA2012981C (fr) 1996-01-16
ES2023624T3 (es) 1994-10-16
EP0438622B1 (fr) 1994-08-10
ES2023624A4 (es) 1992-02-01
CA2012981A1 (fr) 1991-09-23

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