EP0438622B1 - Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff - Google Patents

Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff Download PDF

Info

Publication number
EP0438622B1
EP0438622B1 EP90101459A EP90101459A EP0438622B1 EP 0438622 B1 EP0438622 B1 EP 0438622B1 EP 90101459 A EP90101459 A EP 90101459A EP 90101459 A EP90101459 A EP 90101459A EP 0438622 B1 EP0438622 B1 EP 0438622B1
Authority
EP
European Patent Office
Prior art keywords
lead
oxygen
cylinder
antimony
melting pot
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
EP90101459A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0438622A1 (de
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
Original Assignee
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.)
Filing date
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/de
Application granted granted Critical
Publication of EP0438622B1 publication Critical patent/EP0438622B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C22B13/06—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 to 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 removed from the lead with caustic soda and a strong oxidizing agent, preferably saltpetre, to form Na3SbO4, Na3AsO4 and Na2SnO3, which are obtained in the form of a liquid salt slag.
  • a strong oxidizing agent preferably saltpetre
  • 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 workup.
  • the 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 for this purpose. 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.
  • the smears are further processed by reducing melting to an alloy containing antimony and arsenic, called raw hard lead, from which subsequent hard lead quality results from subsequent refining.
  • the silver contained therein changes into the hard lead, from which it cannot be removed, so that a corresponding loss of valuable metal occurs.
  • 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 carried out in 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 in a separate process step before reduction to raw hard lead .
  • the Seiger process is carried out, for example, in a short drum oven or in a Herdseiger oven. The additional effort for the segregation considerably reduces the advantage of boiler refining.
  • the invention is therefore based on the object of specifying a device 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 is carried out using technical oxygen 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 vessel, 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 a melting vessel and 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.
  • 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.
  • 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.
  • a lead pump 2 With a lead pump 2, the lead from the boiler into that in the cylinder 1 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 into the lead smelting boiler at the bottom of the cylinder through the opening 3 located there.
  • Technical oxygen is blown into the reaction tube through a lance 5.
  • the strong turbulent flow mixes the oxygen and the lead intimately.
  • the oxygen is entrained in the lead bath of cylinder 1, so that rapid oxidation primarily of the secondary metals takes place due to the good dispersion.
  • 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 is always 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 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.
  • the amount of smear decreased 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 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.
  • 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.

Landscapes

  • 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)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP90101459A 1988-09-20 1990-01-25 Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff Expired - Lifetime EP0438622B1 (de)

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 (en) 1988-09-20 1990-03-23 Removal of arsenic, tin and antimony from crude lead containing silver

Publications (2)

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

Family

ID=25674028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90101459A Expired - Lifetime EP0438622B1 (de) 1988-09-20 1990-01-25 Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff

Country Status (4)

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

Families Citing this family (3)

* 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
RU2259411C2 (ru) * 2003-11-11 2005-08-27 Чекушин Владимир Семенович Способ окислительного щелочного рафинирования свинца

Family Cites Families (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

Also Published As

Publication number Publication date
CA2012981A1 (en) 1991-09-23
ES2023624T3 (es) 1994-10-16
DE3831898A1 (de) 1990-03-29
CA2012981C (en) 1996-01-16
DE3831898C2 (enrdf_load_stackoverflow) 1991-07-18
EP0438622A1 (de) 1991-07-31
ES2023624A4 (es) 1992-02-01

Similar Documents

Publication Publication Date Title
US4489046A (en) Method for working-up arsenic-containing waste
DE3321687A1 (de) Verfahren und vorrichtung zum kontinuierlichen windfrischen von nichteisen-lechen
DE2521830C2 (de) Verfahren zur Raffination von stark verunreinigtem Schwarzkupfer
DE3045030A1 (de) Verfahren zum gewinnen von kupfer in anodenguete
DE69520523T2 (de) Anlage zum Schmelzen von Kupfer
EP0438622B1 (de) Verfahren und Vorrichtung zur Entfernung von Arsen, Zinn und Antimon aus Werkblei mit Sauerstoff
DE2602827C2 (de) Verfahren zum Auflösen von Edelmetallen aus edelmetallhaltigen Konzentraten, die sekundäres Platinmetall enthalten
DE40870T1 (de) Verfahren zur behandlung blei- und zinkhaltigen staubs der eisen- oder stahlerzeugung.
US5053076A (en) Process and device for removal of arsenic, tin & artimony from crude lead containing silver
EP0099711B1 (en) Continuous method of removing tin from lead
EP0633324A1 (de) Verfahren zum Entfernen von Zinn, Arsen und Antimon aus schmelzflüssigem Blei
DE3303810C2 (enrdf_load_stackoverflow)
DE1483165A1 (de) Verfahren und Anlage zur kontinuierlichen Raffination von Blei
SE0950219A1 (sv) Metod för att raffinera kopparbullion som innehåller antimon och/eller arsenik
DE2645585A1 (de) Verfahren zur freisetzung von wertmetallinhalten aus schlacken durch aufblasen
DE2036391C3 (de) Verfahren und Vorrichtung zum Rückgewinnen des Kupfergehaltes aus Rest- oder Nebenprodukten metallurgischer Verfahren
DE3332796C1 (de) Verfahren zur Raffination von antimonhaltigen Bleischmelzen unter Zufuhr von Luft, die mit Sauerstoff angereichert wird
DE1229736B (de) Verfahren zur Gewinnung von Blei aus zinkhaltigen sulfidischen Bleikonzentraten
DE3031007A1 (de) Verfahren zur verarbeitung von sulfidischen zinkerzen
DE654528C (de) Verfahren zur Entfernung von Arsen, Antimon und/oder Zinn aus Blei
DE745190C (de) Verfahren zur Entfernung von Zinn aus Bleilegierungen
DE2707578B2 (de) Verfahren zur gewinnung von rohkupfer aus kupfererzen oder -konzentraten, welche schaedliche oder wirtschaftlich bedeutsame mengen an anderen nichteisenmetallen enthalten
DE3631196C2 (enrdf_load_stackoverflow)
DE2027636C3 (de) Verfahren zur Abtrennung von Stoffen aus einer Schmelze guter elektrischer Leitfähigkeit
DE3125888C2 (de) Gasreinigungsanlage innerhalb einer Kupferraffinieranlage

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL SE

ITCL It: translation for ep claims filed

Representative=s name: DE DOMINICIS & MAYER S.R.L.

TCNL Nl: translation of patent claims filed
17P Request for examination filed

Effective date: 19910817

EL Fr: translation of claims filed
17Q First examination report despatched

Effective date: 19931222

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL SE

REF Corresponds to:

Ref document number: 109839

Country of ref document: AT

Date of ref document: 19940815

Kind code of ref document: T

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940810

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59006768

Country of ref document: DE

Date of ref document: 19940915

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2023624

Country of ref document: ES

Kind code of ref document: T3

EAL Se: european patent in force in sweden

Ref document number: 90101459.7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20011204

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20011210

Year of fee payment: 13

Ref country code: AT

Payment date: 20011210

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20011218

Year of fee payment: 13

Ref country code: GB

Payment date: 20011218

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20011219

Year of fee payment: 13

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20020118

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20020213

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030125

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030801

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030801

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030930

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050125