US1428041A - Process for the separation and recovery of metals from metal alloys - Google Patents

Process for the separation and recovery of metals from metal alloys Download PDF

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US1428041A
US1428041A US41175120A US1428041A US 1428041 A US1428041 A US 1428041A US 41175120 A US41175120 A US 41175120A US 1428041 A US1428041 A US 1428041A
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Kroll Guillaume Justine
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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
    • 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
    • C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
    • 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • 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 mventlon relates a process for the purpose of separating individual constituents from metal alloys (including impure metals) in order either to free the metal alloys from the injurious metallic constituents contained therein, or to recover the eliminated constituents.
  • T he invention is based on the observation that when alkaline-earth metals (including magnesium) are introduced into fused metal alloys they combine with certain metals of the alloy under treatment to form alloys or other compounds or mixtures which, inasmuch as they have a different fusing point and a different specific gravity from the remaining part of the alloy under treatment, can be easily separated. from the latter by known methods.
  • the present invention consists in introducing alkaline-earth metals, or alloys (mixtures) of said metals between themselves or with other metals. into the fused metal alloys under treatment.
  • the separable alloys or other compounds or mixtures above mentioned are thereby formed within the metal'alloys, and separate from the remaining part of the metal alloy under treatment by Stratification either immediately or after cooling; or if they remain distributed throughout the mass of the metal, they may be separated out by one or more segregation or liquation processes or, by crystallization or otherwise.
  • antimony, bismuth, arsenic, tellurium in a less easy manner, also tin, copper, zinc and the noble metals
  • lead alloys by introducing sodium, calcium, strontium, barium or ma nesium.
  • Antimony, arsenic and bismuth may be separated from alloys of tin; antimony, arsenic, tin, and tellurium from alloys which mainly contain bismuth; antimony and arsenic from alloys of zinc in the same manner.
  • Calcium is, in general, the most efiicient alkali earth metal for carrying out the present invention.
  • the alkali metals and the rare eartlf metals act in a similar manner as the alkali earth metals. It may be advantageous in the present method to use the alkali earth metals or the rare earth metals in combination with alkali metals. This can be eifec-ted by using an alloy (mixture) of alkali earth metals and alkali metals or rare earth metals.
  • alkali earth metals or metal such as calcium
  • the alkali metals or metal such as sodium
  • the rare earth metals may also be, preferable to first cause the alkali earth metals or metal (such as calcium) to act upon the metal alloy under treatment in order to remove part of the constituents to be se arated, and subsequently cause the alkali metals or metal (such as sodium) or the rare earth metals to act upon the remaining part of the metal alloy under treatment in order to remove the remaining constituents to be separated, or these subsequent operations may be effected vice versa.
  • alkaline-earth metal or alkali metal or rare earth metal may also be added to the metal alloy under treatment in any other form, for example inthe form of an alloy, or they may be incorporated into the metal alloy under treatment by electrolysis or a chemical rocess.
  • alkaline-earth metal or alkali metal or rare earth metal
  • the treatment may be effected in a series of successive working stages with successive, portions of the required amounts of alkaline-earth metals (or alkali or rare earth metals.)
  • different alkali earth metals may be made use 0.26% of bismuth. This lead was treated with 0.3% calcium. A more or less solidified mass raised to the surface of the metal bath and was skimmed ofl f The analysis of this mass showed 2.0% of bismuth, while in the remaining lead the bismuth content was reduced to 0.049%.
  • the method of separating and recovering metallic constituents from metal alloys which comprises introducing an alkali-earth metal (including magnesium) into said metal alloys, forming thereby a compound of the alkali-earth metal with the metallic constituents to be separated, this compound having a dverent melting point from and a specific gravity not more than that of the main metal, and
  • the method of separating and recovering metallic constituents from metal alloys which comprises introducing a plurality of alkali-earth metals (including magnesium) into said metal alloys, forming thereby a compound of the alkali earth metals with the metallic constituents to be separated, this compound having a difi'erent melting point from and a specific gravity not more than that of the main metal, and eliminatin this compound from the remaining part 01? the metal alloy under treatment.
  • the method of separating and recovering metallic constituents from metal alloys which comprises introducing an alloy (mixture) of one or more alkali-earth metals (including magnesium) with other metals into said metal alloy forming thereby a compound of the alkali earth metals with the metallic constituents to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating this compound from the remaining part of the metal alloy under treatment.
  • the method of separating and recovering metallic impuritiesfrom impure lead which comprises introducing calcium into the impure lead, forming thereby a compound of calicum and the metallic impurities to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating said compound from the lead under treatment.
  • the method of separating and recovering bismuth from impure lead which comprises introducing calcium into the impure ead, forming thereby a compound of calcium and bismuth, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating said compound from the lead under treatment.
  • the method of separating and recovering bismuth from impure lead which comprises introducing an alloy (mixture) of calcium with other metals into the impure lead, forming thereby a compound of calcium and bismuth, this compound having a difierent melting point from and a specific gravity not more than that of the main metal.
  • the method of separating and recovering metallic constituents from metal alloys which comprises introducing an alloy (mixture) containing alkali-earth metals (including magnesium) and alkali metals into said metal alloy, forming thereby a compound of the alkali-earth metals and alkali metals with the metallic constituents to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating this compound from the remaining part of the metal alloy under treatment.
  • the method of separating and recovering subse uently metallic constituents from metal al oys- which comprisesintroducing an alkali metal into said metal alloys, forming thereby a compound of the alkali metal with one or more of the metallic constituents to be separated, eliminating this compound from the remaining part of the metal alloy under treatment, introducing an alkali-earth metal (including;1 magnesium) into the remaining part of t e metal alloy under treatment, forming thereby a compound of the alkaliearth metal with the remaining part of the metallic constituents to be separated, and
  • the method of separating and recov-' ering subseguently metallic impurities from impure lea WhlCll comprises introducing sodium into the impure lead, forming thereby a compound of sodium with part of the a metallic impurities to be separated, eliminating this compound from the remaining part of the lead under treatment, introducing calcium into this remaining part of the lead under treatment, forming thereby a compound of calcium with the remaining part of the metallic impurities to be separated, and eliminating this compound from the remaining part of the lead under treatment the compounds being eliminated havin a difierent melting point from and a speci e gravity not greater than that of the main metal.
  • the method of separating and recovering metallic constituents from metal alloys which comprises introducing an alloy (mixture) containing alkali-earth metals, (including magnesium) and rare earth metals into said metal alloy, forming thereby a compound of the alkali-earth metals and rare earth metals with the metallic constituents to be separated, and eliminating this com ound from the remaining part of the meta alloy under treatment.
  • the method of separating and recovering subsequently metallic constituents from metal alloys which comprises introducing an alkali-earth metal (including magnesium) into said metal alloys forming thereby a compound of the alkali-earth metal with one or more of the metallic constituents to be separated, eliminating this compound from the remaining part of the metal alloy under treatment, introducing rare earth metals into the remaining part of the metal alloy under treatment, forming thereb a compound of the rare earth metals with the remaining part of the metallic constituents to be separated, and eliminating this compound from the remaining part of the metal alloy under treatment.
  • the method of separating and recovering subsequently metallic impurities from impure lead, wh1ch comprises introducing calcium into the impure lead, forming thereby a compound of calcium with part of the metallic impurities to be separated, eliminating this compound from the remaining part of the lead under treatment, introducing rare earth metals into this remainin part of the lead under treatment, forming t ereby a compound of the rare earth metals with the remaining part of the metallic impurities to be separated, and eliminating this compound fromthe remaining part of the lead under treatment.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

Patented Sept. 5, 1922.
UNITED STATES PATENT OFFICE.
comm-0mm JUSTINE KROLL, or tuxnmnoao, tuxnmnuao.
PBO CESS FOR THE SEPARATION AND RECOVERY OF METALS FROM METAL ALLOYS.
No Drawing.
To all whom it may concern:
Be it knownthat I, GUILLAUME Jos'rmn KROLL, metallurgical engineer, a subject of the Grand Duchess of Luxemburg, residing at Rue Schmilz-Hollerich 52, Luxemburg, Grand Duchy of Luxemb'urg, have invented certain new and useful Improvements in Processes for the Separation and Recovery of Metals from Metal Alloys, of which the following is a specification.
The present mventlon relates a process for the purpose of separating individual constituents from metal alloys (including impure metals) in order either to free the metal alloys from the injurious metallic constituents contained therein, or to recover the eliminated constituents.
T he invention is based on the observation that when alkaline-earth metals (including magnesium) are introduced into fused metal alloys they combine with certain metals of the alloy under treatment to form alloys or other compounds or mixtures which, inasmuch as they have a different fusing point and a different specific gravity from the remaining part of the alloy under treatment, can be easily separated. from the latter by known methods.
Accordingly,- the present invention consists in introducing alkaline-earth metals, or alloys (mixtures) of said metals between themselves or with other metals. into the fused metal alloys under treatment. The separable alloys or other compounds or mixtures above mentioned are thereby formed within the metal'alloys, and separate from the remaining part of the metal alloy under treatment by Stratification either immediately or after cooling; or if they remain distributed throughout the mass of the metal, they may be separated out by one or more segregation or liquation processes or, by crystallization or otherwise.
To mention a few examples, it is possible to separate antimony, bismuth, arsenic, tellurium (in a less easy manner, also tin, copper, zinc and the noble metals) from lead alloys, by introducing sodium, calcium, strontium, barium or ma nesium. Antimony, arsenic and bismuth, may be separated from alloys of tin; antimony, arsenic, tin, and tellurium from alloys which mainly contain bismuth; antimony and arsenic from alloys of zinc in the same manner.
The choice of the alkaline-earth metal to Application filed September 21, 1920. Serial No. 411,751.
be used depends on the kind of the metal alloy and on the constituents which have to be separated out therefrom. Calcium is, in general, the most efiicient alkali earth metal for carrying out the present invention.
The alkali metals and the rare eartlf metals act in a similar manner as the alkali earth metals. It may be advantageous in the present method to use the alkali earth metals or the rare earth metals in combination with alkali metals. This can be eifec-ted by using an alloy (mixture) of alkali earth metals and alkali metals or rare earth metals. It may also be, preferable to first cause the alkali earth metals or metal (such as calcium) to act upon the metal alloy under treatment in order to remove part of the constituents to be se arated, and subsequently cause the alkali metals or metal (such as sodium) or the rare earth metals to act upon the remaining part of the metal alloy under treatment in order to remove the remaining constituents to be separated, or these subsequent operations may be effected vice versa.
It is obvious that the alkaline-earth metal or alkali metal or rare earth metal may also be added to the metal alloy under treatment in any other form, for example inthe form of an alloy, or they may be incorporated into the metal alloy under treatment by electrolysis or a chemical rocess.
For carrying out the process it is, of course, unnecessary to add the required amount of alkaline-earth metal (or alkali metal or rare earth metal) in one portion; but the treatment may be effected in a series of successive working stages with successive, portions of the required amounts of alkaline-earth metals (or alkali or rare earth metals.) In these successive operations different alkali earth metals may be made use 0.26% of bismuth. This lead was treated with 0.3% calcium. A more or less solidified mass raised to the surface of the metal bath and was skimmed ofl f The analysis of this mass showed 2.0% of bismuth, while in the remaining lead the bismuth content was reduced to 0.049%.
What I claim as new and desire to secure *by Letters Pia-tent of the United States is:
1. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing an alkali-earth metal (including magnesium) into said metal alloys, forming thereby a compound of the alkali-earth metal with the metallic constituents to be separated, this compound having a diilerent melting point from and a specific gravity not more than that of the main metal, and
eliminating this compound from the remaining part of the metal alloy under treatment.
2. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing a plurality of alkali-earth metals (including magnesium) into said metal alloys, forming thereby a compound of the alkali earth metals with the metallic constituents to be separated, this compound having a difi'erent melting point from and a specific gravity not more than that of the main metal, and eliminatin this compound from the remaining part 01? the metal alloy under treatment.
3. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing an alloy (mixture) of one or more alkali-earth metals (including magnesium) with other metals into said metal alloy forming thereby a compound of the alkali earth metals with the metallic constituents to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating this compound from the remaining part of the metal alloy under treatment.
4. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing calcium into said metal alloys,
forming thereby a compound of calcium with the metallic constituents'to be separated, this compound having a different melting point froIn' anda specific gravity not more than that of the main metal, and eliminating this compound from the remaining part of the metal alloy under treatment.
5. The method of separating and recovering metallic impuritiesfrom impure lead, which comprises introducing calcium into the impure lead, forming thereby a compound of calicum and the metallic impurities to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating said compound from the lead under treatment.
6. The method of separating and recovering bismuth from impure lead, which comprises introducing calcium into the impure ead, forming thereby a compound of calcium and bismuth, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating said compound from the lead under treatment.
7. The method of separating and recovering bismuth from impure lead, which comprises introducing an alloy (mixture) of calcium with other metals into the impure lead, forming thereby a compound of calcium and bismuth, this compound having a difierent melting point from and a specific gravity not more than that of the main metal.
and eliminating said compound from the lead under treatment.
8. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing an alloy (mixture) containing alkali-earth metals (including magnesium) and alkali metals into said metal alloy, forming thereby a compound of the alkali-earth metals and alkali metals with the metallic constituents to be separated, this compound having a different melting point from and a specific gravity not more than that of the main metal, and eliminating this compound from the remaining part of the metal alloy under treatment.
9. The method of separating and recovering subse uently metallic constituents from metal al oys- (including impure metals) which comprisesintroducing an alkali metal into said metal alloys, forming thereby a compound of the alkali metal with one or more of the metallic constituents to be separated, eliminating this compound from the remaining part of the metal alloy under treatment, introducing an alkali-earth metal (including;1 magnesium) into the remaining part of t e metal alloy under treatment, forming thereby a compound of the alkaliearth metal with the remaining part of the metallic constituents to be separated, and
Ill
10. The method of separating and recov-' ering subseguently metallic impurities from impure lea WhlCll comprises introducing sodium into the impure lead, forming thereby a compound of sodium with part of the a metallic impurities to be separated, eliminating this compound from the remaining part of the lead under treatment, introducing calcium into this remaining part of the lead under treatment, forming thereby a compound of calcium with the remaining part of the metallic impurities to be separated, and eliminating this compound from the remaining part of the lead under treatment the compounds being eliminated havin a difierent melting point from and a speci e gravity not greater than that of the main metal.
11. The method of separating and recovering metallic constituents from metal alloys (including impure metals), which comprises introducing an alloy (mixture) containing alkali-earth metals, (including magnesium) and rare earth metals into said metal alloy, forming thereby a compound of the alkali-earth metals and rare earth metals with the metallic constituents to be separated, and eliminating this com ound from the remaining part of the meta alloy under treatment.
12. The method of separating and recovering subsequently metallic constituents from metal alloys (including impure metals) which comprises introducing an alkali-earth metal (including magnesium) into said metal alloys forming thereby a compound of the alkali-earth metal with one or more of the metallic constituents to be separated, eliminating this compound from the remaining part of the metal alloy under treatment, introducing rare earth metals into the remaining part of the metal alloy under treatment, forming thereb a compound of the rare earth metals with the remaining part of the metallic constituents to be separated, and eliminating this compound from the remaining part of the metal alloy under treatment.
13. The method of separating and recovering subsequently metallic impurities from impure lead, wh1ch comprises introducing calcium into the impure lead, forming thereby a compound of calcium with part of the metallic impurities to be separated, eliminating this compound from the remaining part of the lead under treatment, introducing rare earth metals into this remainin part of the lead under treatment, forming t ereby a compound of the rare earth metals with the remaining part of the metallic impurities to be separated, and eliminating this compound fromthe remaining part of the lead under treatment.
In testimon whereof I afiix my signature in presence 0- two witnesses.
V. MULLER, R. HENPEN.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2517380A (en) * 1947-08-26 1950-08-01 Bell Telephone Labor Inc Method of analysis and control of the composition of lead alloys
US2849309A (en) * 1954-12-22 1958-08-26 Ethyl Corp Preparation of alkaline earth metal alloys
US3259490A (en) * 1963-05-07 1966-07-05 Motorola Inc Gettering in semiconductor devices
US3442643A (en) * 1965-12-08 1969-05-06 Ernest B Ackerman Recovery of electroplate utilizing molten lead
US3463637A (en) * 1966-08-26 1969-08-26 Dow Chemical Co Water disintegrable lead shot
US3481732A (en) * 1966-08-26 1969-12-02 Dow Chemical Co Processing lead alloy containing magnesium
FR2372240A1 (en) * 1976-11-26 1978-06-23 Westinghouse Electric Corp PROCESS FOR THE PRODUCTION OF TITANIUM AND ZIRCONIUM BY REDUCTION IN AN ARC HEATING ELEMENT
US4333762A (en) * 1980-03-20 1982-06-08 Asarco Incorporated Low temperature, non-SO2 polluting, kettle process for the separation of antimony values from material containing sulfo-antimony compounds of copper
FR2519026A1 (en) * 1981-12-29 1983-07-01 Gould Inc METHOD FOR REFINING IMPURED LEAD
EP0343012A3 (en) * 1988-05-20 1991-01-09 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
US5041160A (en) * 1988-05-20 1991-08-20 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
US5100466A (en) * 1991-05-02 1992-03-31 E. I. Du Pont De Nemours And Company Process for purifying lead using calcium/sodium filter cake
FR2764905A1 (en) * 1997-06-23 1998-12-24 Pechiney Electrometallurgie PROCESS FOR TREATMENT OF CALCIUM MELT LEAD AND CALCIUM-BASED WIRE FOR THIS TREATMENT

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2517380A (en) * 1947-08-26 1950-08-01 Bell Telephone Labor Inc Method of analysis and control of the composition of lead alloys
US2849309A (en) * 1954-12-22 1958-08-26 Ethyl Corp Preparation of alkaline earth metal alloys
US3259490A (en) * 1963-05-07 1966-07-05 Motorola Inc Gettering in semiconductor devices
US3442643A (en) * 1965-12-08 1969-05-06 Ernest B Ackerman Recovery of electroplate utilizing molten lead
US3463637A (en) * 1966-08-26 1969-08-26 Dow Chemical Co Water disintegrable lead shot
US3481732A (en) * 1966-08-26 1969-12-02 Dow Chemical Co Processing lead alloy containing magnesium
FR2372240A1 (en) * 1976-11-26 1978-06-23 Westinghouse Electric Corp PROCESS FOR THE PRODUCTION OF TITANIUM AND ZIRCONIUM BY REDUCTION IN AN ARC HEATING ELEMENT
US4333762A (en) * 1980-03-20 1982-06-08 Asarco Incorporated Low temperature, non-SO2 polluting, kettle process for the separation of antimony values from material containing sulfo-antimony compounds of copper
FR2519026A1 (en) * 1981-12-29 1983-07-01 Gould Inc METHOD FOR REFINING IMPURED LEAD
US4410361A (en) * 1981-12-29 1983-10-18 Gnb Batteries Inc. Method for desilverizing and removal of other metal values from lead bullion
EP0343012A3 (en) * 1988-05-20 1991-01-09 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
US5041160A (en) * 1988-05-20 1991-08-20 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
US5100466A (en) * 1991-05-02 1992-03-31 E. I. Du Pont De Nemours And Company Process for purifying lead using calcium/sodium filter cake
FR2764905A1 (en) * 1997-06-23 1998-12-24 Pechiney Electrometallurgie PROCESS FOR TREATMENT OF CALCIUM MELT LEAD AND CALCIUM-BASED WIRE FOR THIS TREATMENT
WO1998059082A1 (en) * 1997-06-23 1998-12-30 Pechiney Electrometallurgie Method for treating molten lead with calcium

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