US20180195149A1 - De-leading treatment method for lead-containing copper alloy and de-leading cored wire used in said method - Google Patents

De-leading treatment method for lead-containing copper alloy and de-leading cored wire used in said method Download PDF

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Publication number
US20180195149A1
US20180195149A1 US15/740,816 US201515740816A US2018195149A1 US 20180195149 A1 US20180195149 A1 US 20180195149A1 US 201515740816 A US201515740816 A US 201515740816A US 2018195149 A1 US2018195149 A1 US 2018195149A1
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Prior art keywords
leading
cored wire
lead
agent
copper alloy
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Abandoned
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US15/740,816
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English (en)
Inventor
Zangsa NOH
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Wing On (japan) Trading Ltd
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Wing On (japan) Trading Ltd
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Assigned to WING ON (JAPAN) TRADING LIMITED reassignment WING ON (JAPAN) TRADING LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NOH, ZANGSA
Publication of US20180195149A1 publication Critical patent/US20180195149A1/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
    • 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
    • C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. 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
    • C22B9/10—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

Definitions

  • the present invention relates to a cored wire for lead removal used for the de-leading treatment of molten metal of a lead-containing copper alloy and to a de-leading treatment method using the same.
  • a copper alloy mainly a brass rod
  • machinability workability
  • lead a copper alloy
  • Examples of the objects in which a brass rod is used include faucets utilized in a water supply system, worked parts of various optical equipment, and automobile parts.
  • the control in the direction of reducing or eliminating lead contained in a brass rod has been strengthened from the point of view of environmental control.
  • Patent Literature 1 a method of removing lead as a compound with calcium by adding metal element calcium and/or a copper-calcium alloy to brass molten metal containing lead. Further, there is proposed a method comprising adding a de-leading material to a copper alloy molten metal followed by mixing to produce a lead compound, adding a desiliconizing agent to liberate the lead compound, and separating and floating the lead compound to eliminate the same (Patent Literature 2).
  • Patent Literature 3 a method of adding a tin blocking agent to a copper alloy molten metal followed by mixing and then adding a de-leading agent thereto followed by mixing, thereby similarly separating and floating the lead compound to eliminate the same.
  • a cored wire there is proposed, for example, a method of charging a cored wire, in which a desulfurizing agent is covered with an iron-based band material or a sheath material, into molten iron or molten steel to allow the desulfurizing agent to react with the molten iron or molten steel to thereby exert a desulfurization effect (Patent Literature 4).
  • Patent Literature 1
  • Patent Literature 2
  • Patent Literature 3
  • Patent Literature 4
  • Patent Literature 1 is a method in which 300 kg of a raw material has been subjected to de-leading and removal in a small crucible, wherein a de-leading agent has been added at a time and allowed to stand to perform component analysis.
  • the method of Patent Literature 2 is a method of using, as an example, 4 kg of bronze, 320 g of a de-leading agent, and 150 g of a desiliconizing agent and feeding nitrogen gas by ejecting it into molten metal.
  • Patent Literature 3 is an experiment in which 5 kg of bronze and 400 g of a deblocking material are used. All of these methods are small-scale experimental methods. For example, the addition, stirring, and mixing of additives can be manually performed.
  • Metal calcium is most effective for the purpose of lead removal.
  • it is a water-reactive combustible substances which generates hydrogen in contact with water particularly when it is in a granular or powdery form. Therefore, it is necessary to keep a water-prohibitive state particularly in a mass production stage, to store in a dry, cool, dark place, and to take care also of the reactivity when charged into molten metal.
  • the handling of metal calcium requires high attention. Also with respect to calcium silicon, the same hazard increases when it takes a granular or powdery form. Therefore, this is a problem in the handling in practical mass production.
  • de-leading agents density of Ca: 1.55
  • coagents, and the like have small specific gravity and float in molten metal of brass or bronze having a specific gravity of more than 8. Therefore, sufficient de-leading effect cannot be obtained only by adding these de-leading agents and coagents to the molten metal.
  • a method of using a stirrer or the like may technically contribute to improve the de-leading effect. However, it will probably be required to install equipment and add treatment steps and time. Therefore, the method has not been established in practical mass production.
  • a cored wire known as an existing technique, has been used in steel and casting industry as a material to be charged into molten iron or molten steel to be treated, the material being prepared by covering an additive raw material required for deoxidation, desulfurization, or graphite spheroidization, singly or in combination, with an iron outer metal band (sheath material).
  • the contents used for conventional cored wires are composed of a combination of various raw materials such as a deoxidizer, a desulfurizing agent, and a graphite spheroidizing agent depending on the purpose of use.
  • the sheath material may be changed depending on the purpose and the object of treatment, but the outer metal band used for products actually circulating in the market is only a thin plate of iron.
  • Metal (for example, aluminum) thin plates other than the iron thin plate which can be theoretically supplied and used have been hardly selected from the point of view of operation technique, cost, and difficulty in supply.
  • an object of the present invention is the de-leading of a copper alloy, and conventionally used iron, aluminum, and the like cannot be used because they affect the quality of a copper alloy to be subjected to de-leading.
  • the components not only the components but also physical properties such as strength (tensile strength), flexibility, and workability are required for the sheath material to be selected in this case.
  • strength tensile strength
  • flexibility flexibility
  • workability are required for the sheath material to be selected in this case.
  • These physical properties are required in order that the contents are reliably fixed after the shape working to form a cored wire and that the sheath material does not cause fracture, rupture, opening, and the like during the feed, so that the core wire is suitably fed to molten metal by a cored wire feeding device.
  • a balance between the strength and the flexibility of a cored wire is required.
  • the main component of a de-leading agent in the present invention is metal calcium and/or calcium silicon, and a de-leading coagent also has a small specific gravity compared with that of the copper alloy molten metal to be subjected to de-leading treatment. Therefore, if the de-leading agent and the de-leading coagent are simply charged into molten metal, they will float on the surface of the molten metal, and reaction will occur only on the surface. Consequently, an expected de-leading effect cannot be obtained.
  • the buoyancy in fluid is determined by the following formula 1.
  • the present invention provides means and a method of solving the above problems in order to perform de-leading in the mass production of a copper alloy.
  • the present invention has minimized contact with water in the air to reduce a hazard by covering metal calcium or/and calcium silicon with a metal sheath material and mitigated and solved safety problems and handling problems in the de-leading treatment in practical mass production by having enabled continuous automatic charge of integrated form of a cored wire by a machine.
  • a copper alloy refers to an alloy comprising copper as main component, and the chief object is brass or bronze, but not particularly limited thereto.
  • the present invention by continuously feeding a cored wire containing a de-leading agent to molten metal, the collective charge of the de-leading agent is first avoided; the resistance per unit time against the buoyancy of the molten metal is suppressed to a minimum level; the de-leading agent is dispersed over the whole molten metal to effectively perform de-leading; the performance of the cored wire that can be mechanically and continuously fed by a cored wire feeding device is achieved; and dangerous work by human power or right above the molten metal is eliminated.
  • the present invention proposes a de-leading treatment method of a lead-containing copper alloy, comprising: successively feeding a cored wire for lead removal to molten metal of a copper alloy containing lead and allowing the cored wire to sink in the molten metal to subject the molten metal to de-leading treatment, the cored wire for lead removal comprising a de-leading agent and/or a de-leading coagent covered, singly or in combination, with a sheath material comprising copper or a copper alloy, wherein the de-leading agent is a granular or powdery de-leading agent containing metal element calcium, and the de-leading coagent is a granular or powdery de-leading coagent containing at least one of a Ca compound, an aggregation/floatation agent for a Pb—Ca compound, a tin blocking material, copper, zinc, tin, and a compound of copper, zinc, or tin.
  • the present invention proposes a de-leading treatment method, wherein a cored wire for lead removal comprising the de-leading agent covered with the sheath material and a cored wire for lead removal comprising the de-leading coagent covered with the sheath material are fed and allowed to sink in the molten metal to treat the molten metal for lead removal.
  • the present invention proposes a de-leading treatment method, wherein a cored wire for lead removal comprising at least one of the de-leading agent and the de-leading coagent covered with the sheath material is fed and allowed to sink in the molten metal once or multiple times to subject the molten metal to de-leading treatment.
  • the present invention proposes a cored wire for lead removal comprising a sheath material comprising copper or a copper alloy having a tensile strength of 150 to 600 N/mm 2 and a ductility of 15 to 60% and a granular or powdery de-leading agent containing metal calcium or/and calcium silicon, wherein the de-leading agent is covered with the sheath material.
  • the present invention proposes a cored wire for lead removal comprising a sheath material comprising copper or a copper alloy having a tensile strength of 150 to 600 N/mm 2 and a ductility of 15 to 60% and a granular or powdery de-leading coagent containing at least one of a Ca compound, an aggregation/floatation agent for a Pb—Ca compound, a tin blocking material, copper, zinc, tin, and a compound of copper, zinc, or tin, wherein the de-leading coagent is covered with the sheath material.
  • the present invention proposes a cored wire for lead removal comprising a sheath material comprising copper or a copper alloy having a tensile strength of 150 to 600 N/mm 2 and a ductility of 15 to 60%, a granular or powdery de-leading agent containing metal calcium or/and calcium silicon, and a granular or powdery de-leading coagent containing at least one of a Ca compound, an aggregation/floatation agent for a Pb—Ca compound, a tin blocking material, copper, zinc, tin, and a compound of copper, zinc, or tin, wherein the de-leading agent and the de-leading coagent are covered with the sheath material.
  • the present invention proposes a cored wire for lead removal, wherein the diameter of the cored wire for lead removal is 4 to 30 mm.
  • the present invention proposes a cored wire for lead removal, wherein the thickness of the sheath material of the cored wire for lead removal is 0.1 to 3 mm.
  • the present invention proposes a method for producing a cored wire for lead removal, comprising: subjecting a sheath material comprising copper or a copper alloy to shape working to thereby closely fix a granular or powdery de-leading agent containing metal calcium or/and calcium silicon and/or a granular or powdery de-leading coagent containing at least one of a Ca compound, an aggregation/floatation agent for a Pb—Ca compound, a tin blocking material, copper, zinc, tin, and a compound of copper, zinc, or tin, to the sheath material to secure the de-leading agent and/or the de-leading coagent so that the de-leading agent and/or the de-leading coagent may not move relative to the sheath material.
  • the fracture, rupture, and opening of a cored wire can be prevented by a structure having suitable strength and flexibility after taking the work hardening of a sheath material into consideration; thereby, continuous feeding of a proper amount of a cored wire to molten metal can be automatically performed; de-leading treatment of a copper alloy molten metal in practical mass production is achieved; the difficulty of mixing treatment of a de-leading agent having a small specific gravity with a large amount of molten metal having a large specific gravity is mitigated; and it has been possible to reduce hazards due to use of a large amount of a highly reactive de-leading agent and operation at a location above molten metal.
  • FIG. 1 is a schematic explanatory diagram of a cored wire feeding device for carrying out the present invention.
  • FIG. 2 is an explanatory diagram of a cross section of a cored wire for lead removal showing an example of the present invention.
  • FIG. 3 is an explanatory diagram of a cross section of a cored wire for lead removal showing an example of the present invention.
  • FIG. 4 is an explanatory diagram of a cross section of a cored wire for lead removal showing an example of the present invention.
  • FIG. 5 is an explanatory diagram of a cross section of a cored wire for lead removal showing an example of the present invention.
  • a cored wire feeding device 10 is a device for feeding a cored wire for lead removal 1 to a treatment container 11 such as a melting furnace for treating a lead-containing copper alloy molten metal which is an object of the present invention.
  • the cored wire for lead removal 1 is pulled out of a coil 12 wound in a coiled form and fed to the treatment container 11 by a feeder 13 .
  • the feeder 13 is installed on a mount 14 and is configured to pull the cored wire for lead removal 1 out of the coil 12 and charge it into the molten metal 17 received in the treatment container 11 .
  • Various types of mechanisms can be employed in this feeder 13 , but in a general mechanism, the cored wire for lead removal 1 is sandwiched by plural rolls rotated by a motor and a plurality of carrying rolls to continuously perform the pulling out and the charge.
  • a plurality of guides 15 for the cored wire for lead removal 1 are provided at suitable places on the mount 14 to smoothly pull out the cored wire for lead removal 1 pulled out of the coil 12 and send it to the feeder 13 .
  • a guide pipe 16 is provided between the feeder 13 and the treatment container 11 and bears the sending of the cored wire for lead removal 1 and the continuous charge thereof in the vertical direction into the molten metal 17 . Further, the guide pipe 16 can be movably supported by a support arm 141 projecting from the mount 14 .
  • the lower end of the guide pipe 16 may project into the treatment container 11 provided that it does not contact molten metal.
  • the cored wire for lead removal 1 is preferably fed near the bottom of the treatment container 11 , and it is preferred to adjust the feeding rate in consideration of the material and the thickness of the sheath material 4 so that it melts near the bottom of the treatment container 11 .
  • metal calcium and calcium silicon are used singly or in combination as a de-leading agent 2 .
  • a granular or powdery de-leading agent 2 may be used.
  • the de-leading agent 2 may be used in combination with the de-leading coagent 3 as the contents, that is, the components, of the cored wire for lead removal ( FIGS. 2 and 3 ), but only one of the de-leading agent 2 and the de-leading coagent 3 may also be used as the content to form an independent separate cored wire for lead removal ( FIGS. 4 and 5 ).
  • the cored wire for lead removal 1 used for lead removal in the present invention includes those in which the de-leading agent 2 and/or the de-leading coagent 3 is used singly or in combination.
  • the present invention is characterized by using a metal such as copper, brass or bronze, or a copper alloy containing zinc, tin, or the like that does not have compositional influence on the copper alloy, as the sheath material 4 for covering the de-leading agent 2 and/or the de-leading coagent 3 .
  • the sheath material of copper or a copper alloy used in the present invention shows high work hardening when it is worked. This is a phenomenon that when stress is given to a metal, hardness of the metal is increased by plastic deformation, and the characteristics are shown by the size of a work hardening factor.
  • a common carbon steel (0.6C steel) has a work hardening factor of 0.15, while 65/35 brass which is one of the sheath materials 4 used in the present invention has a work hardening factor of 0.53, which is a numerical value 3 times or more larger than that of the common carbon steel. This means that when the copper alloy is worked as the sheath material 4 , the function such as flexibility that is expected from the cored wire for lead removal 1 will be lost.
  • a cored wire for lead removal 1 that endures practical use must be prepared by changing production conditions of the cored wire taking the type and physical properties of the sheath material 4 into account.
  • the metal to be used for the sheath material 4 has been tested in the present invention, and it has been elucidated that, with respect to the physical properties required for the cored wire for lead removal, tensile strength is desirably in the range of 150 to 600 N/mm 2 , and ductility is desirably from 15 to 60%.
  • the diameter of the cored wire for lead removal is preferably 4 to 30 mm for the purpose of facilitating production and working of the cored wire for lead removal and keeping the shape thereof during feed.
  • the thickness of the sheath material 4 used in the present invention is desirably in the range of 0.1 mm to 3.0 mm. This is because when the thickness is less than 0.1 mm, strength is low, which may cause tearing and cutting, and when the thickness is more than 3.0 mm, it is difficult to bend a cored wire for lead removal 1 , which makes it difficult to produce and feed the cored wire.
  • the best material and thickness of the sheath 41 used in the present invention can be selected in the range proposed above in consideration of the matrix of physical properties and the de-leading effect also taking the result of calculation of the position and time to melt into account so that the contents may act more efficiently in the molten metal to be de-leaded.
  • the material of the sheath material 4 those having the quality described in JIS material symbols C1020-1441 and C2100-4640 correspond to the material used in the present invention, and it is practically convenient to use these materials.
  • the de-leading coagent 3 for increasing the de-leading effect.
  • a granular or powdery coagent can be used as the de-leading coagent 3 .
  • Examples include a Ca compound 31 such as CaF2, CaCO3, and CaO which contributes to the fixing of the de-leading agent in the cored wire for lead removal and is used for the flux after the reaction, an aggregation/floatation agent for a Pb—Ca compound 32 , a mineral containing sodium fluoride and alumina silica glass or the like 33 , which is generally called a tin blocking agent, a metal such as copper, zinc, and tin, or a compound thereof 34 , which is a component constituting the copper alloy itself to be de-leaded and which contributes to the fixing of the de-leading agent in the cored wire for lead removal and the adjustment of components of the molten metal after de-leading.
  • a Ca compound 31 such as CaF2, CaCO3, and CaO which contributes to the fixing of the de-leading agent
  • the cored wire for lead removal can be contained in the cored wire for lead removal by selecting desired additives. Further, as an alternative in the present invention, it is possible to produce a cored wire for lead removal containing only one of these additives, for example, only a Ca compound ( FIG. 5 ), only an aggregation floatation agent, only a tin blocking agent, or only a metal such as copper or a compound thereof.
  • the cored wire containing only the de-leading coagent may also be referred to as an auxiliary cored wire for lead removal.
  • the cored wire for lead removal 1 include those in which one or more de-leading agents and one or more de-leading coagents are covered with a sheath material, those in which one or more de-leading agents are covered with a sheath material, and those in which one or more de-leading coagents are covered with a sheath material. Further, the cored wire for lead removal 1 include those in which one or more de-leading agents and one de-leading coagent are covered with a sheath material and those in which one de-leading agent and one or more de-leading coagents are covered with a sheath material.
  • the ductility of the sheath material 4 is exhibited during the working of the cored wire for lead removal 1 , and the cored wire for lead removal 1 is compressed while closely contacting the de-leading agent 2 and the de-leading coagent 3 as the contents with the cored wire for lead removal 1 .
  • both ends of the sheath material 4 are preferably secured, for example, by caulking 5 to cover the contents.
  • Example 1 Wire contents Metal calcium (mass %) 90 90 Specific gravity (g/cm 3 ) 1.55 1.55 Fluorite (mass %) 10 10 Specific gravity (g/cm 3 ) 3.18 3.18 Sheath material Material Brass Brass Wire diameter (mm) 13 13 Sheath material thickness (mm) 0.35 0.4 Wire average specific gravity (g/cm 3 ) 4.6 5.0 Copper alloy Material Brass Brass molten metal Specific gravity (g/cm 3 ) 8.3 8.2 Molten metal weight (kg) 4000 4500 Molten metal temperature (° C.) 950 950 Number of wires 1 1 Wire feed length (m) 350 450 Wire feed time (min) 10 15 Amount of removed lead (kg) 40 70
  • the present invention extremely efficiently removes lead contained in a copper alloy, allows mass remaking of a copper alloy in a good condition, and can achieve quality improvement of copper alloy products and cost reduction of the products produced therefrom.
  • the present invention has a large in-use effect.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Ropes Or Cables (AREA)
US15/740,816 2015-11-13 2015-11-13 De-leading treatment method for lead-containing copper alloy and de-leading cored wire used in said method Abandoned US20180195149A1 (en)

Applications Claiming Priority (1)

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PCT/JP2015/082039 WO2017081824A1 (fr) 2015-11-13 2015-11-13 Procédé de traitement d'élimination du plomb pour alliage de cuivre contenant du plomb et fil fourré d'élimination du plomb utilisé dans ledit procédé

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US (1) US20180195149A1 (fr)
EP (1) EP3375896A4 (fr)
JP (1) JP5940746B1 (fr)
KR (1) KR20180034643A (fr)
CN (1) CN107849638A (fr)
WO (1) WO2017081824A1 (fr)

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IT201800008041A1 (it) 2018-08-10 2020-02-10 Almag Spa Azienda Lavorazioni Metallurgiche Ed Affini Gnutti Processo per l’ottenimento di una billetta di ottone a ridotto tenore di piombo e billetta così ottenuta
CN109371248B (zh) * 2018-12-04 2020-01-14 宁波长振铜业有限公司 一种降低废旧黄杂铜中铅含量的方法

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CA1095259A (fr) * 1978-03-14 1981-02-10 Derek E. Tyler Methode d'addition a des alliages de cuivre, d'elements reactifs sous forme de poudre placee dans un tube
JPH0250924A (ja) * 1988-08-10 1990-02-20 Hitachi Cable Ltd 銅の還元処理方法
JPH10140254A (ja) * 1996-11-05 1998-05-26 Kobe Steel Ltd 黄銅中の鉛の除去方法
US20020030070A1 (en) * 2000-06-01 2002-03-14 Hugens John R. Method and apparatus for treatment of metal cascades in flame and gas
JP4599521B2 (ja) * 2004-12-10 2010-12-15 株式会社九州タブチ 銅合金中の鉛除去方法
CN102424891A (zh) * 2011-12-09 2012-04-25 郑州万隆冶金炉料有限公司 炼钢用纯钙实芯包芯线的生产方法
CN103146939B (zh) * 2013-02-06 2015-01-28 江西理工大学 一种降低铅黄铜中铅含量的方法
CN104250694B (zh) * 2014-07-08 2016-07-13 宁波长振铜业有限公司 一种废杂黄铜熔炼制备易切削黄铜的除铁精炼工艺
CN104357699B (zh) * 2014-09-29 2016-06-15 苏州有色金属研究院有限公司 一种除锡精炼剂及其用途
CN104894412A (zh) * 2015-04-16 2015-09-09 新疆大学 一种铜及铜合金熔炼过程中的除杂方法

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JPWO2017081824A1 (ja) 2017-11-09
EP3375896A1 (fr) 2018-09-19
WO2017081824A1 (fr) 2017-05-18
CN107849638A (zh) 2018-03-27
EP3375896A4 (fr) 2019-05-22
KR20180034643A (ko) 2018-04-04
JP5940746B1 (ja) 2016-06-29

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