WO2017081824A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2017081824A1
WO2017081824A1 PCT/JP2015/082039 JP2015082039W WO2017081824A1 WO 2017081824 A1 WO2017081824 A1 WO 2017081824A1 JP 2015082039 W JP2015082039 W JP 2015082039W WO 2017081824 A1 WO2017081824 A1 WO 2017081824A1
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WO
WIPO (PCT)
Prior art keywords
lead
cored wire
deleading
agent
copper
Prior art date
Application number
PCT/JP2015/082039
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English (en)
Japanese (ja)
Inventor
庄司 盧
Original Assignee
株式会社ウィング・オン
クサカファンドリーサプライズ株式会社
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 株式会社ウィング・オン, クサカファンドリーサプライズ株式会社 filed Critical 株式会社ウィング・オン
Priority to PCT/JP2015/082039 priority Critical patent/WO2017081824A1/fr
Priority to US15/740,816 priority patent/US20180195149A1/en
Priority to JP2015557248A priority patent/JP5940746B1/ja
Priority to CN201580081517.0A priority patent/CN107849638A/zh
Priority to KR1020187006012A priority patent/KR20180034643A/ko
Priority to EP15908341.9A priority patent/EP3375896A4/fr
Publication of WO2017081824A1 publication Critical patent/WO2017081824A1/fr

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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 lead-free cored wire used for lead removal treatment of molten lead-containing copper alloy and a lead removal treatment method using the same.
  • brass bars In order to obtain workability (free machinability) for copper alloys, mainly brass bars, it is effective to contain about 2 to 4 wt% of lead.
  • the target used for the brass rod is, for example, a tap for waterworks, a processed part for various optical devices, or an automobile part.
  • regulations in the direction of reducing or eliminating lead contained in brass bars from the viewpoint of environmental regulations are being strengthened.
  • Patent Document 1 a method has been proposed in which metallic element calcium and / or copper calcium alloy is added to a molten brass containing lead to remove lead as a compound with calcium.
  • Patent Document 2 a method in which lead-free inclusions are produced by adding a lead-free material to the molten copper alloy, and then adding a desiliconizing agent to release the lead-containing inclusions, which are separated and levitated to eliminate them.
  • Patent Document 3 a method has been proposed in which a tin blocking agent and then a deleading agent are added and mixed in a molten copper alloy, and lead-containing inclusions are similarly levitated and removed.
  • Patent Document 1 is a method in which 300 kg of raw material is deleaded and removed with a small crucible, and a deleading agent is added at a time and left to perform component analysis.
  • the method of Patent Document 2 uses 4 kg of bronze as an example, and 320 g of deleading agent and 150 g of desiliconizing agent are used to blow and supply nitrogen gas into the molten metal.
  • Patent Document 3 is an experiment using 5 kg bronze and 400 g deblocking material. These are all small-scale experimental methods, and are, for example, manually possible regardless of whether an additive is added or stirred.
  • Calcium metal is most effective for the purpose of deleading, but it is a water-reactive flammable substance that generates hydrogen when it comes into contact with water, especially when it is granular or powdery. Keeping it in a dry, cool and dark place and paying attention to the reactivity when thrown into the molten metal makes handling difficult. Calcium silicon is also a problem in handling in practical mass production because the same danger increases by making it granular or powdery.
  • these deleading agents (Ca density 1.55) and auxiliary agents have a small specific gravity and rise to a molten brass or bronze having a specific gravity of more than 8, and a sufficient deleading effect can be obtained simply by adding them. Cannot be obtained. Even if a method such as using a stirrer contributes technically, it is not established in practical mass production because it is expected that equipment will be installed and processing steps and time will be added.
  • the cored wire known as an existing technology wraps an additive raw material necessary for deoxidation, desulfurization, and graphite spheroidization in a single or mixture form in an iron outer metal strip (sheath material). It is used in the steel industry and casting industry as a material that is put into hot metal to be processed and molten steel.
  • the contents used in conventional cored wires are a combination of various raw materials such as deoxidizers, desulfurizers, and graphite spheroidizers depending on the purpose of use, and the sheath material can be changed depending on the purpose and the object to be processed.
  • the outer metal strip used in products that are actually distributed in the market is only an iron sheet, and other metal (for example, aluminum) sheets that can theoretically be procured and used are the technical and cost of operation. Most have not been selected from the viewpoint of target and procurement difficulty.
  • the object of the present invention is the deleading of copper alloys, and iron, aluminum, etc. that have been used in the past can not be used because they affect the quality of the deleaded copper alloy.
  • the sheath material to be selected is not only a component but also appropriately supplied to the molten metal by the cored wire supply device, so that the content after the shape processing to the cored wire is securely fixed, and it is torn during the supply. Physical properties such as strength (tensile strength), flexibility, and workability are required to prevent breakage and opening.
  • tensile strength tensile strength
  • flexibility flexibility
  • workability are required to prevent breakage and opening.
  • a balance between strength and flexibility of the cored wire is required.
  • the main component of the deleading agent in the present invention is metallic calcium and / or calcium silicon, and the deleading auxiliary agent has a lower specific gravity than the molten copper alloy to be deleaded. Therefore, the expected deleading effect cannot be obtained because the reaction occurs only on the surface.
  • the force required to settle 10 kgs of calcium metal with a density of 1.55 against a brass melt with a density (specific gravity) of 8.2 is determined by the resultant force obtained by subtracting the weight of the object from buoyancy.
  • the present invention is a means and method for solving the above problems in order to perform lead removal in mass production of copper alloys.
  • metal calcium or / and calcium silicon is coated with a metal sheath material, so that contact with moisture in the air is minimized, and the risk is reduced.
  • the copper alloy refers to an alloy containing copper as a main component, and is mainly brass or bronze, but is not particularly limited thereto.
  • the cored wire including the deleading agent is first supplied to the molten metal to avoid the batch introduction of the deleading agent, minimizing the resistance per unit time against the buoyancy of the molten metal,
  • the lead-free agent is dispersed in the core, the lead-free lead is effectively executed, and the cored wire performance that can be mechanically and continuously supplied by the cored-wire feeding device is realized, eliminating dangerous work directly on the manpower or molten metal.
  • a granular or powdery deleading agent and / or Ca compound a Pb—Ca compound aggregating / floating agent, tin block material, copper, zinc, tin, or copper containing the metal element calcium
  • a granular or powdery deleading auxiliary agent containing at least one of zinc or tin compounds, and a sheath material composed of copper or a copper alloy, each of the deleading agent and the deleading auxiliary agent alone or in combination.
  • a lead-free copper alloy deleading method is proposed, in which a lead-free cored wire configured by coating is sequentially fed into a molten copper alloy containing lead, and then deleaded.
  • a lead-free cored wire constituted by coating the deleading agent with the sheath material and a lead-free cored wire constituted by covering the deleading auxiliary agent with the sheath material are supplied into the molten metal.
  • a lead removal cored wire constituted by covering at least one of the lead removal agent and / or the lead removal auxiliary agent with the sheath material is supplied and settled in the molten metal once or a plurality of times to remove the lead.
  • a sheath material made of copper or copper alloy having a tensile strength of 150 to 600 N / mm 2 and stretchability of 15 to 60%
  • a granular or powdered deleading agent containing metallic calcium or / and calcium silicon. Then, the present invention proposes a lead-free cored wire characterized in that the sheath material is coated with the de-leading agent.
  • a sheath material composed of copper or a copper alloy having a tensile strength of 150 to 600 N / mm 2 and stretchability of 15 to 60%, an agglomeration / floating agent of Ca compound and Pb—Ca compound, tin block material, copper, zinc , Tin, or a particulate or powdery deleading adjuvant containing at least one of copper, zinc or tin compounds, and the sheath material is coated with the deleading adjuvant
  • a sheath material made of copper or copper alloy having a tensile strength of 150 to 600 N / mm 2 and an extensibility of 15 to 60%, and a granular or powdery deleading agent and a Ca compound containing metallic calcium or / and calcium silicon
  • a lead-free cored wire is proposed in which the sheath material is coated with the lead-free agent and the lead-free auxiliary agent.
  • a lead-free cored wire characterized in that the diameter of the lead-free cored wire is 4 to 30 mm.
  • a lead-free cored wire characterized in that the sheath material of the lead-free cored wire has a thickness of 0.1 to 3 mm.
  • a granular or powdery deleading agent containing calcium metal and / or calcium silicon and / or agglomeration / floating agent of Ca compound and Pb-Ca compound by shape processing of a sheath material made of copper or copper alloy A tin block material, copper, zinc, tin, or a granular or powdery deleading auxiliary agent containing at least one of copper, zinc, or a tin compound is closely fixed to the sheath material, and the deleading agent and / or
  • the present invention proposes a method for producing a lead-free cored wire, wherein the lead-free auxiliary agent is fastened so as not to move with respect to the sheath material.
  • the structure having an appropriate strength and flexibility in consideration of the work-hardening property of the sheath material can prevent the cored wire from being torn, broken, and opened, and thus, continuous to the molten metal.
  • Supply can be carried out automatically, enabling practical mass-production deleading treatment of molten copper alloy, and further reducing the difficulty of mixing deleading agent with low specific gravity and large amount of molten metal with high specific gravity.
  • the cored wire supply device 10 is a device for supplying the lead-free cored wire 1 to a processing vessel 11 such as a melting furnace for processing the lead-containing copper alloy molten metal which is the object of the present invention.
  • the lead-free cored wire 1 is drawn out from a coil 12 wound in a coil shape and fed into a processing container 11 by a feeder 13.
  • the feeder 13 is installed on the gantry 14 and is configured to draw the lead-free cored wire 1 from the coil 12 and into the molten metal 17 accommodated in the processing container 11.
  • the feeder 13 can employ various mechanisms, but the lead wire cored wire 1 is sandwiched by a plurality of rolls and a plurality of feed rolls rotated by a motor, and the above-described drawing and feeding are continuously performed. Mechanism.
  • a plurality of guides 15 for the lead-free cored wire 1 are provided at appropriate positions on the gantry 14, and the lead-free cored wire 1 drawn from the coil 12 is smoothly drawn out to the feeder 13.
  • a guide pipe 16 is provided between the feeder 13 and the processing container 11, and is responsible for feeding the lead-free cored wire 1 and continuously feeding it into the molten metal 17. Further, the guide pipe 16 can be supported by a support arm 141 extending from the gantry 14.
  • the lower end of the guide pipe 16 may protrude into the processing container 11 on the assumption that it does not touch the molten metal.
  • the lead-free cored wire 1 is preferably fed close to the bottom of the processing vessel 11, and the feeding speed is adjusted in consideration of the material and thickness of the sheath material 4, near the bottom of the processing vessel 11. It is preferable to dissolve.
  • metallic calcium and calcium silicon are used alone or in combination as the lead-free agent 2.
  • the deleading agent 2 can be granular or powdery.
  • the lead-free agent 2 and the lead-free auxiliary agent 3 are mixed and mixed with the contents of the lead-free cored wire, that is, the constituent elements.
  • FIGS. 2 to 5 which are sectional views of the lead-free cored wire
  • the lead-free agent 2 and the lead-free auxiliary agent 3 are mixed and mixed with the contents of the lead-free cored wire, that is, the constituent elements.
  • FIGS. 2 and 5 it is also possible to make an independent separate lead-free cored wire 1 containing only one of the de-leading agent 2 or the de-leading auxiliary agent 3 (FIGS. 4 and 5).
  • the lead-free cored wire 1 used for lead removal includes those in which the lead removal agent 2 and / or the lead removal auxiliary agent 3 are used alone or in combination.
  • a sheath material that covers a deleading agent 2 and / or a deleading auxiliary agent 3 with a metal that does not affect the composition of the copper alloy, such as copper, brass, bronze, or a copper alloy containing zinc or tin, etc. 4 is used.
  • the copper or copper alloy sheath material used in the present invention exhibits high work hardening when processed, unlike iron cored wires that have been manufactured using existing technology. This is a phenomenon in which the hardness of the metal increases due to plastic deformation when stress is applied to the metal, and this characteristic is indicated by the magnitude of the work hardening coefficient. In contrast to 0.15 for normal carbon steel (0.6C steel), 65/35 brass, which is one of the sheath materials 4 used in the present invention, shows a value of 0.53, which is three times or more. This means that when a copper alloy is processed as the sheath material 4, the functions such as flexibility expected as the lead-free cored wire 1 are lost.
  • the lead wire cored wire 1 In general, the tensile strength and stretchability vary greatly depending on the material. Therefore, the lead wire cored wire 1 must be able to withstand actual use by taking into account the type and physical characteristics of the sheath material 4 and changing the cored wire manufacturing conditions. .
  • the metal used for the sheath material 4 is tested, and the tensile strength as a physical property required for the lead-free cored wire is in the range of 150 to 600 N / mm 2 and stretched. Regarding the sex, it was clarified that it is desirable to be 15 to 60%.
  • the tensile strength is less than 150 N / mm 2 , there is a large risk of cutting, and if it exceeds 600 N / mm 2 , it is too strong and affects the production of lead-free cored wire. The use of was also difficult. With regard to stretchability, if it is less than 15%, there is no room for deformation and it is difficult to produce and supply lead-free cored wire. Arise.
  • the diameter of the lead-free cored wire is preferably 4 to 30 mm for the purpose of facilitating the manufacturing process of the lead-free cored wire and maintaining the shape during supply.
  • the thickness of the sheath material 4 used in the present invention is in the range of 0.1 mm to 3.0 mm. If it is less than 0.1 mm, the strength is weak, and there is a risk of breaking and cutting. If it is greater than 3.0 mm, it becomes difficult to bend as the lead-free cored wire 1, and it becomes difficult to manufacture and supply the cored wire. .
  • the material and thickness of the sheath 41 used in the present invention is more effective in considering the position and time of melting because the contents act more efficiently in the molten metal to be deleaded.
  • the optimum one can be selected within the above proposed range considering the matrix of characteristics and deleading effect.
  • the material of the sheath material 4 those described in JIS standard product numbers C1020-1441 and C2100-4640 correspond to the materials used, and it is convenient to use them in practice.
  • the deleading adjuvant 3 can be granular or powdery.
  • Ca compound 31 such as CaF2, CaCO3, CaO, etc.
  • Pb-Ca compound agglomeration / floating agent 32 which contributes to fixation of the deleading agent in the cored wire for deleading and is used as a post-reaction agent Copper for deleading treatment that contributes to fixing of deleading agent in core lead wire for deleading and adjustment of molten metal components after deleading, such as minerals containing sodium fluoride and alumina silicate glass called tin blocking agent Metals such as copper, zinc, tin, etc., or their compounds 34, which are components constituting the alloy itself.
  • the lead-free cored wire 1 is obtained by coating one or more types of deleading agents and one or more types of deleading auxiliary agents with a sheath material, and one or more types of deleading agents with a sheath material.
  • one or more deleading aids coated with a sheath material coated with a sheath material.
  • one or more types of deleading agents and one type of deleading aid are covered with a sheath material, and one type of deleading agent and one or more types of deleading aids are covered with a sheath material. It is.
  • the lead removal agent 2 and the lead removal auxiliary material 3 are integrated and fixed on the cored wire 1, the lead wire cored wire 1 and the content of lead removal are made to exhibit its extensibility when processing the leadless cored wire 1.
  • the agent 2 and the deleading adjuvant 3 are condensed while being adhered.
  • the sheath material 4 may be fastened and covered by, for example, caulking both ends 5.
  • the lead-free cored wire 1 was continuously supplied into the molten brass 17.
  • the lead-free cored wire 1 of the present invention can be charged into the molten metal in a predetermined quantity (length) without causing problems such as tearing, breaking, and opening, and the indicated lead removal was performed. From the examples, it is judged that it is possible to manufacture the optimum lead-free cored wire according to the weight of the molten metal, the temperature, and the shape of the container, and to set the supply conditions. From the results of the above examples, it was proved that deleading in units of several tens of kilograms on a mass production scale using an actual machine that could not be realized in the prior art example was possible.
  • the characteristics required for the sheath material specified in this patent are: It is judged that the conditions that can withstand the supply by the machine are satisfied.
  • the present invention is very efficient in removing lead contained in a copper alloy, enables mass production of a good-quality copper alloy, and improves the quality of the copper alloy product and thereby reduces the cost of the manufactured product. Can be practically used.

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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)

Abstract

Les alliages de cuivre tel que le laiton ou le bronze, principalement des produits en forme de barreau nécessitant une découpe libre, contiennent une certaine quantité de plomb. Dans le passé, des déchets de tels produits ont été réutilisés à un pourcentage élevé. L'emploi recyclé de ces déchets de produits pour fabriquer des produits à faible teneur en plomb requiert une étape d'élimination du plomb et nécessite de développer une technologie d'élimination du plomb. Pour éliminer le plomb d'alliages de cuivre, des matériaux contenant l'élément métallique calcium ont montré leur efficacité. Cependant, en raison des différences de densité et de point de fusion entre l'agent d'élimination du plomb et l'alliage de cuivre, il est nécessaire de disposer d'un procédé d'élimination du plomb qui puisse être mis en œuvre à échelle industrielle. Pour résoudre ledit problème, la présente invention propose un fil fourré d'élimination du plomb destiné à un traitement d'élimination du plomb d'un métal d'alliage de cuivre fondu, le fil fourré étant caractérisé en ce que : une bande métallique qui n'affecte pas les composants du métal d'alliage de cuivre fondu est utilisée comme matériau de gaine ; son contenu est un agent d'élimination de plomb seul et/ou un agent auxiliaire d'élimination du plomb tel qu'un floculant ou réactif de flottation de composé Pb-Ca, etc. requis par le procédé ; et le fil fourré possède des propriétés physiques pouvant résister à une alimentation mécanique continue par un dispositif d'avance de fil fourré.
PCT/JP2015/082039 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 WO2017081824A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
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
US15/740,816 US20180195149A1 (en) 2015-11-13 2015-11-13 De-leading treatment method for lead-containing copper alloy and de-leading cored wire used in said method
JP2015557248A JP5940746B1 (ja) 2015-11-13 2015-11-13 鉛含有銅合金の脱鉛処理方法及びその方法に用いる脱鉛用コアードワイヤー
CN201580081517.0A CN107849638A (zh) 2015-11-13 2015-11-13 含铅铜合金的去铅处理方法及使用此方法的去铅用芯线
KR1020187006012A KR20180034643A (ko) 2015-11-13 2015-11-13 납 함유 동 합금의 무연 처리 방법 및 그 방법에 사용하는 무연용 코아드 와이어
EP15908341.9A EP3375896A4 (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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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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WO2017081824A1 true WO2017081824A1 (fr) 2017-05-18

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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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JP2006161136A (ja) * 2004-12-10 2006-06-22 Kyushu Tabuchi:Kk 銅合金中の鉛除去方法

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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
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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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JPH10140254A (ja) * 1996-11-05 1998-05-26 Kobe Steel Ltd 黄銅中の鉛の除去方法
JP2006161136A (ja) * 2004-12-10 2006-06-22 Kyushu Tabuchi:Kk 銅合金中の鉛除去方法

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Title
See also references of EP3375896A4 *

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JPWO2017081824A1 (ja) 2017-11-09
US20180195149A1 (en) 2018-07-12
EP3375896A1 (fr) 2018-09-19
CN107849638A (zh) 2018-03-27
EP3375896A4 (fr) 2019-05-22
KR20180034643A (ko) 2018-04-04
JP5940746B1 (ja) 2016-06-29

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