JP6050222B2 - Disposal of electrical and electronic parts waste - Google Patents
Disposal of electrical and electronic parts waste Download PDFInfo
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- JP6050222B2 JP6050222B2 JP2013270166A JP2013270166A JP6050222B2 JP 6050222 B2 JP6050222 B2 JP 6050222B2 JP 2013270166 A JP2013270166 A JP 2013270166A JP 2013270166 A JP2013270166 A JP 2013270166A JP 6050222 B2 JP6050222 B2 JP 6050222B2
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- 239000002699 waste material Substances 0.000 title claims description 133
- 238000003723 Smelting Methods 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 44
- 238000010298 pulverizing process Methods 0.000 claims description 30
- 239000012141 concentrate Substances 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000003672 processing method Methods 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 150000002739 metals Chemical class 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、電気・電子部品屑の処理方法に関する。 The present invention relates to a method for treating electrical / electronic component waste.
近年、電気・電子部品製造業やそれら電気・電子部品を利用する製品および産業から発生するスクラップ類（電線屑、リードフレーム、ＩＣチップ、樹脂付き基板屑、超小型コイル、スイッチ等々）の発生量が大幅に増大する傾向にある。これらスクラップ類は、金属、樹脂、セラミック等を含む複合材料であり、具体的には電気導体として使われる銅や、接点、メッキ皮膜等に使用された金、銀、白金、パラジウム等の有価金属が含まれている。この有価金属の回収は、資源のリサイクルによる省資源の観点からも重要である。 In recent years, the amount of scraps (electric wire scrap, lead frame, IC chip, substrate scrap with resin, ultra-small coil, switch, etc.) generated from the electrical / electronic component manufacturing industry and products and industries that use these electrical / electronic components Tend to increase significantly. These scraps are composite materials including metals, resins, ceramics, and more specifically, copper used as electrical conductors, and valuable metals such as gold, silver, platinum, and palladium used for contacts and plating films. It is included. This recovery of valuable metals is also important from the viewpoint of resource saving through resource recycling.
上記のようなスクラップ類はもちろん以前からも発生しており、そのリサイクル方法は多様である。銅分が多くて、他の有価金属（貴金属）の含有率が低ければ、単純に、溶融した銅の中にスクラップ類を投入し、銅や有価金属を回収することができる。 Of course, such scraps have been generated for some time, and their recycling methods are diverse. If the copper content is high and the content of other valuable metals (noble metals) is low, scraps can be simply thrown into the molten copper and the copper and valuable metals can be recovered.
電気・電子部品屑から銅および有価金属を回収する方法としては、従来、種々の研究・開発がなされている。例えば、特許文献１には、有価金属を含有するスクラップ類を銅鉱石溶錬用自溶炉へシャフト天井部から装入し、有価金属を炉内に滞留するマットへ回収することを特徴とするスクラップ類からの有価金属のリサイクル方法が開示されている。そして、このような構成によれば、銅溶錬自溶炉での銅製錬にスクラップ処理を組み合わせるため、有価金属含有率が低いスクラップ類からでも、低コストで有価金属を回収することができると記載されている。 As a method for recovering copper and valuable metals from electrical / electronic component waste, various researches and developments have been made. For example, Patent Document 1 is characterized in that scraps containing valuable metals are charged into a copper ore smelting flash furnace from the shaft ceiling, and the valuable metals are collected in a mat that stays in the furnace. A method for recycling valuable metals from scraps is disclosed. And according to such a configuration, since scrap processing is combined with copper smelting in a copper smelting flash furnace, valuable metals can be recovered at low cost even from scraps having a low valuable metal content. Have been described.
従来、製錬所で受け入れる電気・電子部品屑は、通常粒度が例えば２０〜８０ｍｍと大きいため、受け入れた電気・電子部品屑の大半は鉱石を溶融製錬する溶錬炉で得られたマットを処理する転炉へ装入して処理している。近年、電気・電子部品屑のリサイクルの需要が増加し、それに伴い電気・電子部品屑の処理量が増加する傾向にある。ここで、従来の電気・電子部品屑の処理方法のように転炉のようなマット製錬炉で処理量を増加させると、溶錬炉に比べて電気・電子部品屑に含まれる不純物を分離する能力がマット製錬炉は劣るために最終的に電解用のアノードを製造する際に不純物が多くなるという問題があった。このため溶錬炉にて電気・電子部品屑を処理する方が望ましいが、溶錬炉において電気・電子部品屑を処理する場合には電気・電子部品屑を構成する樹脂等の有機物に含まれる炭素成分が増加し、これによって溶錬炉の処理時に過還元によるトラブルが発生するため溶錬炉において処理量を増加させることができなかった。より具体的には、溶錬炉において以下のような問題があった。特許文献１では実施例として溶錬炉の１種である自溶炉において電気・電子部品屑スクラップの処理方法が開示されており、銅鉱石処理量６５ｔｏｎ／ｈに対して電気・電子部品屑のスクラップ装入量は０．５５ｔｏｎ／ｈと銅鉱石に対して１％未満であった。現在の自溶炉の操業技術は当時から進歩して銅精鉱の処理量が２００ｔｏｎ／ｈを超える処理量も可能となっているが、この増加した銅精鉱処理量に対して特許文献１の実施例と同等の比率でスクラップ装入量を維持すると溶錬炉において過還元によるトラブルが増加していた。このような問題は他の溶錬炉でも同様に発生することが十分に考えられる。このため、従来の乾式製錬工程における電気・電子部品屑の処理方法では、近年のリサイクル需要を満足させるだけの電気・電子部品屑の処理効率が得られていない。 Conventionally, since the electrical / electronic component waste received at a smelter is usually as large as 20 to 80 mm in particle size, most of the received electrical / electronic component waste is a mat obtained in a smelting furnace that melts and smelts ore. It is charged in the converter to be processed. In recent years, the demand for recycling electrical / electronic component waste has increased, and the amount of electrical / electronic component waste processing has increased accordingly. Here, when the amount of treatment is increased in a mat smelting furnace such as a converter as in the conventional method for treating electrical and electronic component waste, impurities contained in electrical and electronic component waste are separated compared to the smelting furnace. Since the mat smelting furnace is inferior in performance, there is a problem that impurities are increased in the final production of an anode for electrolysis. For this reason, it is desirable to treat electric / electronic component waste in a smelting furnace, but when treating electric / electronic component waste in a smelting furnace, it is contained in organic matter such as resin that constitutes electric / electronic component waste. The carbon component increased, and this caused troubles due to over-reduction during the treatment of the smelting furnace, so the amount of treatment in the smelting furnace could not be increased. More specifically, the smelting furnace has the following problems. Patent Document 1 discloses a method for treating scraps of electrical / electronic components in a flash smelting furnace, which is a type of smelting furnace, as an example. The scrap charge was 0.55 ton / h and less than 1% based on copper ore. The current flash smelting furnace operation technology has progressed since that time, and the processing amount of copper concentrate exceeding 200 ton / h is also possible. When the amount of scrap charging was maintained at the same ratio as in the above example, troubles due to over-reduction increased in the smelting furnace. Such a problem is considered to occur in other smelting furnaces as well. For this reason, the processing method of the electrical / electronic component waste in the conventional dry smelting process cannot obtain the processing efficiency of the electrical / electronic component waste sufficient to satisfy the recent recycling demand.
そこで、本発明は、溶錬炉における過還元の発生を抑制し、電気・電子部品屑をできる限り多く効率的に溶錬炉で処理することができる電気・電子部品屑の処理方法を提供することを課題とする。 Accordingly, the present invention provides a method for treating electrical / electronic component waste that can suppress the occurrence of over-reduction in the smelting furnace and can efficiently process as much electrical / electronic component waste as possible in the smelting furnace. This is the issue.
本発明者らは、上記課題を解決するために鋭意検討した結果、電気・電子部品屑を溶錬炉で処理する前に、所定のサイズ以下に粉砕することで上記課題を解決することができることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors can solve the above-mentioned problems by pulverizing electrical / electronic component scraps to a predetermined size or less before processing them in a smelting furnace. I found.
従って、本発明は一側面において、銅を含む電気・電子部品屑を粉砕し、気流分級を用いて体積基準のＤ５０で１５０μｍ以下のサイズにする工程と、前記粉砕された電気・電子部品屑を銅の溶錬炉で処理する工程とを備えた電気・電子部品屑の処理方法である。 Therefore, in one aspect of the present invention, the electric / electronic component waste containing copper is pulverized to have a volume-based D50 size of 150 μm or less using airflow classification, and the pulverized electric / electronic component waste is And a method for treating electrical / electronic component waste comprising a step of treating in a copper smelting furnace.
本発明の電気・電子部品屑の処理方法は一実施形態において、前記粉砕工程の前に、前記銅を含む電気・電子部品屑の少なくとも一部を焼却する工程をさらに備える。 In one embodiment, the method for treating electrical / electronic component waste according to the present invention further includes a step of incinerating at least part of the electrical / electronic component waste containing copper before the pulverization step.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記粉砕工程が、前記銅を含む電気・電子部品屑を粉砕し、気流分級を用いて体積基準のＤ５０で１５０μｍ以下且つ体積基準のＤ８０で２５０μｍ以下のサイズにする工程である。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, the pulverization step pulverizes the electrical / electronic component waste containing copper, and the airflow classification is used to reduce the volume based D50 to 150 μm or less. In addition, the volume-based D80 is a size of 250 μm or less .
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記粉砕工程後の電気・電子部品屑中の炭素濃度が３％以上である。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, the carbon concentration in the electrical / electronic component waste after the crushing step is 3% or more.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉で処理する工程において、前記粉砕された電気・電子部品屑に銅精鉱を混合して処理する。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, in the step of treating in the smelting furnace, the crushed electrical / electronic component waste is mixed and treated.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉で処理する工程において、前記粉砕された電気・電子部品屑に銅精鉱を混合して溶錬炉のバーナーから投入して処理する。 In another embodiment of the method for treating electrical / electronic component waste according to the present invention, in the step of treating in the smelting furnace, a copper concentrate is mixed with the crushed electrical / electronic component waste in a smelting furnace. Insert from the burner and process.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉で処理する工程において、前記粉砕された電気・電子部品屑の燃焼熱を反応熱として利用する。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, the heat of combustion of the pulverized electrical / electronic component waste is used as reaction heat in the process in the smelting furnace.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉が自溶炉である。 In another embodiment of the method for treating electrical / electronic component waste according to the present invention, the smelting furnace is a flash furnace.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記粉砕工程において、前記電気・電子部品屑を、前記溶錬炉にて前記銅精鉱と共に装入する珪酸鉱と混ぜて粉砕する。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, in the pulverization step, the electrical / electronic component waste is charged together with the copper concentrate in the smelting furnace; Mix and grind.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記粉砕工程において、前記電気・電子部品屑の少なくとも一部を竪型ローラーミルを用いて粉砕する。 In still another embodiment of the method for treating electrical / electronic component waste according to the present invention, in the grinding step, at least a part of the electrical / electronic component waste is ground using a vertical roller mill.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記粉砕工程の前に、前記銅を含む電気・電子部品屑の少なくとも一部を焼却する工程をさらに備える。 In another embodiment, the method for treating electrical / electronic component waste according to the present invention further includes a step of incinerating at least part of the electrical / electronic component waste containing copper before the pulverization step.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉で処理する工程において、前記銅精鉱に対する前記粉砕された電気・電子部品屑の重量比率を１％以上で混合する。 In still another embodiment of the method for treating electrical / electronic component waste of the present invention, in the step of treating in the smelting furnace, the weight ratio of the crushed electrical / electronic component waste to the copper concentrate is 1%. Mix with the above.
本発明の電気・電子部品屑の処理方法は更に別の一実施形態において、前記溶錬炉で処理する工程において、前記粉砕された電気・電子部品屑を重量で３ｔｏｎ／ｈ以上６ｔｏｎ／ｈ以下で処理する。 In yet another embodiment of the method for treating electrical / electronic component waste according to the present invention, in the step of treating in the smelting furnace, the pulverized electrical / electronic component waste is 3 ton / h or more and 6 ton / h or less by weight. Process with.
本発明は、銅を含む電気・電子部品屑を所定のサイズ以下に粉砕した後、粉砕された電気・電子部品屑を銅の溶錬炉で処理するため、銅の溶錬炉、例えば自溶炉の単位処理時間当たりの部品屑処理量をより多くすることができる。このため、溶練炉における炭素成分による過還元現象の発生を抑え、効率的に電気・電子部品屑を処理すること可能となる。 The present invention is a copper smelting furnace, for example, self-melting, in order to process the crushed electrical / electronic component waste in a copper smelting furnace after pulverizing the electrical / electronic component waste containing copper to a predetermined size or less. It is possible to increase the amount of scraps per unit processing time of the furnace. For this reason, generation | occurrence | production of the overreduction phenomenon by the carbon component in a melting furnace can be suppressed, and it becomes possible to process an electrical / electronic component waste efficiently.
以下に、本発明に係る電気・電子部品屑の処理方法の実施形態を、図を参照しながら説明する。 Embodiments of a method for treating electrical / electronic component waste according to the present invention will be described below with reference to the drawings.
図１に、本発明の実施形態に係る電気・電子部品屑の処理方法のフローチャートを示す。本発明に係る電気・電子部品屑の処理方法は、銅を含む電気・電子部品屑を所定のサイズに粉砕する工程と、粉砕された電気・電子部品屑を銅の溶錬炉で処理する工程とを備える。 In FIG. 1, the flowchart of the processing method of the electrical / electronic component waste which concerns on embodiment of this invention is shown. The electrical / electronic component waste processing method according to the present invention includes a step of pulverizing electrical / electronic component waste containing copper into a predetermined size, and a step of processing the pulverized electrical / electronic component waste in a copper smelting furnace. With.
本発明では、粉砕及び溶錬炉での処理の前に、まず電気・電子部品屑の少なくとも一部、好ましくは全部を焼却するのが好ましい。電気・電子部品屑を粉砕する前に焼却するため、電気・電子部品屑に含まれている樹脂等の有機物の少なくとも一部を焼却により除去することで容量を小さくすることができる。このため、より効率的な処理を行うことができる。また、電気・電子部品屑に含まれている樹脂等の有機物の少なくとも一部を焼却により除去することで、溶錬炉の処理等での電気・電子部品屑に含まれる炭素成分による過還元トラブルの発生をより良好に抑制し、炉体レンガおよびジャケットの損傷等を抑制することができる。さらに、電気・電子部品屑に含まれている金属が脆くなり、後段の粉砕工程で粉砕が容易になる。また、焼却することで、電気・電子部品屑中の揮発成分を除去することができる。このため、溶錬炉にフッ素、塩素、臭素等の好ましくない成分が混入することを抑制することができる。 In the present invention, it is preferable to first incinerate at least part, preferably all, of the electric / electronic component waste before pulverization and treatment in the smelting furnace. Since the electric / electronic component waste is incinerated before being crushed, the capacity can be reduced by removing at least a part of the organic matter such as resin contained in the electric / electronic component waste by incineration. For this reason, more efficient processing can be performed. In addition, by removing at least part of the organic substances such as resin contained in electrical / electronic component waste by incineration, over-reduction troubles caused by carbon components contained in electrical / electronic component waste during smelting furnace treatment, etc. Can be suppressed more favorably, and damage to the furnace brick and the jacket can be suppressed. Furthermore, the metal contained in the electrical / electronic component waste becomes brittle, and pulverization becomes easy in the subsequent pulverization step. Moreover, the volatile component in electrical / electronic component waste can be removed by incineration. For this reason, it can suppress that undesirable components, such as a fluorine, chlorine, a bromine, mix in a smelting furnace.
焼却工程は、特に限定されないが、例えば、ロータリーキルンによって電気・電子部品屑を５５０〜６５０℃程度で焼却した後、冷却し、１０ｍｍ〜２０ｍｍの篩目で篩い分けしてもよい。 Although an incineration process is not specifically limited, For example, after incinerating electric / electronic component waste at about 550-650 degreeC with a rotary kiln, you may cool and sieve through 10 mm-20 mm sieve mesh.
また、従来は、特許文献１に記載のように溶錬炉で処理するために電気・電子部品屑を珪酸鉱と共にボールミルで粉砕することもあったが、メタルやガラス繊維のような粉砕困難物も含まれるため、このときの電気・電子部品屑の珪酸鉱に対する比率は約１／１０以下に混合し、これを例えば自溶炉へ装入しており、自溶炉の部品屑処理量が少量であった。また、従来の他の方法としては、部品屑処理量を増加させるために粒径１０ｍｍ以下または２０ｍｍ以下に篩い分けした部品屑を粉砕せずに自溶炉へ装入していた。これに対し、焼却した電気・電子部品屑をさらに粉砕して自溶炉で処理するため、電気・電子部品屑の処理量が増加する。 Conventionally, as described in Patent Document 1, electrical and electronic component waste was sometimes pulverized with a silicate ore in a ball mill for treatment in a smelting furnace, but difficult to grind such as metal and glass fiber. Therefore, the ratio of electrical / electronic component scrap to silicate ore at this time is mixed to about 1/10 or less, and this is charged into, for example, a flash smelting furnace. It was a small amount. Further, as another conventional method, in order to increase the processing amount of the part waste, the part waste which has been sieved to a particle size of 10 mm or less or 20 mm or less has been charged into the flash furnace without being pulverized. On the other hand, since the incinerated electrical / electronic component waste is further pulverized and processed in the flash smelting furnace, the processing amount of electrical / electronic component waste increases.
本発明の粉砕工程における粉砕は、焼却部品屑が溶錬炉（例えば自溶炉）セットラー底部まで沈降する前に、又は、マットやスラグの排出部から排出されるまでに、未燃焼カーボン分が酸化し、Ｃｕ分は銅精鉱中のＳ分と反応してマットとなり、Ｆｅ分は酸素と反応してスラグ化させることが可能な粒度まで行うことが好ましい。特に溶錬炉装入前に焼却しても残存するＣｕ分やＦｅ分にはメタル状のものが存在し、このメタル状のものが炭素成分と同様に炉体ベコのような酸化物を還元させ、過還元トラブルを発生させることがある。メタル状のＣｕ分、Ｆｅ分を炉体や排出樋と接触する前にＣｕ分は原料中のＳ分と反応させてマットとし、Ｆｅ分は酸素と反応させてスラグ化させるためには粒度が小さくなるように所定サイズまで粉砕して溶錬炉に装入する。具体的には、溶錬炉に挿入する精鉱と同等かそれ以下の粒度であればよい。より具体的には、溶錬炉に装入される精鉱は一般的には体積基準のＤ５０（メディアン径）として１０〜１５０μｍであることから、例えば、電気・電子部品屑を体積基準のＤ５０が１５０μｍ以下まで粉砕するのが好ましい。また、体積基準のＤ８０が２５０μｍ以下まで粉砕してもよい。このような構成によれば、焼却電気・電子部品屑を体積基準のＤ５０が１５０μｍ以下又は体積基準のＤ８０が２５０μｍ以下となるサイズ（粒度）まで粉砕して自溶炉処理するため、自溶炉内の過還元によるトラブルがより低減する。ここで、Ｄ５０が１５０μｍ以下である粉体、及び、Ｄ８０が２５０μｍ以下である粒体は、パウダーのように細かいものであり、砂粒の大きさの砂状体よりもずっと細かな粒体である。電気・電子部品屑の処理において、本発明の好ましい形態では、このようなパウダーのように細かな粒体となるまで粉砕する。
当該Ｄ５０は１２０μｍ以下、１００μｍ以下、８０μｍ以下としてもよい。また、当該Ｄ８０は２２０μｍ以下、２００μｍ以下、１８０μｍ以下としてもよい。
The pulverization in the pulverization process of the present invention is performed before the incinerated part waste settles to the bottom of the smelting furnace (for example, a flash smelting furnace) or until it is discharged from the discharge part of the mat or slag. It is preferable that the Cu content reacts with the S content in the copper concentrate to form a mat and the Fe content reacts with oxygen to a particle size that can be slagged. In particular, even if incinerated before charging into the smelting furnace, the remaining Cu and Fe components are in the form of metal, and this metal-like component reduces oxides such as furnace bodies as well as the carbon component. May cause over-reduction troubles. Before contacting the metal-like Cu and Fe components with the furnace body and discharge rod, the Cu component reacts with the S component in the raw material to form a mat, and the Fe component reacts with oxygen to form a slag. It grind | pulverizes to a predetermined size so that it may become small, and it charges in a smelting furnace. Specifically, the grain size may be equal to or less than that of the concentrate to be inserted into the smelting furnace. More specifically, the concentrate charged into the smelting furnace is generally 10 to 150 μm in terms of volume-based D50 (median diameter). Is preferably pulverized to 150 μm or less. The volume-based D80 may be pulverized to 250 μm or less. According to such a configuration, the incineration electric / electronic component waste is pulverized to a size (particle size) with a volume-based D50 of 150 μm or less or a volume-based D80 of 250 μm or less. Troubles due to overreduction in the inside are further reduced. Here, the powder having a D50 of 150 μm or less and the granule having a D80 of 250 μm or less are fine like powder and are much finer than a sandy body having the size of a sand grain. . In the treatment of electrical / electronic component waste, in a preferred form of the present invention, the powder is pulverized until it becomes a fine particle such as powder.
The D50 may be 120 μm or less, 100 μm or less, or 80 μm or less. The D80 may be 220 μm or less, 200 μm or less, or 180 μm or less.
なお、自溶炉内の過還元によるトラブルとしては、例えば、自溶炉の内壁にセルフコーティングとしての炉体ベコ（例えば、マグネタイトを主成分とする酸化物）が形成されているが、これが過還元によって融解して除去されてしまい、炉体レンガおよびジャケットの損傷等が発生するもの等が挙げられる。 In addition, as a trouble due to overreduction in the flash smelting furnace, for example, a furnace body beco (eg, an oxide containing magnetite as a main component) is formed on the inner wall of the flash smelting furnace. Examples include those that are melted and removed by reduction and cause damage to furnace bricks and jackets.
より詳細には、従来は電気・電子部品屑を珪酸鉱と共にボールミルで粉砕しているが、電気・電子部品屑にはボールミルで粉砕されずに滞留する粉砕困難物が含まれるため、上述したような珪酸鉱に対する電気・電子部品屑の投入比率を高くしてボールミルに導入するとメタルや、メタルのような比重の大きいもの等の粉砕困難物がボールミル内に蓄積しボールミルの容積を徐々に減少させることで粉砕処理速度の低減につながっていた。これに対し、本発明のように焼却電気・電子部品屑を精鉱と同じ体積基準のＤ５０が１５０μｍ以下又は体積基準のＤ８０が２５０μｍ以下まで粉砕して自溶炉に装入することにより、精鉱と同程度の反応速度が見込まれるため炉壁や炉底に到達する前にシャフト部や溶湯内で残留炭素の還元反応を完了させ、自溶炉内の過還元によるトラブルが低減する。したがって、溶錬炉において電気・電子部品屑処理量を制限する必要が無くなり、製錬工程において従来以上に電気・電子部品屑の処理量を増加させることができる。また、本発明では、溶錬炉で処理する工程において、粉砕された電気・電子部品屑に銅精鉱を混合して溶錬炉のバーナーから投入して処理してもよい。また、本発明では、溶錬炉で処理する工程において、粉砕された電気・電子部品屑の燃焼熱を反応熱として利用することができ、このような構成によって良好なコストで効率的な電気・電子部品屑の処理を行うことができる。 More specifically, in the past, electrical / electronic component waste was pulverized with a silicate ore with a ball mill, but the electrical / electronic component waste contains difficult-to-crush materials that remain without being pulverized by the ball mill. When the ratio of electric and electronic component waste to high silicate ore is increased and introduced into a ball mill, metal and difficult-to-crush materials such as metal with high specific gravity accumulate in the ball mill and gradually reduce the volume of the ball mill. This led to a reduction in the pulverization speed. On the other hand, as in the present invention, the incinerated electrical / electronic component waste is crushed to the same volume standard D50 as that of the concentrate to 150 μm or less or the volume standard D80 is 250 μm or less and charged into the flash smelting furnace. Since a reaction rate similar to that of ore is expected, the reduction reaction of residual carbon is completed in the shaft and molten metal before reaching the furnace wall and bottom, and troubles due to overreduction in the flash furnace are reduced. Therefore, there is no need to limit the amount of waste of electric / electronic parts in the smelting furnace, and the amount of waste of electric / electronic parts can be increased more than before in the smelting process. In the present invention, in the step of treating in the smelting furnace, the copper concentrate may be mixed with the crushed electrical / electronic component waste and charged from the burner of the smelting furnace. Further, in the present invention, in the process in the smelting furnace, the heat of combustion of the crushed electrical / electronic component waste can be used as reaction heat, and with such a configuration, efficient electrical / Electronic component waste can be processed.
また、本発明の電気・電子部品屑の処理方法においては、粉砕工程において、電気・電子部品屑を、溶錬炉にて銅精鉱と共に装入する珪酸鉱と混ぜて粉砕してもよい。通常、非鉄製錬炉においてはスラグの流動性を良好にするために珪酸鉱などの溶剤を原料精鉱とともに溶錬炉に装入するが、溶剤を購入する際には安価な塊状で購入する場合が多く、ボールミルなどを用いて自社で粉砕している場合が多い。したがって、溶剤ミルの能力に余裕がある場合は、電気・電子部品屑を溶錬炉にて銅精鉱と共に装入する珪酸鉱と混ぜて粉砕処理することで、破砕設備導入コストを要することなく実施することができる。 In the method for treating electrical / electronic component waste according to the present invention, in the pulverization step, electrical / electronic component waste may be mixed and pulverized with silicate ore charged together with copper concentrate in a smelting furnace. Usually, in non-ferrous smelting furnaces, silicate ore and other solvents are charged into the smelting furnace together with the raw material concentrate in order to improve the slag fluidity. In many cases, they are pulverized in-house using a ball mill. Therefore, when there is a margin in the capacity of the solvent mill, electric and electronic parts scraps are mixed with silicate ore charged with copper concentrate in a smelting furnace and pulverized, so there is no need to introduce crushing equipment. Can be implemented.
粉砕工程後の電気・電子部品屑は、当該部品屑に含まれている樹脂等の有機物等に起因する炭素成分が残存していてもよい。ここで、当該粉砕工程後の電気・電子部品屑中の炭素濃度が３％以上であってもよく、５％以上であってもよく、１０％以上であってもよい。また、炭素濃度の上限としては、３０％以下であってもよい。 In the electric / electronic component waste after the pulverization step, a carbon component derived from organic matter such as resin contained in the component waste may remain. Here, the carbon concentration in the electric / electronic component waste after the pulverization step may be 3% or more, 5% or more, or 10% or more. Further, the upper limit of the carbon concentration may be 30% or less.
また、本発明の電気・電子部品屑の処理方法においては、粉砕工程において、電気・電子部品屑の少なくとも一部を、竪型ローラーミルを用いて粉砕してもよい。図２は、竪型ローラーミルの模式図である。竪型ローラーミルを用いた粉砕方式としては、まず、粉砕対象の電気・電子部品屑をスクリューフィーダを通して水平回転するテーブル中央へ供給する。テーブルには、外周側に沿って設けられた凹部が形成されている。テーブル中央に供給された電気・電子部品屑は、遠心力でテーブル外周方向に移動する。このとき、テーブルの凹部上面に沿うように取り付けられたローラ（２〜３個）と、テーブルとの間で電気・電子部品屑が粉砕される。粉砕されて微粉となった電気・電子部品屑は、さらに外周方向に移動して、下方から上方へと流れる上昇気流（大気を利用）で吹き上げられ、分級（気流分級）されて上方に設けられたロータ内へ運ばれて回収される。 Moreover, in the processing method of the electrical / electronic component waste of this invention, you may grind | pulverize at least one part of electrical / electronic component waste using a vertical roller mill in a grinding | pulverization process. FIG. 2 is a schematic view of a vertical roller mill. As a pulverization method using a vertical roller mill, first, electric / electronic component waste to be pulverized is supplied through a screw feeder to the center of a table that rotates horizontally. The table is formed with a recess provided along the outer peripheral side. The electrical / electronic component waste supplied to the center of the table moves in the direction of the outer periphery of the table by centrifugal force. At this time, electrical / electronic component waste is pulverized between the table (2 to 3 rollers) attached along the upper surface of the concave portion of the table and the table. The electric and electronic component waste that has been pulverized into fine powder moves further in the outer peripheral direction, and is blown up by an updraft (using the atmosphere) that flows from below to above, and is classified (airflow classification) and provided above. It is transported into the rotor and collected.
竪型ローラーミルを用いた粉砕方式によれば、気流分級効果を利用して風量を調節することにより、電気・電子部品屑の粉砕後の粒度を制御することができる。すなわち、比重の大きいメタルは細かく粉砕されていなければ気流によって上方へ運べないため、この作用を利用して所定の大きさ以下のメタルのみを気流で上方へ運び、それ以上の大きさのメタルから分離（気流分級）することができる。
また、未粉砕物はテーブル下に落ちて溜まるため、未粉砕物が発生する場合は定期的に排出運転をすることによって未粉砕物を排出することができる。また、熱風を導入することができるため、乾燥粉砕が可能である。また、動力源単位が小さく、高効率な粉砕が可能である。また、電気・電子部品屑の粉砕で発生するメタル等の比重の大きい未粉砕物を自動排出することで、連続的な運転が可能である。
According to the pulverization method using the vertical roller mill, the particle size after pulverization of the electric / electronic component waste can be controlled by adjusting the air volume using the airflow classification effect. In other words, a metal with a large specific gravity cannot be carried upward by an air current unless it is finely crushed. Therefore, using this action, only a metal having a predetermined size or less is carried upward by an air current, and from a metal having a larger size than that. Separation (airflow classification) can be performed.
Moreover, since the unground product falls and accumulates under the table, when the unground product is generated, the unground product can be discharged by periodically performing a discharging operation. Further, since hot air can be introduced, dry pulverization is possible. In addition, the power source unit is small, and highly efficient pulverization is possible. Moreover, continuous operation is possible by automatically discharging unpulverized material having a large specific gravity, such as metal, generated by pulverization of electrical / electronic component waste.
また、本発明では、上述のように銅を含む電気・電子部品屑を所定のサイズ以下に粉砕する工程と、粉砕された電気・電子部品屑を銅の溶錬炉で処理する工程とを備えるため、溶錬炉で処理する工程において、銅精鉱に対する粉砕された電気・電子部品屑の重量比率を１％以上で混合することができ、従来に比べ、所定処理量の銅精鉱に対してより多くの電気・電子部品屑の処理が可能となる。さらに、本発明では、溶錬炉で処理する工程において、粉砕された電気・電子部品屑を重量で３ｔｏｎ／ｈ以上６ｔｏｎ／ｈ以下で処理することができ、従来に比べ、効率的な電気・電子部品屑の処理が可能となる。 Moreover, in this invention, the process of grind | pulverizing the electrical / electronic component waste containing copper to below a predetermined size as mentioned above, and the process of processing the grind | pulverized electrical / electronic component waste in a copper smelting furnace are provided. Therefore, in the process in the smelting furnace, the weight ratio of the crushed electrical / electronic component waste to the copper concentrate can be mixed at 1% or more, and compared to the conventional processing, This makes it possible to dispose of more electrical and electronic component waste. Further, in the present invention, in the process of processing in the smelting furnace, the crushed electric / electronic component waste can be processed at a weight of 3 ton / h or more and 6 ton / h or less, which is more efficient than conventional methods. Electronic component waste can be processed.
以下、本発明の実施例を説明するが、実施例は例示目的であって発明が限定されることを意図しない。 Examples of the present invention will be described below, but the examples are for illustrative purposes and are not intended to limit the invention.
以下に示すように、本発明の電気・電子部品屑の処理方法を実操業で実施するための模擬試験を行った。
Ｃｕ：３０質量％、Ｆｅ：４．２質量％、ＳｉＯ2：２０質量％、：Ａｌ2Ｏ3：１０質量％を含む電気・電子部品屑を準備し、当該電気・電子部品屑をロータリーキルンによって５５０〜６５０℃で焼却した後、冷却し、１０ｍｍの篩目で篩い分けした。焼却後の電気・電子部品屑は、焼却前の電気・電子部品屑に対して２５体積％減少していた。当該減少分は、電気・電子部品屑に含まれていた有機物の炭素成分がＣＯ2となって除去されたものと考えられる。
次に、篩い分け後の篩下の電気・電子部品屑を図２に示すような竪型ローラーミルを用いて体積基準のＤ５０が１００μｍ以下まで粉砕した。なお、体積基準のＤ５０は日機装社製マイクロトラックＭＴ３３００にて測定した。ミル内のテーブルは１２００ｍｍ径、ローラ数を３つ、駆動方式を竪型減速機（カップリング直結型）、電動機の出力を３４０ｋＷ（ミル本体）とした。
粉砕されて微粉となった電気・電子部品屑は、ミル内において下方から上方へと流れる上昇気流（大気を利用）で吹き上げ、風量を調節することで分級（気流分級）して、上方に設けたロータ内へ運んで回収した。
回収後の電気・電子部品屑の組成は、Ｃｕ：２７質量％、Ｆｅ：４．１質量％、ＳｉＯ2：２１質量％、：Ａｌ2Ｏ3：１１質量％であった。
また、水分含有量は、焼却前の電気・電子部品屑においては１５％以下、回収後の電気・電子部品屑においては３％以下であった。
As shown below, a simulation test for carrying out the method for treating electrical / electronic component waste according to the present invention in actual operation was performed.
Electrical / electronic component waste containing Cu: 30% by mass, Fe: 4.2% by mass, SiO 2 : 20% by mass, and Al 2 O 3 : 10% by mass is prepared, and the electrical / electronic component waste is removed by a rotary kiln. After incineration at 550 to 650 ° C., the mixture was cooled and sieved with a 10 mm sieve mesh. The electrical / electronic component waste after incineration was reduced by 25% by volume with respect to the electrical / electronic component waste before incineration. The decrease is considered to be due to the removal of the organic carbon component contained in the electrical / electronic component waste as CO 2 .
Next, the electric / electronic component waste under the sieve after sieving was pulverized to a volume-based D50 of 100 μm or less using a vertical roller mill as shown in FIG. The volume-based D50 was measured by Nikkiso Microtrack MT3300. The table in the mill had a diameter of 1200 mm, the number of rollers was 3, the drive system was a vertical reduction gear (coupled type), and the output of the motor was 340 kW (mill main body).
The electric and electronic component waste that has been pulverized into fine powder is blown up by an updraft (using the atmosphere) that flows from the bottom to the top in the mill, and is classified (airflow classification) by adjusting the air volume, and provided above It was collected in the rotor.
The composition of the electric / electronic component waste after the recovery was Cu: 27 mass%, Fe: 4.1 mass%, SiO 2 : 21 mass%, and: Al 2 O 3 : 11 mass%.
Further, the moisture content was 15% or less for the electric / electronic component waste before incineration, and 3% or less for the electric / electronic component waste after the recovery.
次に、粉砕後、気流分級によって回収した電気・電子部品屑を銅の溶錬炉の１種である自溶炉で処理した。自溶炉の原料処理条件は、銅精鉱処理量が２１５ｔｏｎ／ｈであり、電気・電子部品屑処理量が銅精鉱処理量に対して２.０％であった。このとき、自熔炉において過還元が発生することなく電気・電子部品屑を良好に処理することができた。溶錬炉で生成したマットを転炉の酸化製錬炉で粗銅とした後、電解用アノードを製造した。このように、上述したような、特許文献１に記載の従来の電気・電子部品屑スクラップの処理方法で、銅鉱石処理量６５ｔｏｎ／ｈに対して電気・電子部品屑のスクラップ装入量が０．５５ｔｏｎ／ｈと銅鉱石に対して１％未満であったものに比べて、処理効率が大きく向上した結果となった。
また、上記実施例では、焼却前の電気・電子部品屑を５，０００ｔｏｎ／月の処理量で処理することができた。
Next, after pulverization, the electrical / electronic component waste recovered by airflow classification was treated in a flash smelting furnace which is a kind of copper smelting furnace. The raw material treatment conditions of the flash smelting furnace were a copper concentrate treatment amount of 215 ton / h, and an electrical / electronic component waste treatment amount of 2.0% with respect to the copper concentrate treatment amount. At this time, it was possible to satisfactorily treat the electrical / electronic component waste without causing excessive reduction in the auto-smelting furnace. After the mat produced in the smelting furnace was made into crude copper in the oxidation smelting furnace of the converter, an anode for electrolysis was produced. Thus, in the conventional method for treating scraps of electrical / electronic parts scrap described in Patent Document 1 as described above, the scrap charge amount of scraps of electrical / electronic parts is 0 with respect to a copper ore throughput of 65 ton / h. As a result, the treatment efficiency was greatly improved as compared with .55 ton / h and less than 1% with respect to copper ore.
Moreover, in the said Example, the electrical / electronic component waste before incineration was able to be processed with the processing amount of 5,000 ton / month.
Claims (12)
前記粉砕された電気・電子部品屑を銅の溶錬炉で処理する工程と、
を備えた電気・電子部品屑の処理方法。 Copper was ground electric and electronic parts scraps containing the steps of the following size 150μm with D50 based on volume using an air classifier,
Processing the crushed electrical / electronic component waste in a copper smelting furnace;
Electrical / electronic component waste processing method with
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| JP7076178B2 (en) * | 2016-11-18 | 2022-05-27 | Ｊｘ金属株式会社 | How to dispose of scraps of electronic and electrical equipment parts |
| JP6967856B2 (en) * | 2017-01-26 | 2021-11-17 | Ｊｘ金属株式会社 | How to dispose of electrical and electronic component waste |
| US11548032B2 (en) | 2018-01-31 | 2023-01-10 | Jx Nippon Mining & Metals Corporation | Method for removing wire-form objects, device for removing wire-form objects, and method for processing electronic/electrical apparatus component scrap |
| CA3090225C (en) | 2018-01-31 | 2023-10-24 | Jx Nippon Mining & Metals Corporation | Processing method for electronic/electric device component waste |
| KR20200129155A (en) | 2018-03-16 | 2020-11-17 | 제이엑스금속주식회사 | Disposal method of electronic and electrical equipment parts debris |
| JP6914220B2 (en) | 2018-03-16 | 2021-08-04 | Ｊｘ金属株式会社 | How to dispose of scraps of electronic and electrical equipment parts |
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| KR20210087056A (en) | 2018-10-31 | 2021-07-09 | 제이엑스금속주식회사 | Composition analysis apparatus for scrap of electronic/electric equipment parts, apparatus for processing electronic/electric equipment scraps, and method for processing scrap of electronic/electric equipment parts |
| JP7076397B2 (en) | 2019-03-29 | 2022-05-27 | Ｊｘ金属株式会社 | How to dispose of scraps of electronic and electrical equipment parts |
| JP7029424B2 (en) | 2019-03-29 | 2022-03-03 | Ｊｘ金属株式会社 | How to dispose of scraps of electronic and electrical equipment parts |
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| JP7282582B2 (en) | 2019-04-22 | 2023-05-29 | Ｊｘ金属株式会社 | Processing method and processing equipment for electronic and electrical equipment parts waste |
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| JP2019202319A (en) * | 2019-08-21 | 2019-11-28 | Ｊｘ金属株式会社 | Vertical pulverizing apparatus and method for operation of vertical pulverizing apparatus |
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