JP7714629B2 - Method for removing bromine compounds and purifying copper from copper-containing recycled materials - Google Patents
Method for removing bromine compounds and purifying copper from copper-containing recycled materialsInfo
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- JP7714629B2 JP7714629B2 JP2023219787A JP2023219787A JP7714629B2 JP 7714629 B2 JP7714629 B2 JP 7714629B2 JP 2023219787 A JP2023219787 A JP 2023219787A JP 2023219787 A JP2023219787 A JP 2023219787A JP 7714629 B2 JP7714629 B2 JP 7714629B2
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- 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
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Description
本発明は電子廃棄物の処理に関し、特に、廃棄されたプリント回路基板に由来する銅含有リサイクル原料の処理方法に関する。 The present invention relates to the treatment of electronic waste, and in particular to a method for treating copper-containing recycled materials derived from discarded printed circuit boards.
廃棄されたプリント回路基板には、銅箔、樹脂、ガラスファイバー布、臭素系難燃剤などの物質が含まれ、廃棄されたプリント回路基板を資源化して回収再利用することは現在の重要な課題であり、特に、廃棄されたプリント回路基板から銅をいかにして回収し、そして廃棄されたプリント回路基板に含まれる臭素系難燃剤による汚染問題をいかにして回避するかが重要視されている。 Discarded printed circuit boards contain substances such as copper foil, resin, glass fiber cloth, and brominated flame retardants, and recovering and reusing discarded printed circuit boards is currently an important issue. In particular, there is a focus on how to recover copper from discarded printed circuit boards and how to avoid contamination issues caused by brominated flame retardants contained in discarded printed circuit boards.
例えば特許文献１には、電子基板の臭素系難燃剤を含む非金属画分を鉄を添加させた水蒸気雰囲気下で熱分解することにより、生成される液体生成物中の有機臭素化合物の脱臭素化を促進するといった、臭素系難燃剤を含む樹脂の熱分解における脱臭素化方法が開示された。また、特許文献２には、漸次に高められた加熱温度と超重力分離技術を利用して、廃棄された電子回路基板の粉からスズ合金液体と鉛基合金液体と亜鉛アルミニウム銅合金液体および粗銅液体を順番に分離させるといった、廃棄された電子回路基板の粉から有価金属を回収する方法が開示された。 For example, Patent Document 1 discloses a debromination method for the thermal decomposition of resins containing brominated flame retardants, in which non-metallic fractions containing brominated flame retardants from electronic circuit boards are thermally decomposed in a steam atmosphere containing added iron to promote debromination of organic bromine compounds in the resulting liquid product. Patent Document 2 also discloses a method for recovering valuable metals from discarded electronic circuit board powder, in which gradually elevated heating temperatures and supergravity separation technology are used to sequentially separate tin alloy liquid, lead-based alloy liquid, zinc-aluminum-copper alloy liquid, and crude copper liquid from the discarded electronic circuit board powder.
従って、本発明の目的は銅含有リサイクル原料から臭素化合物を除去し且つ銅を精製する方法を新規に提供することである。 Accordingly, an object of the present invention is to provide a novel method for removing bromine compounds from copper-containing recycled materials and purifying copper.
上記目的を達成すべく、本発明は銅及び臭素化合物を含む銅含有リサイクル原料に対して低温熱分解を行うことで前記臭素化合物により形成される臭化水素ガスと前記銅を含む処理待ち銅粉末とに分離し、
前記臭化水素ガスを金属酸化物と反応させて金属臭素化合物の固体を形成し、前記処理待ち銅粉末に対して加熱純化処理を行うことで、前記処理待ち銅粉末の中の前記銅を溶融させて液体の銅に変化させて不純物を含む熔湯を得て、
前記熔湯にスラグ除去剤を投入して前記熔湯の中にある前記液体の銅以外の物質と前記スラグ除去剤とにより前記液体の銅の上に浮き上がるスラグ相層を形成させてから、前記スラグ相層を除去することで前記液体の銅を分離させる、銅含有リサイクル原料から臭素化合物を除去し且つ銅を精製する方法を提供する。
In order to achieve the above object, the present invention provides a method for separating a copper-containing recycled raw material containing copper and a bromine compound into hydrogen bromide gas formed by the bromine compound and copper powder to be processed,
The hydrogen bromide gas is reacted with a metal oxide to form a solid metal bromine compound, and the copper powder to be treated is subjected to a heat purification treatment, thereby melting the copper in the copper powder to be treated and changing it into liquid copper, thereby obtaining a molten metal containing impurities;
The method for removing bromine compounds from copper-containing recycled raw materials and purifying copper includes adding a slag remover to the molten metal to form a slag phase layer that floats on the liquid copper by the slag remover and substances other than the liquid copper in the molten metal, and then removing the slag phase layer to separate the liquid copper.
本発明の方法は臭素化合物を汚染性もしくは危険性のない金属臭素化合物の固体に転換させるだけでなく、銅含有リサイクル原料から銅を回収して高純度の銅を得ることができる。 The method of the present invention not only converts bromine compounds into solid metal bromine compounds that are not polluting or hazardous, but also enables the recovery of copper from copper-containing recycled feedstocks, resulting in high-purity copper.
以下は図面を参照して本発明の銅含有リサイクル原料から臭素化合物を除去し且つ銅を精製する方法の１つの実施例について詳しく説明する。 The following describes in detail one embodiment of the method for removing bromine compounds and purifying copper from copper-containing recycled material of the present invention, with reference to the drawings.
図１は本発明の銅含有リサイクル原料から臭素化合物を除去し且つ銅を精製する方法が示されるフローチャートである。 Figure 1 is a flow chart showing the method of the present invention for removing bromine compounds and purifying copper from copper-containing recycled materials.
図示のように、まずは銅及び臭素化合物を含む銅含有リサイクル原料に対して低温熱分解処理を行うことで前記臭素化合物の熱分解により形成された臭化水素ガスと、前記銅を含む処理待ち銅粉末とに分離する。前記臭素化合物として例えばテトラブロモビスフェノールＡエポキシ樹脂等の臭素系難燃剤が挙げられるが、これに限られない。詳しく説明すると、前記銅含有リサイクル原料は、廃棄されたプリント回路基板に対してリサイクル処理を行うことで得られたものであり、前記リサイクル処理は、前記廃棄されたプリント回路基板を粉砕してなった多量の廃材から、銅を含む廃材を前記銅含有リサイクル原料として選出することが含まれる。前記廃棄されたプリント回路基板には、銅箔、樹脂、ガラスファイバー布、臭素系難燃剤などが元々含まれていたため、前記銅含有リサイクル原料には、前記銅と臭素系難燃剤に加えてガラスファイバー布と樹脂が含まれる。ちなみに、低温熱分解処理によれば、臭素化合物を臭素化ダイオキシンではなく臭化水素ガスに変化させることができる。この実施例では流動床反応器の中で前記銅含有リサイクル原料に対して前記低温熱分解処理を行う。具体的には、前記低温熱分解処理は３００℃～５００℃の温度範囲で行われる。蛍光Ｘ線分析装置を用いて前記銅含有リサイクル原料及び前記処理待ち銅粉末を分析したところ、前記銅含有リサイクル原料の中で銅が占めるパーセンテージは８０％であり、臭素が占めるパーセンテージは０.０３２６％であり、前記処理待ち銅粉末の中で臭素が占めるパーセンテージは０.００７３％であった。 As shown in the figure, copper-containing recycled material containing copper and bromine compounds is first subjected to low-temperature pyrolysis to separate hydrogen bromide gas formed by pyrolysis of the bromine compounds and copper powder containing the copper, ready for processing. Examples of the bromine compounds include, but are not limited to, brominated flame retardants such as tetrabromobisphenol A epoxy resin. More specifically, the copper-containing recycled material is obtained by recycling discarded printed circuit boards, which involves selecting copper-containing waste material from the large amount of waste material obtained by crushing the discarded printed circuit boards. Because the discarded printed circuit boards originally contained copper foil, resin, glass fiber cloth, and brominated flame retardants, the copper-containing recycled material contains glass fiber cloth and resin in addition to the copper and brominated flame retardants. Incidentally, low-temperature pyrolysis converts bromine compounds into hydrogen bromide gas rather than brominated dioxins. In this example, the copper-containing recycled material is subjected to low-temperature pyrolysis in a fluidized-bed reactor. Specifically, the low-temperature pyrolysis treatment is carried out at a temperature range of 300°C to 500°C. Analysis of the copper-containing recycled material and the copper powder awaiting treatment using an X-ray fluorescence analyzer revealed that the percentage of copper in the copper-containing recycled material was 80%, the percentage of bromine was 0.0326%, and the percentage of bromine in the copper powder awaiting treatment was 0.0073%.
それから、前記臭化水素ガスを金属酸化物と反応させることで、前記臭化水素ガスを分解させると共に、前記金属酸化物により金属臭素化合物の固体を形成する。詳しく説明すると、前記金属酸化物とは砂鉄であり、前記砂鉄に酸化第二鉄が含まれ、Ｘ線回折装置を利用して前記金属臭素化合物の固体を分析したところ、前記金属臭素化合物の固体に臭化鉄（ＩＩ）が含まれることが分かる。 Then, the hydrogen bromide gas is reacted with a metal oxide to decompose the hydrogen bromide gas and form a solid metal bromine compound with the metal oxide. More specifically, the metal oxide is iron sand, which contains ferric oxide. Analysis of the solid metal bromine compound using an X-ray diffraction device reveals that it contains iron(II) bromide.
それから、前記処理待ち銅粉末に対して加熱純化処理を実行することで、前記処理待ち銅粉末の中にある前記銅を溶融させて液体の銅に変化させて不純物を含む熔湯を得る。詳しく説明すると、前記銅含有リサイクル原料に前記ガラスファイバー布及び前記樹脂が更に含まれるため、前記加熱純化処理では、前記樹脂を熱分解させると共に、前記ガラスファイバー布を溶融してガラス滓にするので、前記熔湯の中には前記ガラス滓及び前記樹脂が熱分解された物質が更に含まれている。この実施例では、前記加熱純化処理は大気誘導溶解装置の中で誘導溶解法を用いて前記処理待ち銅粉末の中の前記銅を１２００℃以上の温度で溶融させて液体の銅にする。詳しく説明すると、前記銅を１２００℃～１７００℃の温度範囲内で溶融させる。 Then, a thermal purification process is performed on the copper powder awaiting processing, melting the copper in the copper powder awaiting processing and converting it into liquid copper, thereby obtaining a molten metal containing impurities. More specifically, because the copper-containing recycled material also contains the glass fiber cloth and resin, the thermal purification process thermally decomposes the resin and melts the glass fiber cloth into glass slag, resulting in the molten metal further containing the glass slag and materials formed by the thermal decomposition of the resin. In this embodiment, the thermal purification process uses induction melting in an atmospheric induction melting apparatus to melt the copper in the copper powder awaiting processing at a temperature of 1200°C or higher to convert it into liquid copper. More specifically, the copper is melted within a temperature range of 1200°C to 1700°C.
それから、前記熔湯にスラグ除去剤を投入して前記熔湯の中にある前記液体の銅以外の物質と前記スラグ除去剤とによりスラグ相層を形成させ、且つ、前記スラグ相層が前記液体の銅の上に浮き上がるため、前記スラグ相層を除去することは、すなわち前記液体の銅を分離させることとなる。前記スラグ除去剤としては、例えばＣａＯ、ＭｇＯ、ＳｉＯ２の金属酸化物や、氷晶石（Ｎａ３ＡｌＦ６）もしくは四ホウ酸ナトリウム（Ｎａ２Ｂ４Ｏ７）など常用のスラグ除去剤が挙げられるが、これらに限らず、そして前記熔湯の実際の内容物に応じてスラグ除去剤を選択利用することができ、本発明において用いられる前記スラグ除去剤はいずれも市販品である。この実施例では、走査型電子顕微鏡（ＳＥＭ）及びエネルギー分散型Ｘ線分析（ＥＤＳ）システムを合わせて成分分析を行った結果、前記スラグ相層の成分に、酸化カルシウム（ＣａＯ）、二酸化ケイ素（ＳｉＯ２）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム（Ａｌ２Ｏ３）により構成されたＣａＯ‐ＳｉＯ２‐ＭｇＯ‐（Ａｌ２Ｏ３）複合相が含まれることを発見し、そして誘導結合プラズマ分光分析装置を用いて前記液体の銅を分析したところ、前記液体の銅において銅が占めるパーセンテージは９９.７％であることが分かったので、前記銅含有リサイクル原料において銅が占めるパーセンテージが８０％であったことと比べ、前記液体の銅に含まれる銅のパーセンテージは明らかに向上したことにより、本発明は前記銅含有リサイクル原料から高純度の銅を精製できることが証明された。 A slag remover is then added to the molten metal to form a slag layer between the molten metal and the materials other than the liquid copper. The slag layer rises to the top of the liquid copper, and removing the slag layer separates the liquid copper. Examples of slag removers include, but are not limited to , metal oxides such as CaO, MgO, and SiO2 , as well as commonly used slag removers such as cryolite ( Na3AlF6 ) and sodium tetraborate ( Na2B4O7 ). The slag remover can be selected based on the actual contents of the molten metal. The slag removers used in the present invention are all commercially available products. In this example, a component analysis was performed using a scanning electron microscope (SEM) and an energy dispersive X-ray analyzer (EDS) system, and it was found that the slag phase layer contained a CaO- SiO2 - MgO-( Al2O3 ) composite phase composed of calcium oxide (CaO), silicon dioxide (SiO2), magnesium oxide (MgO), and aluminum oxide ( Al2O3 ) . Furthermore, an inductively coupled plasma spectrometer was used to analyze the copper in the liquid, and it was found that the copper content in the liquid was 99.7%. This is significantly higher than the 80% copper content in the copper-containing recycled material, and proves that the present invention can refine high-purity copper from the copper-containing recycled material.
以上、本発明の実施形態を説明したが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で種々の変更が可能である。 The above describes an embodiment of the present invention, but the present invention is not limited to this and various modifications are possible without departing from the spirit of the invention.
Claims (9)
前記臭化水素ガスを金属酸化物と反応させて金属臭素化合物の固体を形成し、前記処理待ち銅粉末に対して加熱純化処理を行うことで、前記処理待ち銅粉末の中の前記銅を溶融させて液体の銅に変化させて不純物を含む熔湯を得て、
前記熔湯にスラグ除去剤を投入して前記熔湯の中にある前記液体の銅以外の物質と前記スラグ除去剤とにより前記液体の銅の上に浮き上がるスラグ相層を形成させてから、前記スラグ相層を除去することで前記液体の銅を分離させ、
前記銅含有リサイクル原料の中にはガラスファイバー布及び樹脂が更に含まれており、前記銅含有リサイクル原料は、廃棄されたプリント回路基板に対してリサイクル処理を行うことで得られたものであり、
前記リサイクル処理には、前記廃棄されたプリント回路基板を粉砕させてなった廃材から、銅を含む廃材を前記銅含有リサイクル原料として選出することが含まれることを特徴とする銅含有リサイクル原料から臭素化合物を除去し且つ銅を精製する方法。 A copper-containing recycled raw material containing copper and a bromine compound is subjected to low-temperature pyrolysis to separate the raw material into hydrogen bromide gas formed by the bromine compound and copper powder containing the copper, and the copper powder is ready for processing.
The hydrogen bromide gas is reacted with a metal oxide to form a solid metal bromine compound, and the copper powder to be treated is subjected to a heat purification treatment, thereby melting the copper in the copper powder to be treated and changing it into liquid copper, thereby obtaining a molten metal containing impurities;
adding a slag remover to the molten metal to form a slag phase layer floating on the liquid copper by the slag remover and the substances other than the liquid copper in the molten metal, and then removing the slag phase layer to separate the liquid copper ;
The copper-containing recycled material further includes glass fiber cloth and resin, and the copper-containing recycled material is obtained by recycling discarded printed circuit boards;
The method for removing bromine compounds from copper-containing recycled raw materials and purifying copper, characterized in that the recycling process includes selecting copper-containing waste materials as the copper-containing recycled raw materials from waste materials obtained by crushing the discarded printed circuit boards .
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| JP2000301131A (en) | 1998-12-11 | 2000-10-31 | Matsushita Electric Ind Co Ltd | Waste printed circuit board treatment method |
| JP2001259603A (en) | 2000-03-15 | 2001-09-25 | Sumitomo Metal Mining Co Ltd | Method for separating valuable resources from used printed wiring boards |
| JP2003301225A (en) | 2002-04-11 | 2003-10-24 | Asahi Pretec Corp | Method for recovering noble metal |
| CN101921915A (en) | 2009-06-12 | 2010-12-22 | 巫协森 | Method and device for recovering substrate from pyrolysis waste printed circuit boards |
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| CN205774730U (en) | 2016-06-22 | 2016-12-07 | 江西自立环保科技有限公司 | A kind of complete set of equipments refining noble metal from wiring board waste material |
| CN212833940U (en) | 2020-07-20 | 2021-03-30 | 中节能（汕头）再生资源技术有限公司 | Copper-based organic solid waste recycling, reduction and harmless treatment device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011062644A (en) * | 2009-09-17 | 2011-03-31 | Hyo Sok Ahn | Method for recovering valuable resource from disposed matter |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000301131A (en) | 1998-12-11 | 2000-10-31 | Matsushita Electric Ind Co Ltd | Waste printed circuit board treatment method |
| JP2001259603A (en) | 2000-03-15 | 2001-09-25 | Sumitomo Metal Mining Co Ltd | Method for separating valuable resources from used printed wiring boards |
| JP2003301225A (en) | 2002-04-11 | 2003-10-24 | Asahi Pretec Corp | Method for recovering noble metal |
| CN101921915A (en) | 2009-06-12 | 2010-12-22 | 巫协森 | Method and device for recovering substrate from pyrolysis waste printed circuit boards |
| JP2014513215A (en) | 2011-05-10 | 2014-05-29 | エコループ ゲーエムベーハー | Methods for obtaining metals and rare earth metals from scrap |
| CN205774730U (en) | 2016-06-22 | 2016-12-07 | 江西自立环保科技有限公司 | A kind of complete set of equipments refining noble metal from wiring board waste material |
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