KR101141542B1 - Method for Glass Fiber Separation from Depolymerization of Waste Circuit Boards Using Organic Solvent - Google Patents
Method for Glass Fiber Separation from Depolymerization of Waste Circuit Boards Using Organic Solvent Download PDFInfo
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- KR101141542B1 KR101141542B1 KR20100032814A KR20100032814A KR101141542B1 KR 101141542 B1 KR101141542 B1 KR 101141542B1 KR 20100032814 A KR20100032814 A KR 20100032814A KR 20100032814 A KR20100032814 A KR 20100032814A KR 101141542 B1 KR101141542 B1 KR 101141542B1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Abstract
본 발명은 폐인쇄회로기판을 이루고 있는 주요성분인 에폭시 수지를 유기용매를 이용하여 유기 용매로 가용화하여 금속류, 유리 섬유, 수지용액 등의 각 소재로 분리하는 기술이다. 본 발명의 특징은 상압에서 유기용매를 이용하여 에폭시수지의 해중합이 이루어진다. 폐회로기판을 차지하는 비율이 30-40중량％인 에폭시수지의 해중합을 통하여 금속소재와 비금속소재를 분리하고 남은 유리섬유의 재활용을 목적으로 하고 있다. 금속류는 현재 이루어지고 있는 금속제련 방법으로 재활용하고 있으며 유리 섬유를 분리하여 재활용할 수 있다. The present invention is a technique of solubilizing an epoxy resin, which is a main component of a closed printed circuit board, with an organic solvent using an organic solvent to separate the materials into metals, glass fibers, resin solutions, and the like. A feature of the present invention is the depolymerization of epoxy resin using an organic solvent at atmospheric pressure. It aims to recycle the remaining glass fibers after depolymerization of metal and nonmetal materials through depolymerization of epoxy resin with 30-40% by weight of closed circuit board. Metals are recycled using current metal smelting methods, and glass fibers can be separated and recycled.
Description
본 발명은 유기용매를 이용하여 폐인쇄회로기판을 해중합에 의해서 유리섬유를 분리하는 방법에 관한 것이다. 따라서 본 발명은 열경화성 수지를 해중합하고, FRP에서 유리섬유를 분리하며, 폐인쇄회로기판에서 금속과 비금속을 분리하는 데 있다.
The present invention relates to a method for separating glass fibers by depolymerization of a waste printed circuit board using an organic solvent. Therefore, the present invention is to depolymerize the thermosetting resin, to separate the glass fiber from the FRP, and to separate the metal and the non-metal from the waste printed circuit board.
인구 밀집 지역에서 배출되는 폐가전제품, 폐휴대폰 등의 폐기물 중에는 산업상 유용한 자원이 함유되어 있으므로 광산(鑛山)으로 간주하여 도시광산(urban mining)의 개념을 도입하여 이들 폐기물로부터 희유금속을 회수하려는 연구개발 사업 및 도시광산 자원과 국제순환 정책을 시행(Horiuchi, H. Shimizu, K. Shibata, Epoxy MCL recycling, Hitachi chemical technical report, 36, 33-36,2001)하고 있다. Since wastes such as household appliances and mobile phones that are discharged from populated areas contain industrial useful resources, they are regarded as mines and introduced the concept of urban mining to recover rare metals from these wastes. It is also conducting R & D projects and urban mining resources and international circulation policies (Horiuchi, H. Shimizu, K. Shibata, Epoxy MCL recycling, Hitachi chemical technical report, 36, 33-36, 2001).
폐금속자원의 재활용은 폐기물 자원순환의 일환으로 국가정책 및 기술개발이 그 간 추진되어 왔다. 요즘 자원난이 날로 심각해짐에 따라 도시광산 사업이 새로운 대안으로 급부상하고 있으며 국제적으로 폐기물 재활용 정책의 선진화(오사카 마케팅소스, 희소금속.귀금속관련 시장의 현상과 장래성, 2008)에 노력을 기울이고 있다. 특히 일본은 희유금속제련, 정련 및 소재화기술을 바탕으로 폐금속자원 내 회유금속 추출 및 재활용 기술 개발 및 기업 육성을 통해 희유금속 재활용을 확대하고 있다. Recycling of waste metal resources is part of the recycling of waste resources, and national policy and technology development have been promoted. As the resource shortages become more severe these days, urban mining projects are rapidly emerging as new alternatives, and international efforts are being made to advance waste recycling policies (Osaka Marketing Sources, Rare Metals, Precious Metals related markets and prospects, 2008). In particular, Japan is expanding the recycling of rare metals through the development of rare metal extraction and recycling technologies and fostering companies based on rare metal smelting, refining and materialization technologies.
본 발명은 고부가가치성의 폐기물을 재자원화하는 기술을 탐색하고 개발하는 데, 목적을 두고 전개하고 자 한다. 본 발명과 관련되는 선행기술이나 문헌은 발명자들이 알아 본 바에 의하면 현재 개발된 기술이 시장에 적용된 사례는 없는 것으로 파악되고 있다.
The present invention seeks to develop and develop a technology for recycling high value-added waste. Prior arts and literature related to the present invention, the inventors have found that there is no case that the currently developed technology is applied to the market.
본 발명은 유기용매를 이용하여 폐인쇄회로기판의 열경화성 수지를 해중합함으로써, 상온 상압으로 FRP에서 유리섬유를 분리할 수 있고, 파쇄 등의 전처리가 필요하지 않으므로 가격이 저렴한 설비로 폐인쇄회로기판에서 금속과 비금속을 연속적으로 분리할 수 있기 때문에 비용절감이 가능한 경쟁력있는 방법이다. The present invention depolymerizes the thermosetting resin of a waste printed circuit board using an organic solvent, so that the glass fiber can be separated from the FRP at room temperature and normal pressure, and does not require pretreatment such as crushing. The ability to continuously separate metals and nonmetals is a cost effective way to cut costs.
종래의 미분쇄에 의한 물리적 선별법은 폐회로기판의 30-40％를 차지하는 에폭시수지를 햄머밀과 같은 충격형 분쇄기나 슈레더를 사용하여 폐인쇄회로기판에서 비금속성분과 금속성분을 분리하는 방법으로서 공정이 간단하고 폐수발생이 없다는 장점을 가지고 있으나 분리효율이 낮다는 단점이 있다. 또한 회수 가능한 글래스섬유(fiber glass)는 섬유 길이가 1㎜의 이하로 분리되기 때문에 용도가 크게 제한된다. The conventional method of physical screening by pulverization is a method of separating non-metal and metal components from the closed printed circuit board by using an impact grinder or a shredder such as a hammer mill, which makes up 30-40% of the closed circuit board. And it has the advantage of no waste water generation, but has the disadvantage of low separation efficiency. In addition, recoverable glass glass is greatly limited in use because the fiber length is separated by less than 1mm.
특히 유리섬유강화플라스틱(FRP; fiber glass reinforced plastic)에서는 25㎜ 이상 길이의 장섬유를 사용하여 높은 기계적 강도를 실현하므로 1㎜ 이하의 단섬유는 FRP의 강화제로 사용하기에는 적합하지 않고, 또한 안전 위생에서 분쇄물의 분진폭발이나 진폐의 위험성이 높은 문제점이 있다.
In particular, glass fiber reinforced plastic (FRP) realizes high mechanical strength by using long fibers of 25 mm or more in length, so short fibers of 1 mm or less are not suitable for use as a reinforcing agent for FRP, and also in safety and hygiene. There is a high risk of dust explosion or dusting of the crushed powder.
본 발명의 유기용매를 이용한 에폭시수지의 해중합에 의한 용해법은 첫째, 상온에서 처리가능하다는 점과 둘째, 파쇄 등의 전처리가 필요하지 않다는 것이다. 또한 상압에서 유기용매로 처리하면 가격이 저렴한 설비로 연속적으로 처리할 수 있으므로 비용절감이 가능하고, 미분쇄 비용을 절감 가능할 뿐 아니라 분진발생이 생기지 않아 안전 위생면에서 유리하다.
The dissolution method by depolymerization of the epoxy resin using the organic solvent of the present invention is that, first, it can be treated at room temperature, and second, pretreatment such as crushing is not necessary. In addition, the treatment with an organic solvent at atmospheric pressure can be continuously processed in a low-cost facility, which can reduce costs, reduce pulverization costs, and is advantageous in terms of safety and hygiene because no dust is generated.
본 발명의 유기용매를 이용한 에폭시수지의 해중합에 의한 용해법은 상압에서 유기용매로 처리하므로 가격이 저렴한 설비로도 연속적인 처리를 할 수 있으므로 비용절감이 가능하고, 분진발생이 없어 안전 위생면에서 유리하다.
The dissolution method by depolymerization of the epoxy resin using the organic solvent of the present invention is treated with an organic solvent at normal pressure, so it can be continuously processed even in a low-cost facility, and thus cost can be reduced and there is no dust generation. Do.
도 1a은 폐인쇄회로기판이고, 도 1b는 폐인쇄회로기판을 분쇄한 분쇄물이다.
도 2는 강염기를 사용하여 폐인쇄회로기판에서 유리섬유를 분리한 것이다.
도 3은 유기용매를 이용하여 폐인쇄회로기판에서 유리섬유를 분리한 것이다.1A is a waste printed circuit board, and FIG. 1B is a pulverized product of a waste printed circuit board.
2 is a glass fiber separated from the printed circuit board using a strong base.
3 is a glass fiber separated from the waste printed circuit board using an organic solvent.
본 발명은 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리방법을 나타낸다.The present invention shows a method for separating glass fibers by depolymerization of a waste printed circuit board using an organic solvent.
본 발명은 폐인쇄회로기판을 절단한 후, 전해질을 넣고 유기용매를 첨가하여 반응시켜 폐인쇄회로기판으로부터 금속류와 유리섬유를 분리시킬 수 있는 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리방법을 나타낸다. The present invention is a glass fiber by depolymerization of a waste printed circuit board using an organic solvent that can cut metal, glass fiber from the waste printed circuit board by reacting by inserting an electrolyte and adding an organic solvent after cutting the waste printed circuit board The separation method of is shown.
본 발명은 폐인쇄회로기판을 1～5cm×1～5cm(가로×세로), 바람직하게는 1～5cm×1～5cm(가로×세로)로 절단한 후, 전해질을 넣고 유기용매를 첨가하여 150～200℃의 범위에서 1～3시간 동안 반응시켜 폐인쇄회로기판으로부터 금속류와 유리섬유를 분리시킬 수 있는 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리방법 According to the present invention, the printed circuit board is cut into 1 to 5 cm x 1 to 5 cm (width × length), preferably 1 to 5 cm × 1 to 5 cm (width × length), and then an electrolyte is added to the organic solvent. Separation method of glass fiber by depolymerization of waste printed circuit board using organic solvent which can react metals and glass fiber from waste printed circuit board by reacting for 1-3 hours in the range of ～ 200 ℃.
상기에서 유기용매는 테트라하이드로퓨란(THF)을 사용할 수 있다.In the organic solvent may be used tetrahydrofuran (THF).
상기에서 유기용매는 에폭시 수지의 유리전이온도보다 높은 극성용매인 디메칠포름아마이드(DMF)를 사용할 수 있다.In the organic solvent, dimethylformamide (DMF), which is a polar solvent higher than the glass transition temperature of the epoxy resin, may be used.
상기에서 유기용매는 에폭시 수지의 유리전이온도보다 높은 극성용매인 N-메틸피롤리돈(NMP)을 사용할 수 있다.In the organic solvent, N-methylpyrrolidone (NMP), which is a polar solvent higher than the glass transition temperature of the epoxy resin, may be used.
상기에서 유기용매는 테트라하이드로퓨란, 디메칠포름아마이드, N-메틸피롤리돈 중에서 선택된 둘 이상을 사용할 수 있다.The organic solvent may be two or more selected from tetrahydrofuran, dimethylformamide, and N-methylpyrrolidone.
상기에서 전해질은 강염기인 NaOH 또는 KOH와, 알칼리족 금속을 포함하는 탄산리튬, 탄산나트륨, 탄산칼륨, 수화탄산리튬, 수화탄산나트륨, 수화탄산칼륨, 인산리튬, 인산나트륨, 인산칼륨, 인산수소칼륨, 인산이수소칼륨, 수화인산리튬, 수화인산나트륨, 수화인산칼륨, 수화인산수소칼륨, 수화인산이수소칼륨 중에서 선택된 어느 하나 또는 둘 이상을 사용할 수 있다.In the electrolyte, NaOH or KOH which is a strong base, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrate, sodium carbonate, potassium hydrate, lithium phosphate, sodium phosphate, potassium phosphate, potassium hydrogen phosphate, phosphoric acid Any one or two or more selected from potassium dihydrogen, lithium hydrated phosphate, sodium hydrated phosphate, potassium hydrated phosphate, potassium hydrogen phosphate and potassium dihydrogen phosphate can be used.
상기에서 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리시 물을 사용할 수 있으며, 이때 물과 전해질의 몰비가 5/1～45/1가 되도록 물과 전해질을 사용할 수 있다. When the glass fiber is separated by depolymerization of the waste printed circuit board using the organic solvent, water may be used, and water and electrolyte may be used so that the molar ratio of water and electrolyte is 5/1 to 45/1.
상기에서 전해질의 양은 0.001～10중량％를 사용할 수 있다.In the above, the amount of the electrolyte can be used from 0.001 to 10% by weight.
상기에서 폐인쇄회로기판은 5～40중량％를 사용할 수 있다.In the above, the closed printed circuit board may be used 5 to 40% by weight.
상기에서 폐인쇄회로기판 5～70중량부에 대해 유기용매는 DMF 또는 NMP 중에서 선택된 어느 하나 이상이 10～100중량부가 되도록 사용할 수 있다.
The organic solvent may be used so that at least one selected from DMF or NMP is 10 to 100 parts by weight based on 5 to 70 parts by weight of the closed printed circuit board.
본 발명의 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리방법에 대해 다양한 조건으로 실시한바, 본 발명의 목적을 달성하기 위해서는 상기에서 언급한 조건에 의해 유기용매를 이용한 폐인쇄회로기판의 해중합에 의한 유리섬유의 분리방법을 제공하는 것이 바람직하다.
The separation method of the glass fiber by depolymerization of the waste printed circuit board using the organic solvent of the present invention was carried out under various conditions. In order to achieve the object of the present invention, the waste printed circuit using the organic solvent under the above-mentioned conditions. It is desirable to provide a method for separating glass fibers by depolymerization of a substrate.
본 발명은 상기에서 언급한 방법에 의해 폐인쇄회로기판으로부터 분리한 유리섬유를 포함한다.
The present invention includes glass fibers separated from a closed printed circuit board by the above-mentioned method.
이하 본 발명의 내용을 보다 상세히 설명하고자 한다.Hereinafter will be described in more detail the contents of the present invention.
본 발명은 폐인쇄회로기판을 이루고 있는 주요성분인 에폭시 수지를 유기용매를 이용하여 유기 용매로 가용화하여 금속류, 유리 섬유 및 수지용액 등의 각 소재로 분리하는 기술이다. The present invention is a technique of solubilizing an epoxy resin, which is a main component of a closed printed circuit board, with an organic solvent using an organic solvent to separate the materials into metals, glass fibers, and resin solutions.
종래의 물리적 선별법은 햄머밀과 같은 충격형 분쇄기나 슈레더를 사용하여 폐인쇄회로기판을 미분쇄하여 비금속성분과 금속성분을 분리하는 방법으로서 공정이 간단하고 폐수발생이 없다는 장점을 갖고 있으나, 분리효율이 낮은 단점이 있다. 또한 회수 가능한 글래스섬유는 섬유길이 1㎜의 이하의 것으로 용도가 크게 제한되어 있다. 특히 FRP에서는 25㎜ 이상 길이의 장섬유를 사용하여 높은 기계적 강도를 실현하므로 1㎜ 이하의 단섬유는 FRP의 강화제로 하기에는 적합하지 않다. 또한 안전 위생에서 분쇄물의 분진폭발, 진폐의 위험성이 높아 바람직하지 않다. 종래의 방법과 본 발명을 비교해 볼 때 유기용매를 이용한 에폭시수지의 해중합에 의한 용해법은 크게 2가지의 특징이 있다. 첫째, 상압에서 처리가능하다는 것과 둘째, 파쇄 등의 전처리가 필요하지 않다는 것이다. 상압에서 유기용매에 의한 처리는 가격이 저렴한 설비로 진행이 가능하고 연속처리에서도 가격경쟁을 가지기 때문에 비용절감이 가능하다. 본 발명은 미분쇄 비용의 절감이 가능할 뿐 아니라 분진발생이 생기지 않아 안전 위생면에서 장점을 갖는다. Conventional physical screening method is a method of separating the non-metallic components and metal components by pulverizing the waste printed circuit board using an impact grinder or a shredder such as a hammer mill, which has the advantages of simple process and no waste water generation, There is a low disadvantage. In addition, recoverable glass fibers have a fiber length of 1 mm or less, and their use is greatly limited. In particular, since FRP realizes high mechanical strength by using long fibers of 25 mm or more in length, short fibers of 1 mm or less are not suitable for use as a reinforcing agent for FRP. In addition, the safety and hygiene is not preferable because of the high risk of dust explosion, dusting. In comparison with the conventional method and the present invention, the dissolving method by depolymerization of epoxy resin using an organic solvent has two characteristics. Firstly, it can be treated at atmospheric pressure and secondly, no pretreatment such as crushing is necessary. Treatment with organic solvents at atmospheric pressure can be carried out with low cost equipment, and cost reduction is possible because of the competitive price in continuous processing. The present invention has the advantage in terms of safety and hygiene because it is possible to reduce the cost of pulverization and not generate dust.
1) 용매의 선정1) Selection of solvent
본 발명에서 예상되는 적정 용매는 비점이 낮은 테트라하이드로퓨란 (THF)이었으나, 기초실험 결과 에폭시 수지의 유리전이온도보다 높은 유기용매를 선정하였다. 그 중 극성용매인 디메칠포름아마이드 (DMF)와 N-메틸피롤리돈 (NMP)이 폐인쇄회로기판의 용해율에 양호한 결과를 보였다.Tetrahydrofuran (THF) having a low boiling point was expected in the present invention, but an organic solvent higher than the glass transition temperature of the epoxy resin was selected. The polar solvents, dimethylformamide (DMF) and N-methylpyrrolidone (NMP), showed good results for the dissolution rate of the waste printed circuit board.
* 폐인쇄회로기판에서 에폭시수지의 용해율은 다음과 같이 나타낼 수 있다.* The dissolution rate of epoxy resin in closed printed circuit board can be expressed as follows.
용해율(％) = (A-B)/(A-C)×100Dissolution rate (%) = (A-B) / (A-C) x 100
A : 용해전 폐PCB 중량, A: weight of waste PCB before melting,
B : 용해 후 폐PCB 중량, B: weight of waste PCB after dissolution,
C : 완전 용해 후 폐PCB 중량
C: Weight of waste PCB after complete dissolution
이하 본 발명의 내용을 실시예 및 시험예를 통하여 구체적으로 설명한다. 그러나, 이들은 본 발명을 보다 상세하게 설명하기 위한 것으로 본 발명의 권리범위가 이들에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail with reference to Examples and Test Examples. However, these are for the purpose of illustrating the present invention in more detail, and the scope of the present invention is not limited thereto.
<실시예 1>≪ Example 1 >
DMF 용매의 양이 500mL에서 시간별 폐인쇄회로기판의 용해율을 150℃에서 반응시간에 따라 실시하였다. At 500 mL of DMF solvent, the dissolution rate of the waste printed circuit board was performed at 150 ° C. according to the reaction time.
폐인쇄회로기판 20wt％을 DMF 용매 500mL에서 2～24시간 동안 용해시 폐인쇄회로기판의 용해율을 아래의 표 1에 나타내었다. The dissolution rate of the waste printed circuit board when 20 wt% of the waste printed circuit board was dissolved in 500 mL of DMF solvent for 2 to 24 hours is shown in Table 1 below.
또한 폐인쇄회로기판의 함량 10중량％, 15중량％, 20중량％, 25중량％, 30중량％, 35중량％, 40중량％을 각각 DMF 용매 500mL에서 4시간 동안 용해시 폐인쇄회로기판의 용해율을 아래의 표 2에 나타내었다. In addition, when the content of 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, and 40% by weight of the waste printed circuit board was dissolved in 500 mL of DMF solvent for 4 hours, Dissolution rates are shown in Table 2 below.
<실시예 2><Example 2>
NMP 용매의 양이 500mL에서 시간별 폐인쇄회로기판의 용해율을 180℃에서 반응시간에 따라 실시하였다. In 500 mL of NMP solvent, the dissolution rate of the waste printed circuit board was performed at 180 ° C. according to the reaction time.
폐인쇄회로기판 20wt％을 NMP 용매 500mL에서 2～24시간 동안 용해시 폐인쇄회로기판의 용해율을 아래의 표 3에 나타내었다. The dissolution rate of the waste printed circuit board when 20 wt% of the waste printed circuit board was dissolved in 500 mL of NMP solvent for 2 to 24 hours is shown in Table 3 below.
또한 폐인쇄회로기판의 함량 10중량％, 15중량％, 20중량％, 25중량％, 30중량％, 35중량％, 40중량％을 각각 NMP 용매 500mL에서 4시간 동안 용해시 폐인쇄회로기판의 용해율을 아래의 표 4에 나타내었다. In addition, when 10%, 15%, 20%, 25%, 30%, 35%, and 40% by weight of the waste printed circuit board was dissolved in 500 mL of NMP solvent for 4 hours, the waste printed circuit board was Dissolution rates are shown in Table 4 below.
2) 온도별 및 용해시간별 변화2) Change by temperature and melting time
온도변화, 용해시간 및 전해질인 염을 변수로 하여 폐인쇄회로기판에서 금속의 분리도와 에폭시 복합체의 용해율을 관찰하였다. 그 결과 용해온도가 150～200℃의 범위에서 1～3시간 동안 반응시키면 금속류가 분리되고, 유리섬유만이 잔존하게 된다. 바람직하게는 160℃ 이상의 용해온도에서 용해시간이 2시간 이상 반응시키면 금속류가 분리되고, 유리섬유만이 잔존하는 좋은 결과를 얻었다. The separation of metals and the dissolution rate of epoxy composites in the waste printed circuit board were observed using temperature change, dissolution time and salt as electrolyte. As a result, when the melting temperature is reacted for 1 to 3 hours in the range of 150 to 200 ° C, metals are separated and only glass fibers remain. Preferably, when the dissolution time is reacted for 2 hours or more at a dissolution temperature of 160 ° C. or more, metals are separated, and only good glass fibers remain.
상압에서 유기용매로 용해처리를 전제로 할 경우, 사용하는 용매의 비점이하에서 해중합반응을 진행할 필요가 있다. 또한 해중합 및 용해가 수지 표면에서만 일어나는 것을 고려할 경우, 분쇄하지 않고 처리하기 위해서는 매우 빠른 해중합반응이 필요하다. 즉 상압에서 비교적 저온으로 진행하는 빠른 해중합 반응을 확보하는 것이 본 발명을 진행하기위해 필수적인 사항이다. 에폭시복합체의 해중합반응 속도를 증가시키는 방법으로 에폭시수지의 결합구조에서 에테르와 탄소결합을 해리시키는 금속염을 포함한 전해질이 중요하다. 전해질은 수용액에서 이온화한 금속양이온이 전자받게로 작용하여 에폭시 수지내에 존재하는 전자주게인 에테르와 결합하여 에폭시 수지가 해중합이 일어나게 된다. 전해질은 강염기인 NaOH, KOH와 알칼리족 금속을 포함한 탄산리튬, 탄산소듐, 탄산포타슘, 수화탄산리튬, 수화탄산소듐, 수화탄산칼륨, 인산리튬, 인산소디움, 인산칼륨, 인산수소칼륨, 인산이수소칼륨, 수화인산리튬, 수화인산소디움, 수화인산칼륨, 수화인산수소칼륨, 수화인산이수소칼륨 등의 염을 0.001 ～ 10 중량％로 에폭시복합체의 용해율을 평가하였다.
If the dissolution treatment is premised with the organic solvent at atmospheric pressure, it is necessary to proceed with the depolymerization reaction under the boiling point of the solvent used. In addition, considering that depolymerization and dissolution occur only on the resin surface, a very fast depolymerization reaction is required for the treatment without grinding. That is, to secure a fast depolymerization reaction proceeding from a normal pressure to a relatively low temperature is essential for the present invention. As a method of increasing the rate of depolymerization of an epoxy composite, an electrolyte containing a metal salt that dissociates ether and carbon bond in the bonding structure of the epoxy resin is important. In the electrolyte, the metal cation ionized in the aqueous solution acts as an electron acceptor and binds to the electron donor ether present in the epoxy resin to depolymerize the epoxy resin. The electrolyte is lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrate, sodium carbonate, potassium hydrate, lithium phosphate, sodium phosphate, potassium phosphate, potassium hydrogen phosphate, dihydrogen phosphate containing NaOH, KOH and alkali metals The dissolution rate of the epoxy composite was evaluated at 0.001 to 10% by weight of salts such as potassium, lithium hydrated phosphate, sodium hydrated potassium phosphate, potassium hydrated potassium phosphate and potassium dihydrogen phosphate.
<실시예 3><Example 3>
NMP용매의 양이 500mL에서 시간별로 물과 인산칼륨의 몰비를 30으로 하여, 폐인쇄회로기판의 용해율을 180℃에서 용해시간에 따라 실시하였다. 폐인쇄회로기판은 10 중량％, 15중량％, 20중량％, 25중량％, 30중량％, 35중량％ 실시하였다. The amount of NMP solvent was 500 mL, and the molar ratio of water and potassium phosphate was 30 per hour. The closed printed circuit board was subjected to 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight and 35% by weight.
<실시예 4><Example 4>
NMP용매의 양이 500mL에서 용해시간을 4시간과 물/인산칼륨의 몰비를 30에서, 폐인쇄회로기판의 중량은 20％로 용해율을 온도에 따라 실시하였다. When the amount of NMP solvent was 500 mL, the dissolution time was 4 hours and the molar ratio of water / potassium phosphate was 30, and the weight of the waste printed circuit board was 20%.
<실시예 5>Example 5
NMP용매의 양이 500 mL에서 4시간 용해시에 물과 인산칼륨의 몰비를 5, 15, 30, 45, 60, 90로 하여, 폐인쇄회로기판의 용해율을 180℃에서 실시하였다. 폐인쇄회로기판은 20중량％에서 실시하였다. When the amount of NMP solvent dissolved in 500 mL for 4 hours, the molar ratio of water and potassium phosphate was 5, 15, 30, 45, 60, 90, and the dissolution rate of the waste printed circuit board was performed at 180 ° C. The closed printed circuit board was carried out at 20% by weight.
<실시예 6><Example 6>
NMP용매의 양이 500 mL에서 4시간 용해시 물과 수화인산칼륨의 몰비를 5, 15, 30, 45, 60로 하여, 폐인쇄회로기판의 용해율을 180℃에서 실시하였다. 폐인쇄회로기판은 20중량％에서 실시하였다.When the NMP solvent was dissolved in 500 mL for 4 hours, the molar ratio of water and potassium phosphate was set to 5, 15, 30, 45, and 60, and the dissolution rate of the waste printed circuit board was performed at 180 ° C. The closed printed circuit board was carried out at 20% by weight.
<실시예 7><Example 7>
NMP용매의 양이 500 mL에서 용해시간에 따라 물과 수화인산칼륨의 몰비를 5로 하여, 폐인쇄회로기판의 용해율을 180℃에서 반응시간별로 실시하였다. 폐인쇄회로기판은 20중량％이다.In 500 mL of NMP solvent, the molar ratio of water and potassium phosphate was set to 5 depending on the dissolution time, and the dissolution rate of the waste printed circuit board was performed at 180 ° C. for each reaction time. The closed printed circuit board is 20% by weight.
<실시예 8><Example 8>
NMP용매의 양이 500 mL에서 금속회수율을 용해시간에 따라 물과 수화인산칼륨의 몰비를 5로 하여, 폐인쇄회로기판의 용해율을 180℃에서 반응시간에 따라 실시하였다. 폐인쇄회로기판은 20중량％에서 실시하였다.When the amount of NMP solvent was 500 mL, the metal recovery rate was set at 5 by the dissolution time, and the molar ratio of water and potassium phosphate was 5, and the dissolution rate of the waste printed circuit board was performed at 180 ° C. according to the reaction time. The closed printed circuit board was carried out at 20% by weight.
<적용예><Application example>
3년 이상 사용된 폐휴대폰을 수집하여 폐인쇄회로기판의 시료로 하여 2cm×2cm로 절단한 후 사용하였다. 전해질인 염은 인산칼륨(K3PO4)과 수화인산칼륨(K3PO4.H2O)이 양호하였다. NMP 용매를 2 L로 하여 인산칼륨은 0.005중량％, 물은 2.3중량％를 첨가하였으며, 물과 인산칼륨의 몰비가 5에서 60범위에서 우수한 용해율을 보였다. 특히 물/인산칼륨은 30/1, 45/1의 몰비에서 최적이고, 물/수화인산칼륨은 5/1, 10/1의 몰비에서 최적이었다.The waste cell phones used for more than three years were collected and cut into 2cm × 2cm as samples of the waste printed circuit board. Salts as electrolytes were good in potassium phosphate (K 3 PO 4 ) and potassium hydrated phosphate (K 3 PO 4 .H 2 O). Potassium phosphate (0.005% by weight) and water (2.3% by weight) were added with 2 L of NMP solvent, and the molar ratio of water and potassium phosphate was excellent in the range of 5 to 60. In particular, water / potassium phosphate was optimal at a molar ratio of 30/1 and 45/1, and water / potassium phosphate was optimal at a molar ratio of 5/1 and 10/1.
용해시간은 140℃ 이상에서 4시간 이상 처리한 결과 금속류가 완전히 분리되고 에폭시 수지가 용해되었다. 온도변화, 용해시간을 변수로 하여 폐인쇄회로기판에서 금속의 분리도와 에폭시 복합체의 용해율을 관찰하였다. 그 결과 용해온도가 160℃이상의 용해온도에서 용해시간이 4시간 이상 진행한 다음 금속류가 분리되고, 유리섬유만이 잔존하는 결과를 얻었다. 에폭시복합체의 용해율이 증가함에 따라 금속회수율이 증가하였다. 용매 대 폐전자회로기판의 함량에 따른 용해율에서 폐전자회로기판의 중량이 15에서 20％에서 양호한 용해율을 보였다. 본 발명을 위한 실시를 통하여 에폭시 수지의 용해율이 증가되므로 금속류, 회로부품 및 유리섬유를 분리하였다. Dissolution time was treated for 4 hours or more at 140 ℃ or more as a result that the metals were completely separated and the epoxy resin was dissolved. The separation of metals and the dissolution rate of epoxy composites were observed in the printed circuit boards using temperature change and dissolution time as variables. As a result, after the dissolution time proceeded for more than 4 hours at a dissolution temperature of 160 ℃ or more, metals were separated, and only glass fibers remained. As the dissolution rate of the epoxy composite increased, the metal recovery rate increased. The dissolution rate according to the solvent to the content of the waste electronic circuit board showed a good dissolution rate of 15 to 20% of the weight of the waste electronic circuit board. Since the dissolution rate of the epoxy resin is increased through the implementation for the present invention, metals, circuit components and glass fibers were separated.
폐인쇄회로기판은 다음의 도 1a과 같으며, 도 1a의 폐인쇄회로기판을 분쇄한 것은 도 1b와 같다. 회수 가능한 글래스섬유는 섬유길이 1㎜의 이하의 것으로 용도가 크게 제한되어 있다. 특히 유리섬유강화플라스틱(FRP)에서는 25㎜ 이상 길이의 장섬유를 사용하여 높은 기계적 강도를 실현하므로 1㎜ 이하의 단섬유는 FRP의 강화제로 하기에는 적합하지 않다. 강염기를 사용하여 폐인쇄회로기판에서 분리한 유리섬유이다. 이 방법은 유리섬유가 강염기에 의해서 침식되어 뭉쳐 있는 형태를 보이고 있다. 강염기인 KOH에 의하여 에폭시 수지의 해중합한 바 있으나, 폐인쇄회로기판에서는 충분한 용해율이 관찰되지 않아 전해질로 부적합하였다. The closed printed circuit board is as shown in FIG. 1A, and the closed printed circuit board of FIG. 1A is pulverized as shown in FIG. 1B. The recoverable glass fiber has a fiber length of 1 mm or less, and its use is greatly limited. In particular, glass fiber reinforced plastic (FRP) realizes high mechanical strength by using long fibers of 25 mm or more in length, so short fibers of 1 mm or less are not suitable for use as a reinforcing agent for FRP. It is a glass fiber separated from waste printed circuit board using strong base. This method shows that the glass fibers are eroded by the strong base and aggregated together. Although depolymerization of epoxy resin was carried out by KOH, which is a strong base, sufficient dissolution rate was not observed in a closed printed circuit board, which was not suitable as an electrolyte.
본 발명은 도 3과 같이 폐인쇄회로기판을 유기용매로 용해한 후 유리섬유가 매트형태로 남아있다. 이러한 결과를 통하여 에폭시수지가 용해되었음을 알 수 있으며 에폭시수지 복합체에서 에폭시수지가 용해되고 남은 유리섬유가 분리되어 FRP를 위한 재료로 재활용도가 높다는 것을 알 수 있다.
In the present invention, after dissolving the waste printed circuit board with an organic solvent as shown in FIG. 3, the glass fibers remain in a mat form. It can be seen from these results that the epoxy resin was dissolved, and the epoxy resin was dissolved in the epoxy resin composite and the remaining glass fibers were separated to show high recyclability as a material for FRP.
상술한 바와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. It will be understood that the present invention can be changed.
본 발명의 유기용매를 이용한 에폭시수지의 해중합에 의한 용해법은 상압에서 저렴한 설비로 연속적인 처리가 가능하기 때문에 비용절감이 가능하다. 또한 분진발생이 생기지 않아 안전 위생면에서 장점을 가지므로 산업상 이용가능성이 있다.The dissolution method by depolymerization of the epoxy resin using the organic solvent of the present invention is possible to reduce the cost because it can be continuously processed in a cheap equipment at normal pressure. In addition, there is no dust generation has an advantage in terms of safety and hygiene, so there is industrial applicability.
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| KR101861095B1 (en) | 2015-07-22 | 2018-05-29 | 한국과학기술연구원 | Method and composition for depolymerization of cured epoxy resin materials |
| CN105369039A (en) * | 2015-12-01 | 2016-03-02 | 林素玉 | Resourceful treatment method of waste glass fiber resin powder |
| KR101781835B1 (en) | 2015-12-16 | 2017-09-28 | 한국과학기술연구원 | Composition and Method For Depolymerization Of Cured Epoxy Resin Using Transition Metal Salts |
| CN107243496B (en) * | 2017-06-15 | 2020-07-07 | 广东环境保护工程职业学院 | Al (aluminum)2O3And Fe3O4Method for composite catalytic pyrolysis of waste circuit board nonmetal powder |
| CN107282591B (en) * | 2017-06-15 | 2020-05-26 | 广东环境保护工程职业学院 | Method for simultaneously debrominating and lightening waste circuit board pyrolysis oil through two-stage catalytic pyrolysis |
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