KR100588667B1 - Recycle method for semiconductor waste - Google Patents

Recycle method for semiconductor waste Download PDF

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KR100588667B1
KR100588667B1 KR1020010020253A KR20010020253A KR100588667B1 KR 100588667 B1 KR100588667 B1 KR 100588667B1 KR 1020010020253 A KR1020010020253 A KR 1020010020253A KR 20010020253 A KR20010020253 A KR 20010020253A KR 100588667 B1 KR100588667 B1 KR 100588667B1
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waste
reaction
semiconductor
semiconductor manufacturing
recycling
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KR20020080604A (en
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남신우
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동부일렉트로닉스 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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  • Organic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract

본 발명은 반도체 폐기물의 재활용 방법에 관한 것으로, 특히 반도체 제조시 발생된 F 폐수에 수산화칼슘(Ca(OH)2)을 투입하여 폐수처리하고 이를 통해 얻어진 침전물 불화칼슘(CaF2)에 강산성의 폐기물을 반응시켜 CaSO4 또는 CaO 원소를 포함한 유가부산물 또는 불소(F) 함유 가스를 생성하고, 이 유가 부산물 또는 불소 가스에 수분(H2O)을 반응시켜 폐수처리의 원료(Ca(OH)2) 또는 불산(HF2)을 생성함으로써 반도체 폐기물을 효율적으로 재활용할 수 있을 뿐만 아니라 반도체 폐기물의 양을 줄일 수 있다.The present invention relates to a method for recycling semiconductor waste, and in particular, calcium hydroxide (Ca (OH) 2 ) is added to the wastewater generated during semiconductor manufacturing to treat wastewater, and the precipitated calcium fluoride (CaF 2 ) is obtained from the waste acid. Reacts to produce valuable by-products or fluorine (F) -containing gas containing CaSO 4 or CaO elements, and react the moisture (H 2 O) with these by-products or fluorine gas (Ca (OH) 2 ) or By generating hydrofluoric acid (HF 2 ), not only can the semiconductor waste be recycled efficiently, but also the amount of semiconductor waste can be reduced.

Description

반도체 폐기물의 재활용 방법{RECYCLE METHOD FOR SEMICONDUCTOR WASTE}Recycling method of semiconductor waste {RECYCLE METHOD FOR SEMICONDUCTOR WASTE}

도 1은 종래 기술에 의한 반도체 제조 공정에서 발생된 폐기물의 처리과정을 나타낸 구성도,1 is a block diagram showing a treatment process of waste generated in the semiconductor manufacturing process according to the prior art,

도 2는 본 발명의 일실시예에 따른 반도체 제조 공정에서 발생된 폐기물의 처리 및 재활용 과정을 나타낸 구성도,2 is a block diagram showing a treatment and recycling process of the waste generated in the semiconductor manufacturing process according to an embodiment of the present invention,

도 3은 본 발명의 일실시예에 따른 반도체 폐기물의 재활용 방법을 나타낸 플로우챠트,3 is a flowchart showing a method of recycling semiconductor waste according to an embodiment of the present invention;

도 4는 본 발명의 다른 실시예에 따른 반도체 제조 공정에서 발생된 폐기물의 처리 및 재활용 과정을 나타낸 구성도,4 is a block diagram showing a treatment and recycling process of the waste generated in the semiconductor manufacturing process according to another embodiment of the present invention,

도 5는 본 발명의 다른 실시예에 따른 반도체 폐기물의 재활용 방법을 나타낸 플로우 챠트. Figure 5 is a flow chart showing a method of recycling semiconductor waste in accordance with another embodiment of the present invention.

＜도면의 주요부분에 대한 부호의 설명＞<Description of the code | symbol about the principal part of drawing>

100 : 반도체 제조 설비 102 : F 함유 폐수100 semiconductor manufacturing facility 102 F containing wastewater

104 : 강산 폐기물(H2SO4, H2O2) 106 : 폐수처리부104: strong acid waste (H 2 SO 4 , H 2 O 2 ) 106: wastewater treatment unit

108 : 폐수처리오니 110, 110' : 폐기물 재활용부108: wastewater treatment sludge 110, 110 ': waste recycling department

본 발명은 폐기물의 재활용 방법에 관한 것으로서, 특히 반도체 제조공정에서 발생하는 폐기물오니(廢棄物汚泥) 및 강산의 액상 폐기물로부터 불산(F) 폐수처리시 사용되는 원료와 유가 부산물을 제조할 수 있어 환경오염물질을 최대한 줄일 수 있는 기술이다.The present invention relates to a waste recycling method, and in particular, raw materials and valuable oil by-products used in hydrofluoric acid (F) wastewater treatment can be produced from waste sludge and strong acid liquid wastes generated in semiconductor manufacturing processes. It is a technology that can reduce pollutants as much as possible.

현재 반도체 제조 설비에서는 여러 가지 가스 및 제조 원료에 의해 폐수 및 폐기물이 다량 발생하므로 이를 정화처리해서 방출하거나 위탁업체에 폐기처리를 위임하고 있는 실정이다. At present, since a large amount of wastewater and wastes are generated by various gases and raw materials in a semiconductor manufacturing facility, they are purified and discharged or delegated to a consignment company for disposal.

도 1은 종래 기술에 의한 반도체 제조 공정에서 발생된 폐기물의 처리과정을 나타낸 구성도로서, 종래 기술의 반도체 폐기물처리는 대부분 두가지 방식으로 구분된다. 먼저, 반도체 업체에서는 반도체 제조 설비(10)에서 발생한 불소(이하 F라 함)를 함유한 폐수(12)의 경우 폐수처리부(16)를 통해 정화처리하여 방류시키거나 폐수처리오니(18) 상태로 위탁업체에 보내어 폐기처리시킨다. 이와 반대로, 정화처리가 되지 않는 액상 타입의 폐기물(14), 예컨대 H2SO4 또는 H2O2 는 주로 위탁업체를 통해 폐기처리된다.1 is a block diagram showing a waste treatment process generated in a semiconductor manufacturing process according to the prior art, the semiconductor waste treatment of the prior art is mainly divided into two ways. First, in the semiconductor company, the wastewater 12 containing fluorine (hereinafter referred to as F) generated in the semiconductor manufacturing facility 10 is purified and discharged through the wastewater treatment unit 16 or discharged to the wastewater treatment sludge 18 state. Send to consignor for disposal. In contrast, liquid type wastes 14, such as H 2 SO 4 or H 2 O 2 , which are not purified, are mainly disposed of through consignment companies.

그런데, 종래 기술의 폐수처리부(16)는 F 폐수를 처리함에 있어서, 가장 일반적인 수산화칼슘(Ca(OH)2), 염화칼슘(CaCl2) 등을 투입하여 불소를 흡착제거한다. 이를 반응식으로 나타내면 다음과 같다.By the way, the wastewater treatment unit 16 of the prior art, by treating the F wastewater, the most common calcium hydroxide (Ca (OH) 2 ), calcium chloride (CaCl 2 ) and the like to adsorb and remove fluorine. This is represented by the following scheme.

H2SiF6 + 4 Ca(OH)2 → 3CaF2 + CaSiO3↓ + 5H2 OH 2 SiF 6 + 4 Ca (OH) 2 → 3CaF 2 + CaSiO 3 ↓ + 5H 2 O

이러한 반응에 의해 폐수처리부(16)는 불화칼슘(CaF2)과 산화실리콘칼슘(CaSiO3)의 폐수처리오니(18)를 생성한다.By this reaction, the wastewater treatment unit 16 generates wastewater treatment sludge 18 of calcium fluoride (CaF 2 ) and calcium oxide (CaSiO 3 ).

이러한 폐수처리오니(18)와 액상 타입의 폐기물(14)은 대부분 오염물질의 배출 허용기준을 상회하는 지정폐기물이기 때문에 이들을 위탁처리하는데 막대한 비용이 소요될 뿐만 아니라 지정폐기물들의 소홀한 폐기처리에 의하여 매립된 폐기물의 침출수 등에서 오염물질이 다량으로 배출되어 환경오염에 심각한 영향을 미치게 된다.Since these wastewater treatment sludge 18 and liquid type waste 14 are mostly designated wastes exceeding the emission allowance standards of contaminants, they are not only enormously expensive to entrust them, but are also buried by neglected disposal of the designated wastes. Pollutants are emitted in a large amount from the leachate of waste, which seriously affects environmental pollution.

한편, 종래에는 황산칼슘(CaSO4), 생석회(CaO), 불산(HF2), 유안비료((NH4)2SO4) 등의 제조 원료는 대부분 자연으로부터 채취하여 사용하였다. 대부분 자연 원료(또는 원석)에는 제조 공정에 요구되는 성분이 미량 함유되어 있는 경우가 많은데, 제조 공정에 사용되는 성분을 획득하기 위해서는 다량의 자연 원료를 필요로 하므로 자원 고갈이 심각해진다. 또한 자연 원료는 대부분 다량의 불순물을 함유하고 있기 때문에 제조 공정에 적용하기 위한 가공처리 과정을 거쳐야만 하는데, 이러한 가공처리의 초기 투자비용 및 공정 비용이 많이 소요된다.On the other hand, conventionally, raw materials such as calcium sulfate (CaSO 4 ), quicklime (CaO), hydrofluoric acid (HF 2 ), and nutrient fertilizer ((NH 4 ) 2 SO 4 ) are mostly collected from nature. Most natural raw materials (or gemstones) often contain trace amounts of components required for the manufacturing process. However, since a large amount of natural raw materials are required to obtain the components used in the manufacturing process, resource depletion becomes serious. In addition, since most natural raw materials contain a large amount of impurities, processing must be performed to be applied to a manufacturing process, which requires a high initial investment cost and a high processing cost.

그리고, 종래에는 재활용이 가능한 폐기물오니, 예컨대 액상 타입의 폐기물도 폐기처분함에 따라 막대한 면적의 매립장이 필요하고 귀중한 자원의 재활용이 어렵다는 문제점이 있었다. 게다가, 반도체 제조공정 중에서 발생되는 불소계 폐수처리오니와 폐황산(H2SO4)과 폐과산화수소(H2O2)는 대부분 고농도의 원료를 함유하고 있음에도 불구하고 이를 폐수처리에 재활용하는 기술은 아직까지 없었다. In addition, in the related art, as wastes that can be recycled, for example, liquid type wastes are disposed of, there is a problem in that a huge landfill is required and it is difficult to recycle valuable resources. In addition, although fluorine-based wastewater treatment sludge, waste sulfuric acid (H 2 SO 4 ) and waste hydrogen peroxide (H 2 O 2 ) generated during the semiconductor manufacturing process mostly contain high concentrations of raw materials, the technology for recycling them to waste water treatment is still There was not until.

본 발명의 목적은 이와 같은 종래 기술의 문제점을 해결하기 위하여 반도체 제조 공정에서 발생된 F 폐수에 수산화칼슘(Ca(OH)2)을 투입하여 폐수처리해서 얻어진 침전물 CaF2에 강산성의 용액을 반응시켜 CaSO4 또는 CaO를 포함한 유가부산물 또는 불소(F) 함유 가스를 생성하고, 이 유가 부산물 또는 가스에 수분(H2O)을 반응시켜 폐수처리의 원료로서 Ca(OH)2를 생성함으로써 반도체 폐기물의 처리에 소요되는 막대한 예산을 절감시키고, 폐기물로부터 얻어지는 귀중한 자원을 폐수처리에 재활용할 수 있는 반도체 폐기물의 재활용 방법을 제공하고자 한다.An object of the present invention is to solve the problems of the prior art by adding Ca hydroxide (Ca (OH) 2 ) to the F wastewater generated in the semiconductor manufacturing process by reacting a strong acid solution to the precipitate CaF 2 obtained by wastewater treatment CaSO 2 Treatment of semiconductor waste by generating valuable by-products or fluorine (F) -containing gas containing 4 or CaO, and reacting the oil by-products or gases with water (H 2 O) to produce Ca (OH) 2 as a raw material for wastewater treatment. In order to reduce the enormous budget required, and to recycle valuable wastes from wastes into wastewater treatment, it is intended to provide a method for recycling semiconductor wastes.

이러한 목적을 달성하기 위하여 본 발명은 반도체 제조 설비에서 생성된 폐기물 및 폐기물오니의 처리 방법에 있어서, 반도체 제조 설비에서 생성된 폐기물오니중에서 적어도 F를 포함한 폐수에 처리 원료를 투입하여 침전물 CaF2를 형성하는 단계와, 반도체 제조 설비에서 생성된 폐기물 중에서 강산과 침전물 CaF2를 1차 반응시켜 CaSO4 또는 CaO 원소를 갖는 유가 부산물을 생성하는 단계와, 1차 반응에 의해 생성된 유가 부산물에 수분을 2차 반응시켜 F 폐수 처리과정에서 사용되는 처리 원료를 재생성하는 단계를 포함한다. In order to achieve the above object, the present invention provides a method for treating waste and sludge generated in a semiconductor manufacturing facility, wherein the treatment raw material is added to wastewater containing at least F among waste sludge generated in a semiconductor manufacturing facility to form precipitate CaF 2 . Generating a valuable by-product having CaSO 4 or CaO element by first reacting strong acid with precipitate CaF 2 in the waste produced in the semiconductor manufacturing facility, and adding water to the oil by-product produced by the first reaction. And subsequently regenerating the treated raw materials used in the F wastewater treatment.

이러한 목적을 달성하기 위하여 본 발명의 다른 방법은 반도체 제조 설비에서 생성된 폐기물 및 폐기물오니의 처리 방법에 있어서, 반도체 제조 설비에서 생성된 폐기물오니중에서 적어도 F를 포함한 폐수에 처리 원료를 투입하여 침전물 CaF2를 형성하는 단계와, 반도체 제조 설비에서 생성된 폐기물 중에서 강산과 침전물 CaF2를 1차 반응시켜 CaSO4 또는 CaO 원소를 갖는 유가 부산물을 생성하는 단계와, 1차 반응에 의해 생성된 유가 부산물에 수분과 이산화탄소 및 질산을 함께 2차 반응시켜 유안비료를 생성하는 단계를 포함한다. In order to achieve the above object, another method of the present invention provides a method for treating waste and sludge generated in a semiconductor manufacturing facility, wherein the treatment raw material is added to a wastewater including at least F among waste sludge generated in a semiconductor manufacturing facility to precipitate precipitate CaF. 2 to produce a valuable by-product having CaSO 4 or CaO element by the first reaction of the strong acid and precipitate CaF 2 in the waste produced in the semiconductor manufacturing equipment, and the oil by-product produced by the first reaction The second step of reacting the water, carbon dioxide and nitric acid together to produce a yuan fertilizer.

그러므로 본 발명에 의하면, 반도체 제조공정 중에서 발생되는 불소계 폐수처리오니와 폐황산(H2SO4)과 폐과산화수소(H2O2)는 대부분 고농도의 원료를 함유하기 때문에 최소한의 공정을 통하여 경제적인 황산칼슘(CaSO4), 생석회(CaO), 불산(HF2) 등의 유가 부산물과 유안 비료((NH4)2SO4)의 원료 제조가 가능하다.Therefore, according to the present invention, fluorine-based wastewater treatment sludge, waste sulfuric acid (H 2 SO 4 ) and waste hydrogen peroxide (H 2 O 2 ) generated in the semiconductor manufacturing process are mostly economical through a minimum process. It is possible to produce crude oil by-products such as calcium sulfate (CaSO 4 ), quicklime (CaO), and hydrofluoric acid (HF 2 ), and yuan fertilizer ((NH 4 ) 2 SO 4 ).

이하 첨부된 도면을 참조하여 본 발명의 바람직한 실시예에 대해 설명하고자 한다.Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.

[일 실시예][Example]

도 2는 본 발명의 일실시예에 따른 반도체 제조 공정에서 발생된 폐기물의 처리 및 재활용 과정을 나타낸 구성도이다. 도 3은 본 발명의 일실시예에 따른 반도체 폐기물의 재활용 방법을 나타낸 플로우챠트이다.2 is a block diagram showing a treatment and recycling process of the waste generated in the semiconductor manufacturing process according to an embodiment of the present invention. 3 is a flowchart illustrating a method of recycling semiconductor waste according to an embodiment of the present invention.

본 발명의 일실시예는 다음과 같은 처리 과정에 따른다. 먼저, 종래 기술과 같이 폐수처리부(106)는 반도체 제조 설비(100)에서 발생한 폐기물오니중에서 적어도 F를 포함한 폐수(102)에 처리 원료로서 수산화칼슘(Ca(OH)2)을 투입하여 폐수처리한다. One embodiment of the present invention is based on the following processing. First, as in the prior art, the wastewater treatment unit 106 adds calcium hydroxide (Ca (OH) 2 ) as a treatment raw material to wastewater 102 containing at least F among waste sludge generated in the semiconductor manufacturing facility 100 and treats wastewater.

H2SiF6 + 4 Ca(OH)2 → 3CaF2 + CaSiO3↓ + 5H2 OH 2 SiF 6 + 4 Ca (OH) 2 → 3CaF 2 + CaSiO 3 ↓ + 5H 2 O

이러한 반응식 2에 의해 폐수처리부(106)는 불화칼슘(CaF2)과 산화실리콘칼슘(CaSiO3)의 폐수처리오니(108)를 생성한다. (S10)By the reaction scheme 2, the wastewater treatment unit 106 generates wastewater treatment sludge 108 of calcium fluoride (CaF 2 ) and calcium oxide (CaSiO 3 ). (S10)

그런데, 본 발명은 반도체 제조 설비(100)에서 발생한 액상 타입의 강산 폐기물(104)을 종래와 같이 위탁업체를 통해 폐기처리하지 않는다. 그 대신, 폐기물 재활용부(110)를 통해 강산 폐기물(104)과 폐수처리오니(108) 중 불화칼슘(CaF2)을 1차 반응시켜 CaSO4 또는 CaO 원소를 갖는 유가 부산물을 생성한다. 이때, CaSO4는 황산칼슘이고 CaO는 생석회이다.(S20) However, the present invention does not dispose of the liquid acid-type strong acid waste 104 generated in the semiconductor manufacturing facility 100 through the contractor as in the prior art. Instead, the strong acid waste 104 and the calcium fluoride (CaF 2 ) in the wastewater treatment sludge 108 are first reacted through the waste recycling unit 110 to generate a valuable by-product having CaSO 4 or CaO elements. At this time, CaSO 4 is calcium sulfate and CaO is quicklime. (S20)

본 일실시예의 1차 반응시 강산 폐기물(104)은 폐황산(H2SO4)을 약 50∼85%, 또는 폐과산화수소(H2O2)를 약 10∼20%의 범위로 한다. 이를 반응식으로 표현하면 다음과 같다.In the first reaction of the present embodiment, the strong acid waste 104 is about 50 to 85% of waste sulfuric acid (H 2 SO 4 ), or about 10 to 20% of waste hydrogen peroxide (H 2 O 2 ). This can be expressed as a reaction equation as follows.

CaF2 + H2SO4 → CaSO4 + 2HF↑CaF 2 + H 2 SO 4 → CaSO 4 + 2HF ↑

불화칼슘(CaF2)과 폐황산(H2SO4)의 반응에 의해 황산칼슘(CaSO4)의 유가 부산물이 생성된다. 이와 동시에 F를 포함한 불화수소(HF) 가스를 포집해서 이후 불산(HF2)의 제조원료로 사용한다.A valuable by-product of calcium sulfate (CaSO 4 ) is produced by the reaction of calcium fluoride (CaF 2 ) with waste sulfuric acid (H 2 SO 4 ). At the same time, hydrogen fluoride (HF) gas containing F is collected and used as a raw material for hydrofluoric acid (HF 2 ).

CaF2 + H2O2 → CaO + 2F↑ + H2OCaF 2 + H 2 O 2 → CaO + 2F ↑ + H 2 O

반응식 4와 같이 불화칼슘(CaF2)과 폐과산화수소(H2O2)의 반응에 의해 생석회(CaO)의 유가 부산물이 생성된다. 이와 동시에 F 가스를 포집하여 이후 불산(HF2)의 제조원료로 사용하고, 수분(H2O)은 그대로 방출한다. As shown in Scheme 4, a valuable by-product of quicklime (CaO) is produced by the reaction of calcium fluoride (CaF 2 ) and waste hydrogen peroxide (H 2 O 2 ). At the same time, the F gas is collected and then used as a raw material for hydrofluoric acid (HF 2 ), and water (H 2 O) is released as it is.

계속해서, 본 발명의 폐기물 재활용부(110)는 1차 반응에 의해 생성된 유가 부산물인 생석회(CaO)에 수분(H2O)을 2차 반응시켜 F 폐수 처리과정에서 사용되는 처리 원료, 수산화칼슘(Ca(OH)2)을 생성한다. (S30)Subsequently, the waste recycling unit 110 of the present invention secondaryly reacts water (H 2 O) with quicklime (CaO), which is a valuable by-product generated by the first reaction, to treat waste raw materials and calcium hydroxide. (Ca (OH) 2 ) is produced. (S30)

CaO + H2O → Ca(OH)2 CaO + H 2 O → Ca (OH) 2

반응식 5와 같이, 폐기물 재활용부(110)를 통해 얻어진 수산화칼슘(Ca(OH)2)의 처리 원료는 F 폐수 처리부(106)에 재활용된다.As shown in Scheme 5, the treated raw material of calcium hydroxide (Ca (OH) 2 ) obtained through the waste recycling unit 110 is recycled to the F wastewater treatment unit 106.

또한, 본 발명의 폐기물 재활용부(110)는 1차 반응에 의해 포집된 불화수소(HF) 가스와 수분(H2O)을 2차 반응시켜 산화불소(H3O) 및 불소(F) 가스를 생성한다. 1차 반응 또는 2차 반응으로 얻어진 불소(F) 가스와 불화수소(HF) 가스를 반응해서 유가 부산물인 불산(HF2)을 생성한다.(S30) 이러한 반응식은 다음과 같다.In addition, the waste recycling unit 110 of the present invention by the secondary reaction of the hydrogen fluoride (HF) gas and water (H 2 O) collected by the first reaction fluorine oxide (H 3 O) and fluorine (F) gas Create Hydrofluoric acid (HF) gas is reacted with fluorine (F) gas obtained by the first reaction or the second reaction to produce hydrofluoric acid (HF 2 ). (S30) Such a reaction scheme is as follows.

HF + H2O → H3O + F- HF + H 2 O → H 3 O + F -

F + HF → HF2 F + HF → HF 2

그러므로, 본 발명의 일실시예는 폐기물 재활용부(110)에서 강산 폐기물의 폐황산(H2SO4) 또는 폐과산화수소(H2O2)와 폐수처리오니(108)의 불화칼슘(CaF2)을 1차 반응해서 황산칼슘(CaSO4) 또는 생석회(CaO)의 유가 부산물을 생성한다. 그리고, 생석회(CaO) 또는 1차 반응에서 생성된 F 가스(F, HF)를 수분(H2O)과 2차 반응시켜 F 폐수 처리과정에서 사용되는 처리 원료, 수산화칼슘(Ca(OH)2) 또는 유가 부산물인 불산(HF2)을 생성한다.Therefore, one embodiment of the present invention is a waste sulfuric acid (H 2 SO 4 ) or waste hydrogen peroxide (H 2 O 2 ) and waste water treatment sludge calcium fluoride (CaF 2 ) of the strong acid waste in the waste recycling unit 110 The first reaction to produce a valuable value by-product of calcium sulfate (CaSO 4 ) or quicklime (CaO). In addition, the raw material used in the F wastewater treatment process, calcium hydroxide (Ca (OH) 2 ) by secondary reaction of the F gas (F, HF) generated in the quicklime (CaO) or the first reaction with water (H 2 O). Or produce hydrofluoric acid (HF 2 ), a byproduct of oil value.

[다른 실시예][Other Embodiments]

도 4는 본 발명의 다른 실시예에 따른 반도체 제조 공정에서 발생된 폐기물의 처리 및 재활용 과정을 나타낸 구성도이다. 도 5는 본 발명의 다른 실시예에 따른 반도체 폐기물의 재활용 방법을 나타낸 플로우 챠트이다.4 is a block diagram showing a treatment and recycling process of the waste generated in the semiconductor manufacturing process according to another embodiment of the present invention. 5 is a flowchart illustrating a method of recycling semiconductor waste according to another embodiment of the present invention.

본 발명의 다른 실시예는 상술한 일실시예와 마찬가지로 폐기물 재활용부(110)에서 강산 폐기물의 폐황산(H2SO4) 또는 폐과산화수소(H2O 2)와 폐수처리오니(108)의 불화칼슘(CaF2)을 1차 반응해서 황산칼슘(CaSO4) 또는 생석회(CaO)의 유가 부산물을 생성하기까지는 동일하다. (S100∼S110)Another embodiment of the present invention is the same as the above-described embodiment waste fluoride (H 2 SO 4 ) or waste hydrogen peroxide (H 2 O 2 ) and waste water treatment sludge 108 of the strong acid waste in the waste recycling unit 110 The same is true until the first reaction of calcium (CaF 2 ) to produce valuable by-products of calcium sulfate (CaSO 4 ) or quicklime (CaO). (S100 to S110)

계속해서, 본 발명의 폐기물 재활용부(110)는 1차 반응에 의해 생성된 유가 부산물로서 황산칼슘(CaSO4)에 수분(H2O)과 이산화탄소(CO2) 및 질산(NH 3)을 함께 2차 반응시켜 유안비료((NH4)2SO4)를 생성한다. (S120)Subsequently, the waste recycling unit 110 of the present invention combines water (H 2 O) with carbon dioxide (CO 2 ) and nitric acid (NH 3 ) in calcium sulfate (CaSO 4 ) as a valuable value by-product generated by the first reaction. The second reaction to produce a yuan fertilizer ((NH 4 ) 2 SO 4 ). (S120)

CaSO4 + H2O + CO2 + NH3 → CaCO3↓ + (NH4 )2SO4 CaSO 4 + H 2 O + CO 2 + NH 3 → CaCO 3 ↓ + (NH 4 ) 2 SO 4

반응식 7에서 반응 조건은 60℃에서 진행한다. 그리고, 상기 반응에 의해 생성된 유안비료((NH4)2SO4)는 반도체 제조 공정의 원료로 사용되고, 탄산칼슘(CaCO3)은 폐기물오니로서 폐기처리하거나 재활용할 수 있다. In Scheme 7, the reaction conditions proceed at 60 ° C. The fertilizer ((NH 4 ) 2 SO 4 ) generated by the reaction may be used as a raw material for a semiconductor manufacturing process, and calcium carbonate (CaCO 3 ) may be disposed of or recycled as waste sludge.

이상 설명한 바와 같이, 본 발명은 반도체 제조시 발생된 F 폐수에 수산화칼슘(Ca(OH)2)을 투입하여 폐수처리해서 얻어진 침전물 CaF2에 강산성의 폐기물을 반응시켜 CaSO4 또는 CaO 원소를 포함한 유가부산물 또는 불소(F) 함유 가스를 생성하고, 이 유가 부산물 또는 불소 가스에 수분(H2O)을 반응시켜 폐수처리의 원료(Ca(OH)2) 또는 불산(HF2)을 생성함으로써 반도체 폐기물을 효율적으로 재활용할 수 있을 뿐만 아니라 반도체 폐기물의 양을 줄일 수 있어 환경 오염물질을 최소화할 수 있다.As described above, in the present invention, calcium hydroxide (Ca (OH) 2 ) is added to the F wastewater generated during semiconductor manufacturing, and the acidic by-product containing CaSO 4 or CaO element is reacted by reacting strongly acidic waste with precipitated CaF 2 . Or by generating a fluorine (F) -containing gas and reacting the oil by-product or fluorine gas with water (H 2 O) to generate raw material (Ca (OH) 2 ) or hydrofluoric acid (HF 2 ) for wastewater treatment. Not only can it be efficiently recycled, but the amount of semiconductor waste can be reduced to minimize environmental pollutants.

한편, 본 발명은 상술한 실시예에 국한되는 것이 아니라 후술되는 청구범위에 기재된 본 발명의 기술적 사상과 범주내에서 당업자에 의해 여러 가지 변형이 가능하다.On the other hand, the present invention is not limited to the above-described embodiment, various modifications are possible by those skilled in the art within the spirit and scope of the present invention described in the claims to be described later.

Claims (7)

반도체 제조 설비에서 생성된 폐기물 및 폐기물오니의 처리 방법에 있어서, In the method for treating waste and waste sludge produced in a semiconductor manufacturing facility, 상기 반도체 제조 설비에서 생성된 폐기물오니중에서 적어도 F를 포함한 폐수에 처리 원료를 투입하여 침전물 CaF2를 형성하는 단계;Injecting a treatment raw material into the wastewater containing at least F among waste sludge produced in the semiconductor manufacturing facility to form precipitate CaF 2 ; 상기 반도체 제조 설비에서 생성된 폐기물 중에서 강산과 상기 침전물 CaF2를 1차 반응시켜 CaSO4 또는 CaO 원소를 갖는 유가 부산물을 생성하는 단계; 및Firstly reacting the strong acid with the precipitate CaF 2 in the waste produced in the semiconductor manufacturing facility to produce a valuable by-product having CaSO 4 or CaO elements; And 상기 1차 반응에 의해 생성된 유가 부산물에 수분을 2차 반응시켜 상기 F 폐수 처리과정에서 사용되는 처리 원료를 재생성하는 단계를 포함하는 것을 특징으로 하는 반도체 폐기물의 재활용 방법.And regenerating the treated raw material used in the F wastewater treatment process by secondly reacting moisture to the oil value by-product generated by the first reaction. 제 1항에 있어서, 상기 1차 반응시 사용되는 폐기물의 강산은 폐황산 및 폐과산화수소 중에서 어느 하나인 것을 특징으로 하는 반도체 폐기물의 재활용 방법.The method of claim 1, wherein the strong acid of the waste used in the first reaction is any one of waste sulfuric acid and waste hydrogen peroxide. 제 1항에 있어서, 상기 2차 반응에 의해 생성되는 F 폐수 처리의 원료는 Ca(OH)2인 것을 특징으로 하는 반도체 폐기물의 재활용 방법.The method of recycling a semiconductor waste according to claim 1, wherein the raw material of the F wastewater treatment produced by the secondary reaction is Ca (OH) 2 . 제 1항에 있어서, 상기 1차 반응시 유가 부산물과 동시에 F를 포함한 가스를 생성하는 단계; 및The method of claim 1, further comprising: generating a gas including F simultaneously with oil value by-products in the first reaction; And 상기 1차 반응에 의해 생성된 F를 포함한 가스에 수분을 2차 반응시켜 불산을 생성하는 단계를 더 포함하는 것을 특징으로 하는 반도체 폐기물의 재활용 방법.And recycling the moisture to the gas including F generated by the first reaction to generate hydrofluoric acid. 반도체 제조 설비에서 생성된 폐기물 및 폐기물오니의 처리 방법에 있어서, In the method for treating waste and waste sludge produced in a semiconductor manufacturing facility, 상기 반도체 제조 설비에서 생성된 폐기물오니중에서 적어도 F를 포함한 폐수에 처리 원료를 투입하여 침전물 CaF2를 형성하는 단계;Injecting a treatment raw material into the wastewater containing at least F among waste sludge produced in the semiconductor manufacturing facility to form precipitate CaF 2 ; 상기 반도체 제조 설비에서 생성된 폐기물 중에서 강산과 상기 침전물 CaF2를 1차 반응시켜 CaSO4 또는 CaO 원소를 갖는 유가 부산물을 생성하는 단계; 및Firstly reacting the strong acid with the precipitate CaF 2 in the waste produced in the semiconductor manufacturing facility to produce a valuable by-product having CaSO 4 or CaO elements; And 상기 1차 반응에 의해 생성된 유가 부산물에 수분과 이산화탄소 및 질산을 함께 2차 반응시켜 유안비료를 생성하는 단계를 포함하는 것을 특징으로 하는 반도체 폐기물의 재활용 방법.Recycling the semiconductor waste, comprising the step of producing a fertilizer by secondary reaction of the oil by-products produced by the first reaction with water, carbon dioxide and nitric acid. 제 5항에 있어서, 상기 1차 반응시 사용되는 폐기물의 강산은 폐황산 및 폐과산화수소 중에서 어느 하나인 것을 특징으로 하는 반도체 폐기물의 재활용 방법.The method of recycling a semiconductor waste according to claim 5, wherein the strong acid of the waste used in the first reaction is any one of waste sulfuric acid and waste hydrogen peroxide. 제 5항에 있어서, 상기 2차 반응에 의해 생성되는 F 폐수 처리의 원료는 Ca(OH)2인 것을 특징으로 하는 반도체 폐기물의 재활용 방법.The method of recycling a semiconductor waste according to claim 5, wherein the raw material of the F wastewater treatment produced by the secondary reaction is Ca (OH) 2 .
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