KR100740621B1 - Fabrication method of ito power from waste ito target by spray pyrolysis process and the ito powder which is processed by the processing method thereof - Google Patents

Fabrication method of ito power from waste ito target by spray pyrolysis process and the ito powder which is processed by the processing method thereof Download PDF

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KR100740621B1
KR100740621B1 KR1020060057110A KR20060057110A KR100740621B1 KR 100740621 B1 KR100740621 B1 KR 100740621B1 KR 1020060057110 A KR1020060057110 A KR 1020060057110A KR 20060057110 A KR20060057110 A KR 20060057110A KR 100740621 B1 KR100740621 B1 KR 100740621B1
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ito
powder
waste
target
spray pyrolysis
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유재근
강성구
진수곤
김규진
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호서대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium

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Abstract

Provided is a preparation method of ITO powder from waste ITO target by spray pyrolysis process to continuously prepare ITO complex oxide powder with average particle size of 50nm or less from a complex chloride solution. The preparation method of ITO powder comprises the steps of: adding a waste ITO target to tin chloride solution; dissolving indium and tin elements at 80-90deg.C and filtering three times to obtain a complex chloride raw material solution having impurities less than 50ppm; spraying the filtered complex chloride solution onto a pyrolysis reactor maintained at 800deg.C or higher; continuously collecting complex oxide powder with a solid particle collector; stirring the ITO powder at room temperature for four hours or longer and washing three times; separating ITO powder from water with a high-speed centrifuge; and drying the ITO powder at 90deg.C or higher for at least 24 hours.

Description

폐 아이티오 타깃을 원료로 하여 분무열분해 공정을 통하여 아이티오 분말을 제조하는 방법 및 이 방법으로 제조된 아이티오 분말{Fabrication method of ITO power from waste ITO target by spray pyrolysis process and the ITO powder which is processed by the processing method thereof}Fabrication method of ITO power from waste ITO target by spray pyrolysis process and the ITO powder which is processed by the processing method

도1은 본 발명에 따른 폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)을 원료로 하여 분무열분해 공정을 통하여 아이티오(ITO) 분말을 제조하는 방법을 나타낸 흐름도이다. FIG. 1 is a flowchart illustrating a method of manufacturing ITO powder through a spray pyrolysis process using a waste indium tin oxide (ITO) target according to the present invention as a raw material.

도2는 본 발명에 따른 분무열분해 방법으로 생성된 평균입도 50nm 이하의 아이티오(ITO) 분말을 전자현미경으로 나타낸 것이다. Figure 2 shows the electron microscope of the ITO (ITO) powder having an average particle size of 50nm or less produced by the spray pyrolysis method according to the present invention.

본 발명은 폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)을 원료로 하여 아이티오(ITO: Indium Tin Oxide) 분말을 제조하는 방법에 관한 것으로서, 보다 상세하게는 유가금속 성분들을 포함하는 고상 폐기물로부터 평균입도 50nm 이하의 나 노분말을 분무열분해 방법으로 연속적으로 제조함으로써 고상폐기물의 효율적인 리싸이클링(recycling) 방법을 제공하기 위한 것이다. The present invention relates to a method for producing ITO (Indium Tin Oxide) powder from a waste Indium Tin Oxide (ITO) target as a raw material, and more particularly, to a solid phase including valuable metal components. It is to provide an efficient recycling method of solid waste by continuously producing nanopowders having an average particle size of 50 nm or less from waste by spray pyrolysis.

일반적으로 아이티오(ITO: Indium Tin Oxide. 이하 'ITO'라 함)에 관련된 기술이나 연구는 주로 생성된 막질과 제조 조건과의 상관관계 규명에 치우쳐 있었으며, 아이티오(ITO) 원료 생산이나 특히 아이티오(ITO) 타깃(target) 리싸이클링(recycling)에 관련된 기술은 거의 보고된 바가 없었다. 따라서 국내 기업들은 외국 기업의 기술에 전적으로 의존해야 하는 문제점이 있었다. In general, technologies and research related to ITO (Indium Tin Oxide) (ITO) have been mainly focused on the correlation between the produced film quality and manufacturing conditions. There have been few reports of techniques related to ITO target recycling. Therefore, domestic companies had to rely solely on the technology of foreign companies.

최근 리싸이클링(recycling)에 대한 연구가 진행되고 있으나 정제 원료의 순도나 회수율의 경제성에서 살펴본다면 크게 미진한 것으로 알려져 있다. Recently, research on recycling has been conducted, but it is known that the refining raw material is considerably inferior in terms of purity and recovery economics.

종래의 분무열분해 공정에 의한 금속산화물의 제조공정으로는 철강 제조공장에서 열연강판의 산세 공정 중 부산물로 생성되는 폐산을 이용한 산화철(Fe2O3) 분말제조 방법, 열연강판의 산세과정에서 발생되는 폐산 내에 망간 페라이트(Mn-ferrite) 조성에 해당되는 망간 성분을 첨가한 복합 산용액을 원료로 하여 망간 폐라이트 복합 산화물 분말 제조 및 PCB 제조공정 중 발생되는 폐동액을 원료로 하여 산화동(CuO) 분말을 제조하는 방법이 있었다. As a conventional process for producing metal oxides by spray pyrolysis, iron oxide (Fe2O3) powder manufacturing method using waste acid generated as a by-product during the pickling process of hot rolled steel sheet in a steel manufacturing plant, and manganese in waste acid generated during pickling of hot rolled steel Manufacturing copper oxide powder (CuO) by using manganese waste-light composite oxide powder and waste copper generated during PCB manufacturing process as a raw material using a composite acid solution containing manganese component corresponding to ferrite (Mn-ferrite) composition There was a way.

상기 제조공정들은 수열합성법 및 졸-겔 합성법 등에 의존한 실험실적 규모의 소량 제조에 불과하여 연속적으로 대량생산 하기에는 문제점이 있었다. The manufacturing processes are only small-scale manufacturing on a laboratory scale depending on hydrothermal synthesis method and sol-gel synthesis method, and thus have problems in mass production continuously.

상기의 문제점을 해결하기 위하여 본 발명은 폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)과 해당되는 조성의 주석을 염산에 용해시킨 복합 염화물 용액으로부터 분무열분해공정에 의해 평균입도 50nm 이하인 아이티오(ITO) 복합 산화물 분말을 연속적으로 제조하기 위하여 폐 아이티오(ITO) 타깃(target)을 원료로 하여 분무열분해 공정을 통하여 아이티오(ITO) 분말을 제조하는 방법 및 이 방법으로 제조된 아이티오(ITO) 분말을 제공하는데 그 목적이 있다. In order to solve the above problems, the present invention has a waste particle size of 50 nm or less by spray pyrolysis from a complex chloride solution in which tin indium tin oxide (ITO) target and tin of a corresponding composition are dissolved in hydrochloric acid. In order to continuously manufacture (ITO) composite oxide powder, a method for producing ITO powder through a spray pyrolysis process using waste ITO target as a raw material, and ITO) powder for this purpose.

본 발명은 아이티오(ITO: Indium Tin Oxide) 박막 증착 공정 후에 발생되는 폐 아이티오(ITO) 타깃(target)과 해당되는 조성의 주석을 염산에 용해시킨 복합 염화물 용액을 원료로 하여 원료용액의 미립화기, 반응로, 분체 포집기 및 유해기체의 청정을 위한 세척기(scrubber)까지 포함하는 분무열분해 장치 내에 열분해 반응에 의해 평균입도 50nm 이하의 아이티오(ITO) 분말을 연속적으로 제조하는 방법 및 이 방법으로 제조된 아이티오(ITO) 분말에 관한 것이다. In the present invention, the raw material solution is atomized using a complex chloride solution in which tin of a waste ITO target generated after an ITO thin film deposition process and tin of a corresponding composition is dissolved in hydrochloric acid. A method of continuously producing an ITO powder having an average particle size of 50 nm or less by pyrolysis reaction in a spray pyrolysis apparatus including a gas, a reactor, a powder collector, and a scrubber for cleaning harmful gases. It relates to the prepared ITO (ITO) powder.

이하, 본 발명의 상세한 설명은 첨부된 도면과 함께 상세히 설명한다.Hereinafter, the detailed description of the present invention will be described in detail with the accompanying drawings.

도1은 본 발명에 따른 폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)을 원료로 하여 분무열분해 공정을 통하여 아이티오(ITO) 분말을 제조하는 방법을 나타낸 흐름도이다. FIG. 1 is a flowchart illustrating a method of manufacturing ITO powder through a spray pyrolysis process using a waste indium tin oxide (ITO) target according to the present invention as a raw material.

폐 아이티오(ITO) 타깃(target)과 주석을 염산 용액에 첨가하는 제1단계와 상기 제1단계에서 염산용액에 첨가한 인듐과 주석 성분들을 80 내지 90 ℃ 에서 용해시킨 후 여과기를 이용하여 3회 여과시켜 철(Fe), 망간(Mn), 알루미늄(Al), 규소(Si) 및 인(P)등의 불순물이 50ppm 이하가 되도록 조절하여 복합 염화물 원료용액을 제조(제2단계)한다. The first step of adding the waste ITO target and tin to the hydrochloric acid solution, and the indium and tin components added to the hydrochloric acid solution in the first step at 80 to 90 ℃ and using a filter 3 Filtration is performed once to adjust the impurities such as iron (Fe), manganese (Mn), aluminum (Al), silicon (Si) and phosphorus (P) to 50 ppm or less to prepare a complex chloride raw material solution (second step).

상기 제2단계에서 여과시킨 복합 염화물 용액을 티타늄 금속으로 제조된 노즐(nozzle)을 이용하여 800℃ 이상의 고온으로 유지된 열분해 반응로에 분무시키는 제3단계와 상기 제3단계에서 분무 후 열분해 반응에 의해 복합 산화물 분말을 연속적으로 형성시킨다. In the third step of spraying the complex chloride solution filtered in the second step to a pyrolysis reactor maintained at a high temperature of 800 ℃ or more using a nozzle made of titanium metal and in the pyrolysis reaction after spraying in the third step Thereby forming a composite oxide powder continuously.

이때 반응식은 다음과 같이 나타낼 수 있다. The reaction formula can be expressed as follows.

2InCl3 + 2SnCl2 + 5H2O = (InSn)2O3 + 10HCl + O2 2InCl 3 + 2SnCl 2 + 5H 2 O = (InSn) 2 O 3 + 10HCl + O 2

상기 노즐(nozzle)에 의해 미립화된 원료용액은 액적 형태로 되며, 상기 액적들은 열분해과정에서 아이티오(ITO: Indium Tin Oxide) 상으로 반응이 진행되면서 액적의 표면과 중심부분에서의 용매의 증발속도 차이로 인하여 분열되게 되며 이 분열은 반응온도가 높을수록 더욱 커지게 된다. The raw material solution atomized by the nozzle is in the form of droplets, and the droplets evaporate at the surface and central portion of the droplet as the reaction proceeds to the indium tin oxide (ITO) phase during pyrolysis. The difference leads to splitting, and the splitter gets larger at higher reaction temperatures.

또한, 이 분열과정에 의해 액적이 더욱 미립화되어 나노 크기의 형태로 된 다. In addition, by this cleavage process, droplets are further atomized into nano-sized forms.

상기 제3단계에서 연속적으로 형성된 분말을 분체포집기에서 포집(제4단계)하게 되며, 도2는 본 발명에 따른 분무열분해 방법으로 반응온도 800 및 900℃에서 생성된 평균입도 50nm 이하의 아이티오(ITO: Indium Tin Oxide) 분말을 전자현미경으로 나타낸 것이다. The powder continuously formed in the third step is collected in the powder collector (fourth step), Figure 2 is a spray pyrolysis method according to the present invention, the average particle size of 50 nm or less produced at the reaction temperature 800 and 900 ℃ ( Indium Tin Oxide (ITO) powder is represented by an electron microscope.

상기 제4단계에서 포집된 아이티오(ITO: Indium Tin Oxide) 분말을 상온의 물에 4시간 이상 저어주면서 3회 수세하는 제5단계와 상기 제5단계에서 수세된 아이티오(ITO) 분말들을 50,000 rpm 이상의 고속 원심분리기에 의해 고상의 아이티오(ITO) 분말을 물에서 분리시키는 제6단계와 상기 제6단계에서 분리된 아이티오(ITO) 분말을 온도 90℃ 이상에서 24시간 이상 건조 시키는 제7단계로 이루어진다.The fifth step of washing three times while stirring the Indium Tin Oxide (ITO) powder collected in the fourth step in water at room temperature for at least 4 hours and 50,000 times the washed ITO (ITO) powder washed in the fifth step a sixth step of separating the solid ITO powder from water by a high-speed centrifuge of rpm or more; and a seventh step of drying the ITO powder separated in the sixth step for more than 24 hours at a temperature of 90 ° C. Consists of steps.

마지막으로 본 발명에서는 폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)과 해당되는 조성의 주석을 염산에 용해시킨 복합 염화물 용액을 원료로 하여 분무열분해 공정에 의해 평균입도 50nm 이하의 아이티오(ITO) 분말을 연속적으로 제조하는 방법을 나타내었다. 평균입도가 50nm 이하일 뿐만 아니라 도2에 나타낸 바와 같이 입자형상 및 입도분포도가 상당히 균일하게 나타나고 있으므로 반도체 및 디스플레이 분야 등에서 요구되는 조건을 충분히 만족시키고 있다. Finally, in the present invention, a composite chloride solution in which a waste Indium Tin Oxide (ITO) target and a corresponding composition of tin is dissolved in hydrochloric acid is used as a raw material and has a mean particle size of 50 nm or less by spray pyrolysis. ITO) shows a method for producing the powder continuously. Not only the average particle size is 50 nm or less, but also the particle shape and particle size distribution are fairly uniform as shown in Fig. 2, which satisfies the requirements of the semiconductor and display fields.

이상의 본 발명의 바람직한 실시 예를 설명하였지만, 본 발명의 범위는 상기에 기재된 실시 예 및 하기의 청구범위에 한정되지 않으며, 본 발명에 속하는 분야에서 통상의 지식을 가진 자라면 본 발명으로부터 다양한 변경 및 균등한 실시가 가능하다.Although the preferred embodiments of the present invention have been described above, the scope of the present invention is not limited to the embodiments described above and the claims below, and those skilled in the art to which the present invention pertains various modifications and Equal implementation is possible.

상기 본 발명에 의하여 아이티오(ITO: Indium Tin Oxide) 박막 증착 공정 후 발생되는 폐 아이티오(ITO) 타깃(target)과 해당되는 조성의 주석을 염산 용액에 용해시킨 복합 염화물 용액을 원료로 하여 분무열분해 공정에 의해 평균입도 50nm 이하인 인듐산화물 분말을 매우 경제적으로 제조할 수 있으며, 이러한 방법으로 반복적으로 대량생산이 가능하여 수입대체의 효과 및 제조 비용의 절감의 효과가 있다. According to the present invention, a sprayed material is used as a raw material of a complex chloride solution in which a waste ITO target generated after an ITO thin film deposition process and tin of a corresponding composition are dissolved in a hydrochloric acid solution. By the pyrolysis process, the indium oxide powder having an average particle size of 50 nm or less can be produced very economically, and in this way, it is possible to repeatedly mass-produce the effect of import substitution and reduction of manufacturing cost.

또한, 분무열분해 공정에 의해 아이티오(ITO) 분말을 연속적으로 제조할 수 있기 때문에 품질의 균일성이 우수한 효과가 있다. In addition, since ITO (ITO) powder can be continuously produced by the spray pyrolysis process, there is an effect of excellent uniformity of quality.

Claims (3)

폐 아이티오(ITO: Indium Tin Oxide) 타깃(target)과 주석을 염산 용액에 첨가하는 제1단계;Adding a waste Indium Tin Oxide (ITO) target and tin to a hydrochloric acid solution; 상기 제1단계에서 염산용액에 첨가한 인듐과 주석 성분들을 80 내지 90 ℃ 에서 용해시킨 후 여과기를 이용하여 3회 여과시켜 복합 염화물 원료용액을 제조하는 제2단계;A second step of preparing a complex chloride raw material solution by dissolving indium and tin components added to the hydrochloric acid solution in the first step at 80 to 90 ° C. and filtration three times using a filter; 상기 제2단계에서 여과시킨 복합 염화물 용액을 티타늄 금속으로 제조된 노즐을 이용하여 800℃ 이상의 고온으로 유지된 열분해 반응로에 분무시키는 제3단계;A third step of spraying the complex chloride solution filtered in the second step into a pyrolysis reactor maintained at a high temperature of 800 ° C. or higher using a nozzle made of titanium metal; 상기 제3단계에서 분무 후 열분해 반응에 의해 복합 산화물 분말을 연속적으로 형성시키고, 상기 연속적으로 형성된 분말을 분체포집기에서 포집하는 제4단계;A fourth step of continuously forming the composite oxide powder by pyrolysis after spraying in the third step, and collecting the continuously formed powder in a powder collector; 상기 제4단계에서 포집된 아이티오(ITO) 분말을 상온의 물에 4시간 이상 저어주면서 3회 수세하는 제5단계;A fifth step of washing three times washing the ITO powder collected in the fourth step with water at room temperature for 4 hours or more; 상기 제5단계에서 수세된 아이티오(ITO) 분말들을 50,000 rpm 이상의 고속 원심분리기에 의해 고상의 아이티오(ITO) 분말을 물에서 분리시키는 제6단계;A sixth step of separating the solid ITO (ITO) powder from water by a high-speed centrifuge of at least 50,000 rpm with the washed ITO powder in the fifth step; 상기 제6단계에서 분리된 아이티오(ITO) 분말을 온도 90℃ 이상에서 24시간 이상 건조 시키는 제7단계;A seventh step of drying the ITO powder separated in the sixth step at a temperature of 90 ° C. or more for at least 24 hours; 로 이루어지는 것을 특징으로 하는 폐 아이티오 타깃을 원료로 하여 분무열분해 공정을 통하여 아이티오 분말을 제조하는 방법. A method for producing Ithio powder through a spray pyrolysis process using as a raw material a waste Ithio target, characterized in that consisting of. 제 1 항에 있어서,The method of claim 1, 상기 제2단계에서 여과과정으로 철(Fe), 망간(Mn), 알루미늄(Al), 규소(Si) 및 인(P)등의 불순물이 50ppm 이하가 되는 것을 특징으로 하는 폐 아이티오 타깃을 원료로 하여 분무열분해 공정을 통하여 아이티오 분말을 제조하는 방법. In the second step, the waste itio target is characterized in that impurities such as iron (Fe), manganese (Mn), aluminum (Al), silicon (Si) and phosphorus (P) are 50 ppm or less. Method for producing the Ithio powder through the spray pyrolysis process. 제 1 항 또는 제 2 항의 방법으로 제조된 것을 특징으로 하는 아이티오 분말.Itio powder prepared by the method of claim 1 or 2.
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Publication number Priority date Publication date Assignee Title
CN103332728A (en) * 2013-06-26 2013-10-02 宁波今心新材料科技有限公司 Preparation method of tin oxide ultrafine powder
KR20190032076A (en) * 2017-09-19 2019-03-27 (주)나노랜드 a manufacturing method of indium tin oxide powder using spray pyrolysis process

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KR20030005407A (en) * 2001-03-28 2003-01-17 가부시키 가이샤 닛코 마테리알즈 Manufacturing method of ito powder with tin dissolved in indium oxide, and manufacturing method of ito target
US6793908B2 (en) 2002-05-09 2004-09-21 Cheng Loong Corporation Method for preparing ITO nanometer powders

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KR20030005407A (en) * 2001-03-28 2003-01-17 가부시키 가이샤 닛코 마테리알즈 Manufacturing method of ito powder with tin dissolved in indium oxide, and manufacturing method of ito target
US6793908B2 (en) 2002-05-09 2004-09-21 Cheng Loong Corporation Method for preparing ITO nanometer powders

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332728A (en) * 2013-06-26 2013-10-02 宁波今心新材料科技有限公司 Preparation method of tin oxide ultrafine powder
KR20190032076A (en) * 2017-09-19 2019-03-27 (주)나노랜드 a manufacturing method of indium tin oxide powder using spray pyrolysis process
KR101976842B1 (en) * 2017-09-19 2019-05-09 (주)나노랜드 a manufacturing method of indium tin oxide powder using spray pyrolysis process

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