Recovery of high-purity phosphoric acid from the waste acids in semiconductor manufacturing process

반도체(半導體) 제조공정(製造工程)에서 발생하는 혼산폐액(混酸廢液)으로부터 고순도(高純度) 인산회수(燐酸回收)

  • Published : 2006.10.27

Abstract

The waste solution discharged from the LCD manufacturing process contains acids like nitric, acetic and phosphoric acid and metal ions such as Al, Mo and other impurities. It is important to remove impurities less than 1 ppm in phosphoric acid to reuse as an etchant because the residual impurities even in sub-ppm concentration in semiconductor materials play a major role on the electronic properties. In this study, a mixed system of solvent extraction, diffusion dialysis and ion-exchange was developed to commercialize in an efficient system fur recovering the high-purity phosphoric acid. By vacuum evaporation, almost 99% of nitric and acetic acid was removed. And by solvent extraction method with tri-octyl phosphate (TOP) as an extractant, the removal of acetic and nitric acid from the acid mixture was achieved effectively at the ratio A/O=1/3 with 4th stage of extraction stage. About 97.5% of Al and 36.7% of Mo were removed by diffusion dialysis. Essentially almost complete removal of metal ions and purification of high-purity phosphoric acid could be obtained by using ion exchange.

LCD와 반도체 제조공정에서 발생하는 인산, 질산, 초산, Al, Mo 등이 혼재하고 있는 인산계 혼산폐액을 액정제조공정에서 사용할 수 있는 고순도 에칭액으로 재활용하기 위해서 용매추출법, 진공증발법, 확산투석법 및 이온교환법의 각각의 기술적 특성을 살린 혼합 처리공정을 이용하여 고순도 인산회수 기술을 확립하고 상용화 시스템을 개발하고자 하였다. 시험 결과 진공증발에 의해 질산과 초산을 100% 제거할 수 있었고, TOP를 이용한 용매추출에서도 추출 4단, 탈거 6단으로 완벽하게 제거할 수 있었다. 이온교환의 전단계로 적용한 확산투석에서 Al 97.5%, Mo 36.7% 제거할 수 있었고 이온교환공정에서 Al 및 Mo를 각각 1ppm이하로 정제할 수 있었다.

Keywords

References

  1. 안재우, 1998: 窒酸 Etching 廢液으로부터 溶媒抽出法에 의한 窒酸의 回收에 관한 研究, 한국자원리싸이클링학회지, 7(5), pp.46-51
  2. 特開 2004-160292 : 酢酸-哨酸-リン酸係混酸廢液からのリン酸の分利回收方法
  3. Shibata, J and Yamamoto,H., 2001: Application of solvent extaction to the treatment of individual wastes, The 6th International Symposium on East Asian Resources Recycling Technology, Gyeongju, Korea, October 23-25, pp.259-263
  4. 이향숙 등, 2005: 醋酸, 窒酸, 燐酸을 함유한 三元係 廢昆酸으로부터 燐酸 回收에 관한 기초 研究, 한국자원리싸이클링학회지 14(5). pp.18-23
  5. 한국공개특허, 10-2004-0105553: 인산 함유 폐식각액의 재생 방법