화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of the Korean Industrial and Engineering Chemistry, Vol.14, No.2, 213-218, April, 2003
Export Citation
Np(V) 용매추출에 미치는 방사선에 의한 TBP 추출제의 분해생성물 영향
Effect of Radiolysis of Tri-butyl Phosphate Extractant on the Extraction of Neptunium (V)
양한범†, 한선호, 이일희, 문형실1
  • 한국원자력연구소, 대전 305-600
  • 1한국화학연구원, 대전 305-600
Han Beon Yang†, Sun Ho Han, Il Hee Lee, and Houng Sil Moon1
  • Korea Atomic Energy Research Institute, Yusong Daejeon 305-600, Korea
  • 1Korea Research Institute of Chemical Technology, Yusong Daejeon 305-600, Korea
E-mail:
초록
금속원소의 용매추출제로 사용되는 tributyl phosphate (TBP)를 60Co γ-선을 조사시킨 후, TBP의 방사선 분해생성물인 dibutyl phosphate (DBP), monobutyl phosphate (MBP) 및 TBP를 LC-MS로 정량분석하였다. TBP 추출제의 방사선분해가 Np(V) 추출에 미치는 영향에 대한 실험하였다. 1M TBP 추출제의 방사선 흡수 선량이 1 x 107rad 일 때 Np(V) 추출율은 0.8 % 이지만 1 x 108 rad일 때는 52.7 %로 급격히 증가하였으며, 증가 원인은 TBP의 방사선 분해 생성물인 DBP가 Np(V) 추출율을 증가시키는 것으로 규명되었다. 그리고 TBP, DBP 및 MBP의 Np(V) 추출에 대한 추출율은, 1M HNO3일 때 1M TBP와 1M DBP의 Np(V) 추출율은 각각 0.5 %와 86 %이며, 0.5 M DBP에 TBP또는 MBP를 첨가시키는 경우에 Np(V)의 추출율이 감소되는 추출 방해현상 (antagonism)이 나타났다. NpO2+ - 1M HNO3 - DBP 추출계에서 유기상으로 추출되는 화학종은 NpO2NO3·3 DBP으로 밝혀졌다. Np(V)의 환원제로 1M H2O2를 사용한 경우에 Np(V)은 TBP에 추출이 잘되는 Np(IV) 로 환원되어 추출율이 91.3 %까지 증가하였다.
This study was carried out to evaluate the effect of radiolysis of tributyl phosphate (TBP) extractant on the extraction of neptunium (V) in HNO3 solution. The contents of DBP and MBP, the degradation products of TBP, were analyzed with LC-MS (liquid chromatography - mass spectrometry). The effects of radiolysis products (DBP and MBP) and H2O2 reductant in this extraction system were discussed. The radiolysis effect of 1M TBP on the extraction yields of Np(V) was shown to vary with the radiation absorbed dose. The extraction yields of Np(V) increased abruptly from 0.8 % at 1 x 107 rad to 52.7 % at 1 x 108 rad because of the TBP degradation product, DBP, formed a strong complex with Np(V). When TBP or MBP was added in the Np(V) - 1M HNO3 - 0.5 M DBP extraction system, antagonism phenomena appeared which diminished the extraction yields of Np(V). In the NpO2+ - 01M HNO3 - DBP extraction system, the chemical species extracted was NpO2NO3·3 DBP.
Keywords:TBP;DBP;radiolysis;Np;extraction
  1. Yang HB, Lee EH, Lim JK, Yoo JH, Park HS, J. Korean Ind. Eng. Chem., 7(1), 153 (1996)
  2. Yoo JH, Lee EH, Kim KW, Yang HB, Chung DY, Lim JK, Shin YJ, Kim HH, Kwon SG, Kim YH, Hwang DS, Development of Long-lived Radionuclide Partitioning Technology, Report KAERI/RR-1632/95 (1996)
  3. Yang HB, Lee EH, Lim JG, Kim JG, Kim JS, Yoo JH, J. Korean Ind. Eng. Chem., 8(6), 1006 (1997)
  4. Ramaniah MV, Patil SK, Ramakrishna VV, Swarup R, Chadha A, Avadhany GVN, Process Chemistry of Neptunium - Part II, Report BARC-736 (1974)
  5. Wisnubroto DS, Nagasaki S, Enokida Y, Suzuki A, J. Nucl. Sci. Technol., 29(3), 263 (1992)
  6. Yang HB, Han SH, Park SC, Yeun JW, Lee EH, 60Co γ-서너 조사에 의한 DEHPA와 TBP 추출제의 방사선 안전성 조사, 한국원자력학회 2001 추계 학술발표회 논문집 (2001)
  7. Yang HB, Lee EH, Han SH, Park SC, Kim DY, Zr 추출에 미치는 TBP 추출제에 의한 방사선 분해효과, 한국원자력학회 2002 춘계 학술발표회 논문집 (2002)
  8. Davis W, Radiolytic bahavior, in Science and Technology of Tributyl Phosphate, Vol. 1, Chap. 7, W.W. Shculz, A.E. Talbot and J.D. Navratil (eds.), CRC Press, Bora Raton (1984)
  9. Drake VA, Extraction Chemistry of Neptunium, Science and Technology of Tributyl Phosphate, Vol. III, Chap. 3 (p. 123), W.W. Schulz, A.E. Talbot and J.D. Vanratil (eds.), CRC Press, Bora Raton (1990)
  10. Byeon KH, Lee IH, Kwon SG, Kim KW, Yang HB, Jung DY, Lim JG, Shin HK, Kim SH, The Extraction behaviors of Transuranic Elements, Report KAERI/AR-550-99 (1999)
  11. Katz JJ, Seaborg GT, Morss LR, Neptunium, in the Chemistry of the Actinide Elements, Vol. 1, Chap. 6 (p. 443), Chapman and Hall (1986)