<sup>60</sup>Co γ-선 조사에 의한 TBP 추출제의 방사선 분해 특성

양한범; 이일회; 한선호; 김원호; 유재형; Han Beom Yang; ILL-HEE Lee; Sun Ho Han; Won Ho Kim; Jae-Hyung Yoo

Journal of the Korean Industrial and Engineering Chemistry, Vol.14, No.3, 320-324, May, 2003

Export Citation

⁶⁰Co γ-선 조사에 의한 TBP 추출제의 방사선 분해 특성

Radiolysis of TBP Extractant by Irradiation with ⁶⁰Co γ-ray

양한범^†, 이일회, 한선호, 김원호, 유재형

한국원자력연구소, 대전 305-600

Han Beom Yang^†, ILL-HEE Lee, Sun Ho Han, Won Ho Kim, and Jae-Hyung Yoo

Korea Atomic Energy Research Institute, Daejeon 305-600, Korea

E-mail:

초록

방사성 액체폐기물에 함유되어 있는 방사성 핵종의 회수 및 처리에 사용되는 용매 추출제인 tributyl phosphate (TBP)를 인위적인 방법인 ⁶⁰Co γ-방사선을 조사시킨 다음 TBP 및 분해생성물을 기체 크로마토그래피 - 질량 분석법, 액체 크로마토그래피 - 질량 분석법, 핵 자기공명법(³¹P-NMR), 이온크로마토그래피, 적외선 분광법으로 측정하여 방사선 분해 생성물의 종류와 농도를 정량분석하고, TBP 추출제의 방사선 분해 특성에 대해 기술하였다. 실험결과로부터 TBP는 방사선에 의해 TBP에 결합되어 있는 3개의 butyl 기가 한 개씩 순차적으로 분해되거나, 두 개, 또는 3개의 butyl 기가 동시에 떨어지면서 TBP → HDBP → H₂MBP → H₃PO₄가 생성되는 반응기구로 분해되는 것으로 생각된다.

This study was carried out to evaluate the radiation stability of tributyl phosphate (TBP) extractant by irradiation of ⁶⁰Co γ-rays. The degradation products of TBP leads to a decrease of extraction yields and/or formation of the third phase in the solvent extraction system of radioactive waste. TBP was irradiated with ⁶⁰Co γ-ray and the degradation products were analysed with gas chromatography - mass spectrometer (GC-MS), liquid chromatography - mass spectrometer (LC-MS), nuclear magnetic resonance (NMR) spectrometer, ion chromatography (IC) and infrared (IR) spectrometer. It was found that the major degradation products from gamma radiolysis of TBP were dibutyl phosphate (HDBP), monobutyl phosphate (H₂MBP) and phosphoric acid. The main radiolysis pathway of TBP may be decomposed to the H₃PO₄ by losing one butyl radical step by step in subsequent reactions or losing two ~ three butyl radicals simultaneously like the following ways, that is TBP → HDBP → H₂MBP → H₃PO₄.

Keywords:TBP;radiolysis;degradation;radiation stability

[References]

Yang HB, Lee EH, Lim JK, Yoo JH, Park HS, J. Korean Ind. Eng. Chem., 7(1), 153 (1996)
Yang HB, Lim JK, Yoo JH, Partitioning of Minor Actinides from Rare Earths by Solvent Extraction with di-(2-ethylhexyl) Phosphoric Acid, 4th OECD/NEA International Exchange Meeting on Partitioning and Transmutation Technology, 1996, Sep. 11 ~ 14, Mito, Japan (1996)
Yang HB, Lee EH, Lim JG, Kim JG, Kim JS, Yoo JH, J. Korean Ind. Eng. Chem., 8(6), 1006 (1997)
Tuck DG, J. Chem. Soc., 2783 (1958)
Han SH, Lee HJ, Yang HB, Park YS, Joe KS, Anal. Sci. Tech., 15, 329 (2002)
Lash RP, Hill CJ, J. Liq. Chromatogr., 2, 417 (1979)
Creech ET, Influence of Uranyl Phosphate on the uv/vis Spectrohotometric on-line Monitoring of Uranium in Tributyl Phosphate/Hydrocarbon Solvent, Y/DK-354 (1983)
Wallace D, Radiolytic Bahavior, Chap. 7, in Science and Technology of Tributyl Phosphate, Vol. I, W.W. Schulz, L.L. Burger and J.D. Navratil (eds.), CRC Press, Bora Raton (1990)

[Related Articles]

[1] Yang HB, Lee EH, Lim JK, Yoo JH, Park HS, J. Korean Ind. Eng. Chem., 7(1), 153 (1996)

[2] Yang HB, Lim JK, Yoo JH, Partitioning of Minor Actinides from Rare Earths by Solvent Extraction with di-(2-ethylhexyl) Phosphoric Acid, 4th OECD/NEA International Exchange Meeting on Partitioning and Transmutation Technology, 1996, Sep. 11 ~ 14, Mito, Japan (1996)

[3] Yang HB, Lee EH, Lim JG, Kim JG, Kim JS, Yoo JH, J. Korean Ind. Eng. Chem., 8(6), 1006 (1997)

[4] Tuck DG, J. Chem. Soc., 2783 (1958)

[5] Han SH, Lee HJ, Yang HB, Park YS, Joe KS, Anal. Sci. Tech., 15, 329 (2002)

[6] Lash RP, Hill CJ, J. Liq. Chromatogr., 2, 417 (1979)

[7] Creech ET, Influence of Uranyl Phosphate on the uv/vis Spectrohotometric on-line Monitoring of Uranium in Tributyl Phosphate/Hydrocarbon Solvent, Y/DK-354 (1983)

[8] Wallace D, Radiolytic Bahavior, Chap. 7, in Science and Technology of Tributyl Phosphate, Vol. I, W.W. Schulz, L.L. Burger and J.D. Navratil (eds.), CRC Press, Bora Raton (1990)