钴离子对阳离子交换树脂氧化裂解反应的催化作用
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摘要
氧化裂解能有效增大放射性废阳离子交换树脂的减容比,但是较高的裂解温度易导致核素挥发。为了降低裂解温度,以硝酸钴和阳离子交换树脂为原料,制备了不同钴含量的含钴树脂,在热重分析仪上考察了钴含量对树脂裂解反应的影响。采用离子交换的方法掺入10～40 g/L的钴离子,可以使树脂共聚物基体裂解峰的峰值温度降低232～263℃,而对减容比的影响较小。通过对残渣的XRD、FT-IR、XPS及元素分析,发现由钴离子转化形成的氧化钴对共聚物基体的裂解具有催化作用,促进了硫键(—S—)的断裂,使裂解温度降低。
Oxidative pyrolysis can effectively increase the volume reduction ratio of radioactive waste cation exchange resin, but higher pyrolysis temperature is likely to cause nuclides to volatilize. However, the high pyrolysis temperature can easily lead to the volatilization of nuclide. To lower the pyrolysis temperature, a series of resins containing an increasing Co loading were prepared by ion exchange method, using Co(NO_3)_2·6H_2O and cation exchange resin(Amberlite IRN-97H) as raw materials. The effect of Co with different contents on the pyrolysis of resin was investigated on a thermogravimetric analyzer. When the Co content was 10-40 g/L, the peak temperature of the mass loss peak of the copolymer matrix of resin was reduced by 232-263℃ compared to that of pure resin,while the volume reduction ratios were almost the same. The XRD, FT-IR, XPS and elemental analysis of the solid residue were performed. The results showed that the CoO formed by the conversion from Co~(2+) had a catalytic effect on the oxidative pyrolysis of the copolymer matrix, which promoted the breakdown of sulfurbridge(—S—).
Oxidative pyrolysis can effectively increase the volume reduction ratio of radioactive waste cation exchange resin, but higher pyrolysis temperature is likely to cause nuclides to volatilize. However, the high pyrolysis temperature can easily lead to the volatilization of nuclide. To lower the pyrolysis temperature, a series of resins containing an increasing Co loading were prepared by ion exchange method, using Co(NO_3)_2·6H_2O and cation exchange resin(Amberlite IRN-97H) as raw materials. The effect of Co with different contents on the pyrolysis of resin was investigated on a thermogravimetric analyzer. When the Co content was 10-40 g/L, the peak temperature of the mass loss peak of the copolymer matrix of resin was reduced by 232-263℃ compared to that of pure resin,while the volume reduction ratios were almost the same. The XRD, FT-IR, XPS and elemental analysis of the solid residue were performed. The results showed that the CoO formed by the conversion from Co~(2+) had a catalytic effect on the oxidative pyrolysis of the copolymer matrix, which promoted the breakdown of sulfurbridge(—S—).
引文
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[2]张立东,李永红.放射性废树脂处理技术调研及路线选择探讨[J].科学时代,2015,14:73-74.Zhang L D,Li Y H.Investigation on treatment technology of radioactive spent resin and discussion on route selection[J].Science Times,2015,14:73-74.
[3]罗上庚.废离子交换树脂的优化处理[J].核科学与工程,2003,23(2):165-172.Luo S G.Optimization treatment of spent ion exchange resin[J].Chinese Journal of Nuclear Science and Engineering,2003,23(2):165-172.
[4]Wang J,Wan Z.Treatment and disposal of spent radioactive ionexchange resins produced in the nuclear industry[J].Progress in Nuclear Energy,2015,78:47-55.
[5]Jantzen C M,Lee W E,Ojovan M I.Radioactive waste conditioning,immobilisation,and encapsulation processes and technologies:overview and advances(chapter 7)[R].Office of Scientific&Technical Information Technical Reports,2012.
[6]Tapete D,Cigna F,Lasaponara R,et al.Thermal analysis and immobilisation of spent ion exchange resin in borosilicate glass[J].New Journal of Glass&Ceramics,2012,2(2):111-120.
[7]Kim K,Son S H,Kim K S,et al.Treatment of radioactive ionic exchange resins by super-and sub-critical water oxidation(SCWO)[J].Nuclear Engineering&Design,2010,240(10):3654-3659.
[8]Nezu A,Morishima T,Watanabe T.Thermal plasma treatment of waste ion-exchange resins doped with metals[J].Thin Solid Films,2003,435(1):335-339.
[9]Moustakas K,Fatta D,Malamis S,et al.Demonstration plasma gasification/vitrification system for effective hazardous waste treatment[J].Journal of Hazardous Materials,2005,123(1):120-126.
[10]Zahorodna M,Bogoczek R,Oliveros E,et al.Application of the Fenton process to the dissolution and mineralization of ion exchange resins[J].Catalysis Today,2007,129(1):200-206.
[11]Wan Z,Xu L,Wang J.Treatment of spent radioactive anionic exchange resins using Fenton-like oxidation process[J].Chemical Engineering Journal,2016,284:733-740.
[12]Eun H C,Yang H C,Cho Y Z,et al.Study on a stable destruction method of radioactive waste ion exchange resins[J].Journal of Radioanalytical&Nuclear Chemistry,2009,281(3):585-590.
[13]Yang H C,Lee M W,Yoon I H,et al.Scale-up and optimization of a two-stage molten salt oxidation reactor system for the treatment of cation exchange resins[J].Chemical Engineering Research&Design,2013,91(4):703-712.
[14]Mason J B,Myers C A.THOR?steam reforming technology for the treatment of ion exchange resins and more complex wastes such as fuel reprocessing wastes[C]//ASME 2010,International Conference on Environmental Remediation and Radioactive Waste Management.2010:171-178.
[15]Pierce E M,Lukens W W,Fitts J P,et al.Experimental determination of the speciation,partitioning,and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form[J].Applied Geochemistry,2014,42(4):47-59.
[16]Mason J B,Oliver T W,Hill G M,et al.Studsvik processing facility update[C]//WM'03 Conference.2003.
[17]Mason J B,Oliver T W,Carson M P,et al.Studsvik processing facility:pyrolysis/steam reforming technology for volume and weight reduction and stabilization of llrw and mixed wastes[C]//WM'00 Conference.2000.
[18]Jantzen C M.Characterization and performance of fluidized bed steam reforming(FBSR)product as a final waste form[J].Environmental Issues&Waste Management Technologies in the Ceramic&Nuclear Industries IX,2004,5:319-329.
[19]Jantzen C,Lorier T H,Pareizs J M,et al.Fluidized bed steam reformed(FBSR)mineral waste forms:characterization and durability testing[J].MRS Online Proceedings Library Archive,2007:985.
[20]Chun U K,Choi K,Yang K H,et al.Waste minimization pretreatment via pyrolysis and oxidative pyrolysis of organic ion exchange resin[J].Waste Management,1998,18(3):183-196.
[21]Matsuda M,Funabashi K,Yusa H,et al.Influence of functional sulfonic acid group on pyrolysis characteristics for cation exchange resin[J].Journal of Nuclear Science&Technology,1987,24(2):124-128.
[22]Mori K,Tamata S,Kikuchi M,et al.Method and apparatus for processing spent ion exchange resin:US4628837[P].1986-12-16.
[23]Singare P U,Lokhande R S,Madyal R S.Thermal degradation studies of some strongly acidic cation exchange resins[J].Open Journal of Physical Chemistry,2011,1(2):45-54.
[24]Matsuda M,Funabashi K,Yusa H.Effect of metallic impurities on oxidation reaction of ion exchange resin(Ⅱ)[J].Journal of Nuclear Science&Technology,1986,23(9):813-818.
[25]Matsuda M,Funabashi K,Yusa H.Effect of metallic impurities on oxidation reaction of ion exchange resin(Ⅰ)[J].Journal of Nuclear Science&Technology,1986,23(3):244-252.
[26]Juang R S,Lee T S.Oxidative pyrolysis of organic ion exchange resins in the presence of metal oxide catalysts[J].Journal of Hazardous Materials,2002,92(3):301-314.
[27]Antonetti P,Claire Y,Massit H.Pyrolysis of cobalt and caesium doped cationic ion-exchange resin[J].Journal of Analytical&Applied Pyrolysis,2000,55(1):81-92.
[28]Luca V,Bianchi H L,Manzini A C.Cation immobilization in pyrolyzed simulated spent ion exchange resins[J].Journal of Nuclear Materials,2012,424(1/2/3):1-11.
[29]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.离子交换树脂预处理方法:GB/T 5476-2013[S].北京:中国标准出版社,2013.General Administration of Quality Supervision,Inspection and Quarantine of the People.s Republic of China,Standardization Administration of the People.s Republic of China.Methods of pretreating ion exchange resins:GB/T 5476-2013[S].Beijing:Standards Press of China,2013.
[30]NIST Standard Reference Database Number 69,Sodium sulphate[DB/OL].[2019-4-12].https://webbook.nist.gov/cgi/cbook.cgi?ID=C7757826&Units=SI&Mask=80#IR-Spec
[31]Huang Y J,Wang H P,Liu S H,et al.Pyrolysis kinetics of spent low-level radioactive resin[J].Nuclear Technology,2005,138(2):355-360.
[32]陈铜,李文钊,张晋芬,等.钴基催化剂上乙烷氧化脱氢的催化作用[J].化学学报,2004,62(18):1760-1764.Chen T,Li W Z,Zhang J F,et al.Investigation of catalysis mechanism for oxidative dehydrogenation of ethane over cobaltbased catalysts[J].Acta Chimica Sinica,2004,62(18):1760-1764.
[33]陈铜,李文钊,Martin G,等.可动氧与载体对钴基催化剂的乙烷氧化脱氢性能的影响[J].催化学报,2000,21(3):204-208.Chen T,Li W Z,Martin G,et al.Effects of support and mobile oxygen species on the behavior of Co-based catalysts for oxidative dehydrogenation of ethane[J].Chinese Journal of Catalysis,2000,21(3):204-208.
[34]Triguero L,de Carolis S,Baudin M,et al.Metal oxides:O2-chemistry and dynamical effects on oxide reactivity[J].Faraday Discussions,1999,114:351-362.