Study on the autocatalytic mechanism of mixed resins in Na2CO3-K2CO3 melt

doi:10.1016/j.cjche.2025.06.037

中国化学工程学报 ›› 2025, Vol. 88 ›› Issue (12): 359-366.DOI: 10.1016/j.cjche.2025.06.037

Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt

Yue-Lin Wang^1,2, Yang-Hai Zheng¹, Sheng-Rong Guo¹, Peng Huang¹, Yun-Xue She¹, Yun Xue², Yong-De Yan²

1. College of Ecology, Lishui University, Lishui 323000, China;
2. Yantai Research Institute & Graduate School, Harbin Engineering University, Yantai 264006, China

收稿日期:2025-03-04 修回日期:2025-06-06 接受日期:2025-06-11 出版日期:2026-02-09 发布日期:2025-09-25
通讯作者: Yang-Hai Zheng,E-mail:zhengyanghai@hrbeu.edu.cn,y5d2006@hrbeu.edu.cn
基金资助:
This work was financially supported by the National Natural Science Foundation of China (22176045 and 21976047), the Natural Science Foundation of Zhejiang Province China (LY19B020001 and LSQN25E030004), the Lishui Industrial Team Dispatch Project (2023GYTPT03).

Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt

Yue-Lin Wang^1,2, Yang-Hai Zheng¹, Sheng-Rong Guo¹, Peng Huang¹, Yun-Xue She¹, Yun Xue², Yong-De Yan²

1. College of Ecology, Lishui University, Lishui 323000, China;
2. Yantai Research Institute & Graduate School, Harbin Engineering University, Yantai 264006, China

Received:2025-03-04 Revised:2025-06-06 Accepted:2025-06-11 Online:2026-02-09 Published:2025-09-25
Contact: Yang-Hai Zheng,E-mail:zhengyanghai@hrbeu.edu.cn,y5d2006@hrbeu.edu.cn
Supported by:
This work was financially supported by the National Natural Science Foundation of China (22176045 and 21976047), the Natural Science Foundation of Zhejiang Province China (LY19B020001 and LSQN25E030004), the Lishui Industrial Team Dispatch Project (2023GYTPT03).

摘要/Abstract

摘要： Thousands of radioactive mixed resins (MR) generated from nuclear industry can be processed by molten salt oxidation. There are three stages during the MSO process of MR: (1) the evaporation process (25-200 ℃); the thermal decomposition of the functional groups (200-450 ℃); (3) the depolymerization of styrene-divinylbenzene (450-800 ℃). Moreover, the thermal decomposition of the functional groups can be further divided into the thermal decomposition of the quaternary ammonium group (200-300 ℃) and the spitting off of the sulfonic acid group (300-450 ℃). NO and SO₂, respectively, were produced by the destruction of these functional groups. The carbonate salt can effectively adsorb NO and SO₂, whose contents decrease from 17.72% to 3.32% to 2.08% and 1.45%. Moreover, the sulfate contents in molten salt can be promoted by the generation of nitrate, which increase from 12.87% to 25.44% at 500 ℃. The change of the standard Gibbs free energy (ΔG_m^θ) of the reactions about the generations of nitrate and sulfur species, and the reactions between the nitrate and sulfur species were also proved by the calculation results of HSC chemistry 6.0. Both experimental and calculated results support the finding that the generation of nitrate from MR can catalyze the further oxidation of residue.

关键词: Molten salt oxidation, Mixed resins, Na₂CO₃-K₂CO₃ melt, Sulfonic acid group, Quaternary ammonium group

Abstract: Thousands of radioactive mixed resins (MR) generated from nuclear industry can be processed by molten salt oxidation. There are three stages during the MSO process of MR: (1) the evaporation process (25-200 ℃); the thermal decomposition of the functional groups (200-450 ℃); (3) the depolymerization of styrene-divinylbenzene (450-800 ℃). Moreover, the thermal decomposition of the functional groups can be further divided into the thermal decomposition of the quaternary ammonium group (200-300 ℃) and the spitting off of the sulfonic acid group (300-450 ℃). NO and SO₂, respectively, were produced by the destruction of these functional groups. The carbonate salt can effectively adsorb NO and SO₂, whose contents decrease from 17.72% to 3.32% to 2.08% and 1.45%. Moreover, the sulfate contents in molten salt can be promoted by the generation of nitrate, which increase from 12.87% to 25.44% at 500 ℃. The change of the standard Gibbs free energy (ΔG_m^θ) of the reactions about the generations of nitrate and sulfur species, and the reactions between the nitrate and sulfur species were also proved by the calculation results of HSC chemistry 6.0. Both experimental and calculated results support the finding that the generation of nitrate from MR can catalyze the further oxidation of residue.

Key words: Molten salt oxidation, Mixed resins, Na₂CO₃-K₂CO₃ melt, Sulfonic acid group, Quaternary ammonium group

Yue-Lin Wang, Yang-Hai Zheng, Sheng-Rong Guo, Peng Huang, Yun-Xue She, Yun Xue, Yong-De Yan. Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt[J]. 中国化学工程学报, 2025, 88(12): 359-366.

Yue-Lin Wang, Yang-Hai Zheng, Sheng-Rong Guo, Peng Huang, Yun-Xue She, Yun Xue, Yong-De Yan. Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt[J]. Chinese Journal of Chemical Engineering, 2025, 88(12): 359-366.

参考文献

[1] J.L. Wang, Z. Wan, Treatment and disposal of spent radioactive ion-exchange resins produced in the nuclear industry, Prog. Nucl. Energy 78 (2015) 47-55.
[2] P. Antonetti, Y. Claire, H. Massit, P. Lessart, C. Pham Van Cang, A. Perichaud, Pyrolysis of cobalt and caesium doped cationic ion-exchange resin, J. Anal. Appl. Pyrolysis 55 (1) (2000) 81-92.
[3] C. A. Cicero-Herman, P. Workman, K. Poole, D. Erich, J. Harden, Commercial Ion Exchange Resin Vitrification in Borosilicate Glass, Office of Scientific & Technical Information Technical Reports, 1998, doi: 10.2172/594501.
[4] Na Li, Xinyu Yan, Yifang Song, Wei Wang, Ping Jiang, Xianwen Huang, Guoxiong Mei, Experimental study on small strain dynamic characteristics of citric acid modified magnesium oxysulfate cement solidified engineering waste soil, Results in Engineering, Volume 27, 2025, 106633.
[5] Q.N. Sun, J.L. Wang, Cementation of radioactive borate liquid waste produced in pressurized water reactors, Nucl. Eng. Des. 240 (10) (2010) 3660-3664.
[6] Xiaosong Huang, Rongjun Zhang, Ziheng Wu, Junjie Zheng, Honglei Sun, Sijie Liu, Dongrui Liu, Comparison between physicochemical combined method and conventional cement solidification method for treating heavy metal-contaminated slurry-like mud, Journal of Cleaner Production, Volume 523, 2025,146460.
[7] I. Plecas, A. Peric, S. Glodic, A. Kostadinovic, Comparative leaching studies of 60CO from spent radioactive ion: Exchange resin incorporated in cement, Cem. Concr. Res. 25 (2) (1995) 314-318.
[8] Q.N. Sun, J. Hu, J.L. Wang, Optimization of composite admixtures used in cementation formula for radioactive evaporator concentrates, Prog. Nucl. Energy 70 (2014) 1-5.
[9] Q.N. Sun, J.F. Li, J.L. Wang, Effect of borate concentration on solidification of radioactive wastes by different cements, Nucl. Eng. Des. 241 (10) (2011) 4341-4345.
[10] Q.N. Sun, J.F. Li, J.L. Wang, Solidification of borate radioactive resins using sulfoaluminate cement blending with zeolite, Nucl. Eng. Des. 241 (12) (2011) 5308-5315.
[11] N. Moriyama, S. Dojiri, S. Emura, T. Sugo, S. Machi, Incorporation of radioactive spent ion exchange resins in plastics, J. Nucl. Sci. Technol. 12 (6) (1975) 362-369.
[12] J.F. Li, J.L. Wang, Advances in cement solidification technology for waste radioactive ion exchange resins: a review, J. Hazard. Mater. 135 (1-3) (2006) 443-448.
[13] C.J. Ren, P. Zhang, Q. Song, Z.L. Huang, Y. Yang, Y.R. Yang, Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin, Chin. J. Chem. Eng. 67 (2024) 135-147.
[14] P. Bingham, N. Hyatt, R. Hand, Vitrification of UK intermediate level radioactive wastes arising from site decommissioning: property modelling and selection of candidate host glass compositions, Glass Technol.: Eur. J. Glass Sci. Technol. Part A 53 (2012) 83-100.
[15] M.J. Quina, J.C.M. Bordado, R.M. Quinta-Ferreira, Chemical stabilization of air pollution control residues from municipal solid waste incineration, J. Hazard. Mater. 179 (1-3) (2010) 382-392.
[16] S. Pettersson, G. Kemmler, Experience of resin pyrolysis, Waste Manage 84 (1984) 223.
[17] A. Koolivand, H. Mazandaranizadeh, M. Binavapoor, A. Mohammadtaheri, R. Saeedi, Hazardous and industrial waste composition and associated management activities in Caspian industrial park, Iran, Environ. Nanotechnol. Monit. Manag. 7 (2017) 9-14.
[18] V. Luca, H.L. Bianchi, A.C. Manzini, Cation immobilization in pyrolyzed simulated spent ion exchange resins, J. Nucl. Mater. 424 (1-3) (2012) 1-11.
[19] M. Matsuda, K. Funabashi, H. Yusa, M. Kikuchi, Influence of functional sulfonic acid group on pyrolysis characteristics for cation exchange resin, J. Nucl. Sci. Technol. 24 (2) (1987) 124-128.
[20] D.L. Mauzerall, B. Sultan, N. Kim, D.F. Bradford, NOx emissions from large point sources: variability in ozone production, resulting health damages and economic costs, Atmos. Environ. 39 (16) (2005) 2851-2866.
[21] K. Kinoshita, M. Hirata, T. Yahata, Overall reaction rate analysis of ion-exchange resins incineration by fluidized bed, J. Nucl. Sci. Technol. 28 (8) (1991) 739-747.
[22] E. Desroches-Ducarne, E. Marty, G. Martin, L. Delfosse, Co-combustion of coal and municipal solid waste in a circulating fluidized bed, Fuel 77 (12) (1998) 1311-1315.
[23] C.Q. Dong, B.S. Jin, Z.P. Zhong, J.X. Lan, Tests on co-firing of municipal solid waste and coal in a circulating fluidized bed, Energy Convers. Manag. 43 (16) (2002) 2189-2199.
[24] J.C. Hu, M.H. Zheng, W.B. Liu, C.L. Li, Z.Q. Nie, G.R. Liu, B. Zhang, K. Xiao, L.R. Gao, Characterization of polychlorinated naphthalenes in stack gas emissions from waste incinerators, Environ. Sci. Pollut. Res. Int. 20 (5) (2013) 2905-2911.
[25] Huihuang Zou, Pinjing He, Fan Lu, Hua Zhang,Practice and challenges for beneficial use of municipal solid waste incineration bottom ash in China,Journal of Environmental Chemical Engineering,Volume 13, Issue 5,2025,117923.
[26] M. Takaoka, P.Y. Liao, N. Takeda, T. Fujiwara, K. Oshita, The behavior of PCDD/Fs, PCBs, chlorobenzenes and chlorophenols in wet scrubbing system of municipal solid waste incinerator, Chemosphere 53 (2) (2003) 153-161.
[27] M.X. Zhan, J.Y. Fu, T. Chen, Y.Q. Li, J. Zhang, X.D. Li, J.H. Yan, A. Buekens, Effects of bypass system on PCDD/F emission and chlorine circulation in cement kilns, Environ. Sci. Pollut. Res. 23 (19) (2016) 19657-19666.
[28] F. N. Rubel, Incineration of Solid Wastes, Noyes Data Corporation, Park Ridge, New Jersey, 1974.
[29] Long,. Jin, Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application, crit rev environ sci technol 42 (3) (2012) 251-325.
[30] Z. Wan, L.J. Xu, J.L. Wang, Disintegration and dissolution of spent radioactive cationic exchange resins using Fenton-like oxidation process, Nucl. Eng. Des. 291 (2015) 101-108.
[31] X.C. Jian, T.B. Wu, G.C. Yun, A study of wet catalytic oxidation of radioactive spent ion exchange resin by hydrogen peroxide, Nucl. Saf., (1996).
[32] J.F. Li, G. Zhao, J.L. Wang, Solidification of low-level-radioactive resins in ASC-zeolite blends, Nucl. Eng. Des. 235 (7) (2005) 817-820.
[33] M. Zahorodna, E. Oliveros, M. Worner, R. Bogoczek, A.M. Braun, Dissolution and mineralization of ion exchange resins: differentiation between heterogeneous and homogeneous (photo-) Fenton processes, Photochem. Photobiol. Sci. 7 (12) (2008) 1480-1492.
[34] A. Akelah, D.C. Sherrington, Application of functionalized polymers in organic synthesis, Chem. Rev. 81 (6) (1981) 557-587.
[35] H.C. Yang, Y.J. Cho, H.C. Eun, E.H. Kim, Destruction of chlorobenzene and carbon tetrachloride in a two-stage molten salt oxidation reactor system, Chemosphere 73 (1) (2008) S311-S315.
[36] J. D. Navratil, A.E. Steward, Waste treatment using molten salt oxidation, Nukleonika 41 (1996) 57-71.
[37] P. C. Hsu, D.L. Hipple, K.G. Foster, T.D. Ford, R.W. Hopper, M.G. Adamson, Molten Salt Oxidation for Treating Low-level Mixed Wastes, Lawrence Livermore National Laboratory, Livermore, CA. 1998.
[38] V. Galek, J. Stoklasa, J. Hadrava, R.Vokaty, Flame-free combustion of radioactive and hazardous wastes in the salt melt, J. Nucl. Eng. Radiat. Sci. 6 (4) (2020) 041305.
[39] H.C. Yang, J.S. Yun, M.J. Kang, J.H. Kim, Y. Kang, Mechanisms and kinetics of cadmium and lead capture by calcined Kaolin at high temperatures, Korean J. Chem. Eng. 18 (4) (2001) 499-505.
[40] H.C. Yang, M.W. Lee, I.H. Yoon, D.Y. Chung, J.K. Moon, Scale-up and optimization of a two-stage molten salt oxidation reactor system for the treatment of cation exchange resins, Chem. Eng. Res. Des. 91 (4) (2013) 703-712.
[41] U.K. Chun, K. Choi, K.H. Yang, J.K. Park, M.J. Song, Waste minimization pretreatment via pyrolysis and oxidative pyroylsis of organic ion exchange resin, Waste Manag. 18 (3) (1998) 183-196.
[42] M. Matsuda, K. Funabashi, T. Nishi, H. Yusa, M. Kikuchi, Decomposition of ion exchange resins by pyrolysis, nucl technol 75 (2) (1986) 187-192.
[43] M.A. Dubois, J.F. Dozol, C. Nicotra, J. Serose, C. Massiani, Pyrolysis and incineration of cationic and anionic ion-exchange resins: Identification of volatile degradation compounds, J. Anal. Appl. Pyrolysis 31 (1995) 129-140.
[44] H.C. Yang, M.W. Lee, H.S. Hwang, J.K. Moon, D.Y. Chung, Study on thermal decomposition and oxidation kinetics of cation exchange resins using non-isothermal TG analysis, J. Therm. Anal. Calorim. 118 (2) (2014) 1073-1083.
[45] J. Jordan, W. B. McCarthy, P. G. Zambonin, Thermochemistry, complexationm, electron and oxygen transfer in fused nitrates, in Molten Salts: Characterisation and Analysis, ed. G Mamantov, Marcel Dekker, N. Y., (1969) 575-592.

Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt

Study on the autocatalytic mechanism of mixed resins in Na₂CO₃-K₂CO₃ melt

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