Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere

doi:10.1016/j.cjche.2025.02.018

中国化学工程学报 ›› 2025, Vol. 85 ›› Issue (9): 206-216.DOI: 10.1016/j.cjche.2025.02.018

Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere

Huagui Jin¹, Xuebin An², Shizhao Wang¹, Yunshan Wang², Gang Yang², Yong Sun³

1. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China;
2. National Engineering Research Center of Green Recycling for Strategic Metal Resources, Chinese Academy of Sciences, Beijing 100190, China;
3. Department of Chemical and Environmental Engineering, University of Nottingham Ningbo China, Ningbo 315100, China

收稿日期:2024-10-30 修回日期:2025-01-15 接受日期:2025-02-20 出版日期:2025-09-28 发布日期:2025-03-17
通讯作者: Yunshan Wang,E-mail:wangys@ipe.ac.cn;Gang Yang,E-mail:yanggang@ipe.ac.cn
基金资助:
This work was funded by the National Key Research and Development Program of China (2018YFC1903500),the National Key Research and Development Program of China (2019YFC1905800), Hebei Provincial Key Research Projects (22373101D) and the commercial project by Beijing Zhong Dian Hua Yuan Environment Protection Technology Co., Ltd. (E01211200005).

Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere

Huagui Jin¹, Xuebin An², Shizhao Wang¹, Yunshan Wang², Gang Yang², Yong Sun³

1. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China;
2. National Engineering Research Center of Green Recycling for Strategic Metal Resources, Chinese Academy of Sciences, Beijing 100190, China;
3. Department of Chemical and Environmental Engineering, University of Nottingham Ningbo China, Ningbo 315100, China

Received:2024-10-30 Revised:2025-01-15 Accepted:2025-02-20 Online:2025-09-28 Published:2025-03-17
Contact: Yunshan Wang,E-mail:wangys@ipe.ac.cn;Gang Yang,E-mail:yanggang@ipe.ac.cn
Supported by:
This work was funded by the National Key Research and Development Program of China (2018YFC1903500),the National Key Research and Development Program of China (2019YFC1905800), Hebei Provincial Key Research Projects (22373101D) and the commercial project by Beijing Zhong Dian Hua Yuan Environment Protection Technology Co., Ltd. (E01211200005).

摘要/Abstract

摘要： This study investigates the removal of fluorine (F) impurities from phosphogypsum (PG) using steam as the reaction medium. The effects of the reaction atmosphere, temperature, time, and steam velocity on F impurities removal were systematically examined. The results showed that with a steam velocity of 0.0184 m·s^-1, a reaction temperature of 700 ℃, and a reaction time of 60 min, the F removal rate reached 95.87%. Further investigations into the defluorination mechanism revealed that steam and SiO₂ synergistically enhance fluoride removal, playing a crucial role in improving the defluorination efficiency. Kinetic analysis of the defluorination process, based on the shrinking core model (SCM), indicated that internal diffusion is the rate-controlling step, with the activation energy of 30.12 kJ·mol^-1. This study identifies optimal conditions for PG defluorination and proposes a defluorination mechanism, contributing to the theoretical understanding of impurity removal through the thermal treatment of PG.

关键词: Phosphogypsum, Defluorination, High-temperature hydrolysis, Steam, Silica, Kinetics

Abstract: This study investigates the removal of fluorine (F) impurities from phosphogypsum (PG) using steam as the reaction medium. The effects of the reaction atmosphere, temperature, time, and steam velocity on F impurities removal were systematically examined. The results showed that with a steam velocity of 0.0184 m·s^-1, a reaction temperature of 700 ℃, and a reaction time of 60 min, the F removal rate reached 95.87%. Further investigations into the defluorination mechanism revealed that steam and SiO₂ synergistically enhance fluoride removal, playing a crucial role in improving the defluorination efficiency. Kinetic analysis of the defluorination process, based on the shrinking core model (SCM), indicated that internal diffusion is the rate-controlling step, with the activation energy of 30.12 kJ·mol^-1. This study identifies optimal conditions for PG defluorination and proposes a defluorination mechanism, contributing to the theoretical understanding of impurity removal through the thermal treatment of PG.

Key words: Phosphogypsum, Defluorination, High-temperature hydrolysis, Steam, Silica, Kinetics

Huagui Jin, Xuebin An, Shizhao Wang, Yunshan Wang, Gang Yang, Yong Sun. Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere[J]. 中国化学工程学报, 2025, 85(9): 206-216.

Huagui Jin, Xuebin An, Shizhao Wang, Yunshan Wang, Gang Yang, Yong Sun. Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere[J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 206-216.

参考文献

[1] D. Li, J. Jiao, D. Liao, The development and thinking of phosphogypsum used in new building materials in China, New Building Materials 48 (11) (2021) 1-4+11. (in Chinese).
[2] H. Deng, S. Hou, Z. Li, G. Xu, R.a. Chi, B. Xi, Update and future of phosphogypsum reuse, Inorg Chem Industry 56 (1) (2023) 1-8+1. (in Chinese).
[3] J. Xia, Bottleneck and key technology of phosphogypsum as building material, Phos & Com Fert 35 (11) (2020) 6. (in Chinese).
[4] X. Li, X.F. Lv, L. Xiang, Review of the state of impurity occurrences and impurity removal technology in phosphogypsum, Materials 16 (16) (2023) 5630.
[5] H.T. Zhao, H.Q. Li, W.J. Bao, C.Y. Wang, S.G. Li, W.G. Lin, Spectral analysis of trace fluorine phase in phosphogypsum, Spectrosc. Spectr. Anal. 35 (8) (2015) 2333-2338.
[6] C. Li, S.Z. Wang, Y.S. Wang, X.B. An, G. Yang, Y. Sun, Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions, Chin. J. Chem. Eng. 65 (2024) 117-129.
[7] D.B. Jiang, J.H. Tan, P. Yuan, H.X. Guan, P.L. Nan, Methods of the harmless treatment of harmful components in phosphogypsum, J. Jilin Inst. Chem. Technol. 31 (1) (2014) 33-36.
[8] F. Arianpour, A.C. Arianpour, B. Aali, Characterization and properties of sodium hexa-fluorosilicate and its potential application in the production of sodium fluoride, Silicon 13 (12) (2021) 4381-4389.
[9] W.X. Cao, W. Yi, J.H. Peng, J. Li, S.H. Yin, Recycling of phosphogypsum to prepare gypsum plaster: Effect of calcination temperature, J. Build. Eng. 45 (2022) 103511.
[10] H.G. Jin, Y.X. Wang, X.B. An, S.Z. Wang, Y.S. Wang, G. Yang, L.F. Shi, Y. Sun, A review of fluoride removal from phosphorous gypsum: a quantitative analysis via a machine learning approach, Materials 17 (14) (2024) 3606.
[11] M. Zeng, Y. Ruan, J. Chen, C. Wang, B. Zhang, Z. Zhou, Effects Comparison of Different Pretreatment Methods to Phosphogypsum, The World Build Mater 32 (02) (2011) 18-21.
[12] H. Zhao, W. Bao, Z. Sun, S. Li, H. Li, W. Lin, Deep removal of impurities from phosphogypsum, Chem Indust and Eng Prog 36 (4) (2017) 1240-1246. (in Chinese).
[13] B. Ping, H. Jun-song, L. Ao-lan, G. Hong, A review on comprehensive utilization and pretreatment method of phosphogypsum, Mod Chem Indust 43 (S2) (2023) 76-79+85. (in Chinese).
[14] Z. Li, J. Chen, Q. Zhang, Z. Shen, A Study on the removal of phosphorus and fluorine impurities from phosphogypsum, Acta Minera Sinica 40 (5) (2020) 639-646. (in Chinese).
[15] M. Yang, Y. Pang, Investigation of cement retarder made of chemically pretreated phosphogypsum, J. Lanzhou Univ. Technol. 33 (6) (2007) 58-60.
[16] Y. Ennaciri, I. Zdah, H. El Alaoui-Belghiti, M. Bettach, Characterization and purification of waste phosphogypsum to make it suitable for use in the plaster and the cement industry, chem eng commun 207 (3) (2020) 382-392.
[17] L. Zou, The effect of additives on the crystallzation process of calcium sulfate, Master Thesis, Tianjin University of Science and Technology, Tianjin, 2000.
[18] Q. Fu, S. Luo, X. Ma, X. Wang, Z. Zhang, X. Wang, L. Yang, Impurities removal from phosphogypsum by leaching neutralization method, Inorg Chem Indust 47 (07) (2015) 44-47. (in Chinese).
[19] M.M. Smadi, R.H. Haddad, A.M. Akour, Potential use of phosphogypsum in concrete, Cem. Concr. Res. 29 (9) (1999) 1419-1425.
[20] T.Y. Ren, J. Zhu, W.C. Liu, X.F. Zhu, J.K. Yang, Water resistance of composite binders containing phosphogpysum with different pretreatment processes, Adv. Cem. Res. 24 (2) (2012) 111-120.
[21] F. Pan, S.G. Ma, Y. Ge, C.L. Fan, Q.S. Zhu, Fluidization thermal decomposition of sodium fluosilicate, Chin. J. Chem. Eng. 57 (2023) 329-337.
[22] V.S. Singh, S.V. Moharil, Synthesis and characterization of K2SiF6 hexafluorosilicate, IOP Conf. Ser.: Mater. Sci. Eng. 1104 (1) (2021) 012004.
[23] N. Soltani, M.I. Pech-Canul, L.A. Gonzalez, A. Bahrami, Mechanism and parameters controlling the decomposition kinetics of Na2SiF6 powder to SiF4, Int. J. Chem. Kinet. 48 (7) (2016) 379-395.
[24] R. Stodolski, L. Kolditz, Some aspects of real structure and thermal decomposition of K2SiF6, J. Fluor. Chem. 29 (1-2) (1985) 73.
[25] C. Liu, J.X. Gu, S. Zhou, B.B. Qian, B. Etschmann, J.Z. Liu, D.X. Yu, L. Zhang, Silica-assisted pyro-hydrolysis of CaCl2 waste for the recovery of hydrochloric acid (HCl): Reaction pathways with the evolution of Ca(OH)Cl intermediate by experimental investigation and DFT modelling, J. Hazard. Mater. 439 (2022) 129620.
[26] C. Liu, J. Gu, S. Zhou, B. Qian, B. Etschmann, J.Z. Liu, D. Yu, L. Zhang, Silica-assisted pyro-hydrolysis of CaCl2 waste for the recovery of hydrochloric acid (HCl): Reaction pathways with the evolution of Ca(OH)Cl intermediate by experimental investigation and DFT modelling, J. Hazard. Mater. 439 (2022) 129620.
[27] Y.J. Liu, The detemination of fluorine content in ground phosphate rock, J. Shenyang Norm. Univ. Nat. Sci. 20 (2) (2002) 124-127.
[28] Y. Kashiwaya, A.W. Cramb, Kinetics of formation and dissociation of Na2SiF6, Metall. Mater. Trans. B 33 (1) (2002) 129-136.
[29] Y. Sun, V. Sage, Z. Sun, An enhanced process of using direct fluidized bed calcination of shrimp shell for biodiesel catalyst preparation, Chem. Eng. Res. Des. 126 (2017) 142-152.
[30] Y.S. Wang, L.F. Shi, H.L. Li, Y.X. Wang, Z.Y. Wang, X.B. An, M.Z. Tang, G. Yang, J. He, J. Hu, Y. Sun, Clean process to utilize the potassium-containing phosphorous rock with simultaneous HCl and KCl production via the steam-mediated reactions, ACS Omega 7 (28) (2022) 24561-24573.
[31] Q. Qi, J. Liu, X. Cao, J. Zhou, S. Zhang, K. Cen, Stability of CaF2 at High Temperature, Envir Sci 23 (03) (2002) 111-114. (in Chinese).
[32] D.L. Deadmore, J.S. Machin, A.W. Allen, Stability of inorganic fluorine-bearing compounds: I, binary metallic fluorides, J. Am. Ceram. Soc. 44 (3) (1961) 105-109.
[33] D.L. Deadmore, J.S. Machin, A.W. Allen, Stability of inorganic fluorine-bearing compounds: II, complex fluorides, J. Am. Ceram. Soc. 45 (3) (1962) 120-122.
[34] M. Kanezashi, T. Matsutani, H. Nagasawa, T. Tsuru, Fluorine-induced microporous silica membranes: Dramatic improvement in hydrothermal stability and pore size controllability for highly permeable propylene/propane separation, J. Membr. Sci. 549 (2018) 111-119.
[35] F.L. Liu, Y.Y. Chen, B. Milicevic, C.Y. Jiang, S.C. Huang, L. Zhou, J.B. Zhou, M.M. Wu, Hydroquinone-modified Mn4+-activated fluoride red phosphors with improved water-resistance, Colloids Surf. A Physicochem. Eng. Aspects 661 (2023) 130954.
[36] J. Yeon, Development of a reaxff reactive force field for silicon/ oxygen/ hydrogen/ fluoride interactions and applications to hydroxylation and friction, Ph. D. Thesis, The Pennsylvania State Univ., USA, 2016.
[37] Y. Xia, J. Li, Y.Z. Zhang, Y.G. Yin, B.L. Chen, Y. Liang, G.B. Jiang, R.N. Zare, Contact between water vapor and silicate surface causes abiotic formation of reactive oxygen species in an anoxic atmosphere, Proc. Natl. Acad. Sci. USA 120 (30) (2023) e2302014120.

Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere

Study of defluorination by thermal treatment of phosphogypsum under steam atmosphere

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Yongbin Shen, Qihe Ma, Hua Yuan, Chuang Liu, Likun Yang, Hao Huang, Bowen Shi, Zhenhua Li, Shunyu Liang, Hu Li, Zhengping Dong. Selective catalytic deoxygenation of 1-octanol from Fischer-Tropsch C10 mixed oil[J]. 中国化学工程学报, 2025, 85(9): 270-279.
[2]	Zhe Wang, Zhengpeng Zhu, Kai Xue, Xingmei Guo, Yuanjun Liu, Xiangjun Zheng, Qianqian Fan, Zhongyao Duan, Qinghong Kong, Junhao Zhang. Fabrication of Sb-based alloys/carbon nanofibers with uniform dispersion as anode material for high efficiency sodium storage[J]. 中国化学工程学报, 2025, 83(7): 208-216.
[3]	Yilun Dong, Kang Xue, Zexing He, Chongjun Li, Ruijie Gao, Zhenfeng Huang, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Jijun Zou. Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions[J]. 中国化学工程学报, 2025, 83(7): 217-228.
[4]	Baoliang Xia, Lirui Mao, Hanxu Li, Chengli Wu, Facun Jiao. Method and theory for optimising ash-fusion characteristics in high-aluminium coal ash via coal blending technology[J]. 中国化学工程学报, 2025, 83(7): 254-265.
[5]	Xintuo Chen, Wencong Chen, Yu Zhou, Liangliang Zhang, Jianfeng Chen. Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene[J]. 中国化学工程学报, 2025, 83(7): 286-297.
[6]	Siwen Huang, Kui Wang, Haibo Wang, Li Lv, Tao Zhang, Wenxiang Tang, Zongpeng Zou, Shengwei Tang. Comprehensive utilization of titanium-bearing blast furnace slag by H₂SO₄ roasting and stepwise precipitation[J]. 中国化学工程学报, 2025, 80(4): 24-37.
[7]	Zhengyang Liu, Xianlong Liu, Shuang Ma, Xiaolei Guo, Minhua Ai, Chengxiang Shi, Zhenfeng Huang, Xiangwen Zhang, Jijun Zou, Lun Pan. One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene[J]. 中国化学工程学报, 2025, 80(4): 61-69.
[8]	Yaqi Qu, Hualiang An, Xinqiang Zhao, Yanji Wang. Heterogeneously catalyzed self-condensation of n-butanal[J]. 中国化学工程学报, 2025, 80(4): 89-99.
[9]	Ting Pu, Junning Lu, Zhirui Liu, Xingxing Zeng, Baoyu Liu. Alkylation of benzene and 1-dodecene over cerium-silicate pillared MWW zeolite[J]. 中国化学工程学报, 2025, 80(4): 110-118.
[10]	Wei Zhang, Yuming Zhang, Haixin Wu, Xinyu Yang, Pei Qiao, Jiazhou Li, Zhewen Chen, Yan Wang. Investigation on the pyrolysis behaviors and kinetics of walnut shell lignocellulosic biomass with additives[J]. 中国化学工程学报, 2025, 80(4): 303-314.
[11]	Aleksey K. Sagidullin, Sergey S. Skiba, Tatyana P. Adamova, Andrey Y. Manakov. Investigation of the formation processes of CO₂ hydrate films on the interface of liquid carbon dioxide with humic acids solutions[J]. 中国化学工程学报, 2025, 79(3): 53-61.
[12]	Pengxing Yuan, Meng Li, Shiyi Chen, Wenguo Xiang. Thermodynamic properties and reaction mechanism of coal reductive decomposition phosphogypsum to prepare CaO and SO₂[J]. 中国化学工程学报, 2025, 79(3): 135-144.
[13]	Yiyang Qiu, Chong Liu, Xueting Meng, Yuesen Liu, Jiangtao Fan, Guojun Lan, Ying Li. Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination[J]. 中国化学工程学报, 2025, 79(3): 145-154.
[14]	Feng Gao, Sixiao Zhu, Liping Chang, Weiren Bao, Jinghong Ma, Junjie Liao. Kinetics of hydrogen sulfide removal from coke oven gas over faujasite zeolite: Experimental and modeling studies[J]. 中国化学工程学报, 2025, 78(2): 232-244.
[15]	Lejun Wu, Jingbo Gao, Jing Li, Haibo Liu, Qiang Sun. The investigation of Gemini surfactant effects on CH₄ and CO₂ hydrates[J]. 中国化学工程学报, 2025, 77(1): 167-174.