Research Status of Phosphogypsum Pyrolysis

Abstract

Abstract: Pyrolysis is the key of resource utilization of phosphogypsum. However, in the absence of reducing agents and catalysts, the disadvantages of phosphogypsum utilization include high energy consumption, high cost and low decomposition rate. Therefore, it is an important challenge to find the reducing agents and catalysts which can reduce the decomposition temperature of phosphogypsum and improve the decomposition rate. In this paper, the research status of the pyrolysis process of phosphogypsum was reviewed in the presence of reducing agents and catalysts. Traditional fuel-based reducing agents, e.g. CO and coke, have more advantages in practical application, which can effectively reduce the initial decomposition temperature of phosphogypsum and improve the decomposition efficiency. The addition of non-traditional reducing agents (sulfur, H₂S) and catalysts can not only reduce the cost of phosphogypsum pyrolysis, but also reduce the emission of greenhouse gas CO₂ during the pyrolysis of phosphogypsum. However, this method is still in the experimental research. Searching for suitable reducing agents and catalysts with higher decomposition efficiency and lower energy consumption and cost in the pyrolysis process is crucial for achieving green, low-carbon and efficient resource utilization of phosphogypsum.

Key words: phosphogypsum, pyrolysis, resource utilization, reducing atmosphere, reducing agent, catalyst

CLC Number:

X705

WU Yonglin, ZHANG Wei, DIAN Bo, CHEN Jianjun. Research Status of Phosphogypsum Pyrolysis[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(9): 3129-3137.

References

[1] WU F H, ZHAO C Y, QU G F, et al. A critical review of the typical by-product clean ecology links in the Chinese phosphorus chemical industry in China: production technologies, fates and future directions[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 106685.
[2] 朱志伟,何东升,陈飞,等.磷石膏预处理与综合利用研究进展[J].矿产保护与利用,2019,39(4):19-25.
ZHU Z W, HE D S, CHEN F, et al. Research progress on pretreatment and comprehensive utilization of phosphogypsum[J]. Conservation and Utilization of Mineral Resources, 2019, 39(4): 19-25 (in Chinese).
[3] LACHEHAB A, MERTAH O, KHERBECHE A, et al. Utilization of phosphogypsum in CO₂ mineral sequestration by producing potassium sulphate and calcium carbonate[J]. Materials Science for Energy Technologies, 2020, 3: 611-625.
[4] ENNACIRI Y, BETTACH M. Procedure to convert phosphogypsum waste into valuable products[J]. Materials and Manufacturing Processes, 2018, 33(16): 1727-1733.
[5] WANG J M, DONG F Q, WANG Z J, et al. A novel method for purification of phosphogypsum[J]. Physicochemical Problems of Mineral Processing, 2020, 56(5): 975-983.
[6] CHERNYSH Y, PLYATSUK L. Environmentally friendly concept of phosphogypsum recycling on the basis of the biotechnological approach[M]. International business, Trade and Institutional Sustainability, 2020: 167-182.
[7] ZHOU Z, LU Y C, ZHAN W, et al. Four stage precipitation for efficient recovery of N, P, and F elements from leachate of waste phosphogypsum[J]. Minerals Engineering, 2022, 178: 107420.
[8] 白海丹.2019年我国磷石膏利用现状、问题及建议[J].硫酸工业,2020(12):7-10.
BAI H D. Current situation, problems and suggestions of phosphogypsum utilization of 2019 in China[J]. Sulphuric Acid Industry, 2020(12): 7-10 (in Chinese).
[9] BENSALAH H, BEKHEET M F, ALAMI YOUNSSI S, et al. Hydrothermal synthesis of nanocrystalline hydroxyapatite from phosphogypsum waste[J]. Journal of Environmental Chemical Engineering, 2018, 6(1): 1347-1352.
[10] CAI Q, JIANG J, MA B, et al. Efficient removal of phosphate impurities in waste phosphogypsum for the production of cement[J]. Science of the Total Environment, 2021, 780: 146600.
[11] LU W D, MA B G, SU Y, et al. Preparation of α-hemihydrate gypsum from phosphogypsum in recycling CaCl₂ solution[J]. Construction and Building Materials, 2019, 214: 399-412.
[12] ZHOU J, LI X Q, ZHAO Y, et al. Preparation of paper-free and fiber-free plasterboard with high strength using phosphogypsum[J]. Construction and Building Materials, 2020, 243: 118091.
[13] WU S, YAO Y G, YAO X L, et al. Co-preparation of calcium sulfoaluminate cement and sulfuric acid through mass utilization of industrial by-product gypsum[J]. Journal of Cleaner Production, 2020, 265: 121801.
[14] 刘琦,敖先权,陈前林,等.磷石膏高温还原分解体系研究进展[J].磷肥与复肥,2021,36(6):25-29.
LIU Q, AO X Q, CHEN Q L, et al. Progression in high-temperature reduction and decomposition system of PG[J]. Phosphate & Compound Fertilizer, 2021, 36(6): 25-29 (in Chinese).
[15] MA L P, DU Y L, NIU X K, et al. Thermal and kinetic analysis of the process of thermochemical decomposition of phosphogypsum with CO and additives[J]. Industrial & Engineering Chemistry Research, 2012, 51(19): 6680-6685.
[16] MSILA X, BARNARD W, BILLING D G. Raman spectroscopic study of phosphogypsum thermal reduction with the carbonaceous material[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2015, 149: 317-322.
[17] ANTAR K, JEMAL M. A thermogravimetric study into the effects of additives and water vapor on the reduction of gypsum and Tunisian phosphogypsum with graphite or coke in a nitrogen atmosphere[J]. Journal of Thermal Analysis and Calorimetry, 2018, 132(1): 113-125.
[18] 肖海平,周俊虎,曹欣玉,等.CaSO₄在不同气氛下分解特性的实验研究[J].动力工程,2004,24(6):889-892.
XIAO H P, ZHOU J H, CAO X Y, et al. Experimental study of decomosition behavior of CaSO₄ in different atmospheres[J]. Power Engineering, 2004, 24(6): 889-892 (in Chinese).
[19] ZHANG X M, SONG X F, SUN Z, et al. Density functional theory study on the mechanism of calcium sulfate reductive decomposition by carbon monoxide[J]. Industrial & Engineering Chemistry Research, 2012, 51(18): 6563-6570.
[20] 郑绍聪,宁平,马丽萍,等.磷石膏在CO气氛下的热分解动力学[J].武汉理工大学学报,2010,32(18):66-69.
ZHENG S C, NING P, MA L P, et al. Kinetics for thermal decomposition of phosphogypsum in CO atmosphere[J]. Journal of Wuhan University of Technology, 2010, 32(18): 66-69 (in Chinese).
[21] 朱凯,解桂林,陈昭睿,等.磷石膏在一氧化碳气氛下的还原反应特性[J].硅酸盐学报,2013,41(11):1540-1545.
ZHU K, XIE G L, CHEN Z R, et al. Reaction characteristics of phosphogypsum under carbon monoxide atmosphere[J]. Journal of the Chinese Ceramic Society, 2013, 41(11): 1540-1545 (in Chinese).
[22] YAN X D, MA L P, ZHU B, et al. Reaction mechanism process analysis with phosphogypsum decomposition in multiatmosphere control[J]. Industrial & Engineering Chemistry Research, 2014, 53(50): 19453-19459.
[23] ZHENG D L, MA L P, WANG R M, et al. Decomposing properties of phosphogypsum with iron addition under two-step cycle multi-atmosphere control in fluidised bed[J]. Waste Management & Research: the Journal of the International Solid Wastes and Public Cleansing Association, ISWA, 2018, 36(2): 183-193.
[24] NING P, ZHENG S C, MA L P, et al. Kinetics and thermodynamics studies on the decompositions of phosphogypsum in different atmospheres[J]. Advanced Materials Research, 2010, 160/161/162: 842-848.
[25] XIA X, ZHANG L Q, LI Z Y, et al. Recovery of CaO from CaSO₄ via CO reduction decomposition under different atmospheres[J]. Journal of Environmental Management, 2022, 301: 113855.
[26] 连艳,马丽萍,刘红盼,等.磷石膏与硫化氢气体反应制硫化钙的实验研究[J].化学工程,2016,44(8):48-52.
LIAN Y, MA L P, LIU H P, et al. Experimental study on preparation of calcium sulfide via phosphogypsum and hydrogen sulfide reaction[J]. Chemical Engineering (China), 2016, 44(8): 48-52 (in Chinese).
[27] 周龙,马华菊,杨杰,等.H₂S气氛中LaCl₃催化磷石膏低温分解制CaS研究[J].化工技术与开发,2018,47(3):51-54.
ZHOU L, MA H J, YANG J, et al. Preparation of CaS via phosphogypsum and H₂S reaction with catalyst of LaCl₃[J]. Technology & Development of Chemical Industry, 2018, 47(3): 51-54 (in Chinese).
[28] 舒艺周.磷石膏碳热分解性能及工艺研究[D].昆明:昆明理工大学,2010.
SHU Y Z. Research on the performance and process of carbon thermal decomposition of phosphogypsum[D]. Kunming: Kunming University of Science and Technology, 2010 (in Chinese).
[29] 任雪娇,夏举佩,张召述.磷石膏还原分解反应热力学分析[J].环境工程学报,2013,7(3):1128-1132.
REN X J, XIA J P, ZHANG Z S. Thermodynamic analysis of reductive decomposition for phosphogypsum[J]. Chinese Journal of Environmental Engineering, 2013, 7(3): 1128-1132 (in Chinese).
[30] JIA X, WANG Q H, CEN K F, et al. An experimental study of CaSO₄ decomposition during coal pyrolysis[J]. Fuel, 2016, 163: 157-165.
[31] LV Q Q, TIAN Y S, ZHOU J L, et al. A comprehensive investigation of the reaction behaviorial features of coke with different CRIs in the simulated cohesive zone of a blast furnace[J]. PloS One, 2021, 16(1): e0245124.
[32] 李建锡,余苏,马丽萍,等.磷石膏预分解的热分析研究[J].环境工程学报,2009,3(10):1861-1864.
LI J X, YU S, MA L P, et al. Thermal analysis of phosphogypsum decomposition[J]. Chinese Journal of Environmental Engineering, 2009, 3(10): 1861-1864 (in Chinese).
[33] ZHENG S C, CHENG F X, WANG Z J. Production of SO₂ and lime from phosphogypsum reduced with lignite in a nitrogen atmosphere[J]. Advanced Materials Research, 2013, 803: 94-98.
[34] 郑绍聪,宁平,马丽萍,等.高硫煤还原磷石膏制SO₂[J].化学工程,2010,38(8):35-38.
ZHENG S C, NING P, MA L P, et al. Reduction of phosphogypsum to sulfur dioxide with high sulfur coal[J]. Chemical Engineering (China), 2010, 38(8): 35-38 (in Chinese).
[35] 郑绍聪,宁平,汪帆,等.磷石膏热分解制备二氧化硫和氧化钙研究[J].无机盐工业,2013,45(9):45-47.
ZHENG S C, NING P, WANG F, et al. Study on preparation of sulfur dioxide and lime by thermal decomposition of phosphogypsum[J]. Inorganic Chemicals Industry, 2013, 45(9): 45-47 (in Chinese).
[36] 万甜明,张志业,王辛龙,等.磷石膏和硫化钙反应过程的熔融特性研究[J].现代化工,2011,31(12):63-67.
WAN T M, ZHANG Z Y, WANG X L, et al. Research on the melting characteristics during the reaction process of phosphogypsum and calcium sulfide[J]. Modern Chemical Industry, 2011, 31(12): 63-67 (in Chinese).
[37] 杨校铃,刘荆风,王辛龙,等.硫磺分解磷石膏制硫化钙工艺研究[J].无机盐工业,2015,47(3):45-48.
YANG X L, LIU J F, WANG X L, et al. Study on preparation of calcium sulfide by using sulphur to reduce phosphogypsum[J]. Inorganic Chemicals Industry, 2015, 47(3): 45-48 (in Chinese).
[38] 王辛龙,张志业,杨守明,等.硫黄分解磷石膏制硫酸关键技术及工程进展[J].磷肥与复肥,2017,32(12):24-28.
WANG X L, ZHANG Z Y, YANG S M, et al. Technology and engineering progress of sulfuric acid production by phosphogypsum decomposition with sulfur[J]. Phosphate & Compound Fertilizer, 2017, 32(12): 24-28 (in Chinese).
[39] YANG X S, ZHANG Z Y, WANG X L, et al. Thermodynamic study of phosphogypsum decomposition by sulfur[J]. The Journal of Chemical Thermodynamics, 2013, 57: 39-45.
[40] LIU S G, WANG J, XIE R S, et al. Phosphogypsum pyrolysis by adding mineralization agent: process and mechanism[J]. Journal of Donghua University (English Edition), 2018, 35(1): 47-51.
[41] FANG R, TAN H, MAO W, et al. Influence of carbon and additives on the high-temperature decomposition behavior of phosphogypsum[J]. Materiali in Tehnologije, 2020, 54(6): 861-865.
[42] YAN B, MA L P, XIE L G, et al. Reaction mechanism for iron catalyst in the process of phosphogypsum decomposition[J]. Industrial & Engineering Chemistry Research, 2013, 52(49): 17383-17389.
[43] YANG C Y, WEI Y, YE F B, et al. Effect of additives on thermal decomposition of phosphogypsum[J]. Advanced Materials Research, 2011, 415/416/417: 735-740.
[44] YANG C Q, XIA J P. Study on the carbon-thermal reaction mechanism of potassium feldspar and phosphogypsum[J]. Advanced Materials Research, 2014, 1073/1074/1075/1076: 308-313.
[45] 谢容生,刘树根,宁平,等.CaF₂作用下磷石膏还原分解过程的动力学特性[J].硅酸盐通报,2016,35(8):2604-2610.
XIE R S, LIU S G, NING P, et al. Kinetic characteristics of phosphogypsum reductive decomposition with mineralization agent CaF₂[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(8): 2604-2610 (in Chinese).
[46] FENG H, XIE R S. Phosphogypsum pyrolysis with mineralization agent under weak reducing atmosphere[J]. IOP Conference Series: Earth and Environmental Science, 2019, 295(5): 052030.
[47] YAN B, MA L P, MA J, et al. Mechanism analysis of Ca, S transformation in phosphogypsum decomposition with Fe catalyst[J]. Industrial & Engineering Chemistry Research, 2014, 53(18): 7648-7654.
[48] DI Z C, YANG F L, CAO Y, et al. The transformation pathways on the catalytic and stability-promoted CaSO₄ reduction in CLC process using Fe₂O₃ supported[J]. Fuel, 2019, 253: 327-338.
[49] ZHENG D L, MA L P, WANG R M, et al. Research on thermal decomposing properties of phosphogypsum with Fe addition under multi-atmosphere control[J]. Thermochimica Acta, 2018, 661: 59-66.
[50] YAN Z Q, WANG Z A, LIU H, et al. Decomposition and solid reactions of calcium sulfate doped with SiO₂, Fe₂O₃ and Al₂O₃[J]. Journal of Analytical and Applied Pyrolysis, 2015, 113: 491-498.
[51] YANG J, ZHU B, MA L P, et al. Investigation of Al₂O₃ and Fe₂O₃ transmission and transformation during the decomposition of phosphogypsum[J]. Chinese Journal of Chemical Engineering, 2019, 27(5): 1125-1131.
[52] SHI T, WAN T M, ZHANG Z Y, et al. Effect of SiO₂ on the melting characteristics of reaction between phosphogypsum and calcium sulfide[J]. Journal of Thermal Analysis and Calorimetry, 2016, 123(2): 1601-1609.
[53] LU D H, CHEN Q L, LI C Q, et al. Effect of potassium feldspar on the decomposition rate of phosphogypsum[J]. Journal of Chemical Technology & Biotechnology, 2021, 96(2): 374-383.
[54] LÜ L, LI C, ZHANG G Q, et al. Decomposition behavior of CaSO₄ during potassium extraction from a potash feldspar-CaSO₄ binary system by calcination[J]. Chinese Journal of Chemical Engineering, 2018, 26(4): 838-844.
[55] YU B Y, ZHAO Z H, ZHANG S, et al. Technological development pathway for a low-carbon primary aluminum industry in China[J]. Technological Forecasting and Social Change, 2021, 173: 121052.
[56] TAN Z F, TAN Q K, WANG Y W. A critical-analysis on the development of energy storage industry in China[J]. Journal of Energy Storage, 2018, 18: 538-548.