Leaching properties of phosphorus and fluorine in hemihydrate phosphogypsum as underground filiing materials and geochemical simulation
ZHU Xue-tao1, DU Bing2, A Man-jiao1, KANG Ti3, CHEN Deng-mei3, SHI Jian-hua4, LIU Jian-guo1
1. School of Environment, Tsinghua University, Beijing 100084, China; 2. Capital Environment Holdings Ltd, Beijing 100088, China; 3. Guizhou Institute of Environmental Scientific Research and Design, China, Guiyang 550081; 4. Guizhou Chuanheng Chemical Corporation, China, Fuquan 550500, China
Abstract:The HPG as backfill material was selected as the research subject. The leaching characteristics and long-term release of phosphorus and fluorine in four kinds of HPG and HPGB cemented paste filling materials were evaluated by pH-dependent and semi-dynamic leaching tests under simulated groundwater leaching conditions. The controlling mechanisms of phosphorus and fluorine leaching characteristics was discussed by geochemical simulation analysis. The results showed that 99.97% soluble phosphorus and 95.92% fluoride were solidified as Ca3(PO4)2 and CaF2 in HPGB which was modified by quicklime. According to the pH-dependent leaching test, the leaching concentration of total phosphorus had no significant relationship with pH under neutral and alkaline conditions. The geochemical simulation results of the semi-dynamic leaching test indicated the controlling phase of phosphorus in HPGB is fluoroapatite. The major controlling phase of fluorine leaching was fluorite and fluoroapatite, and the proportion of fluorite controlling phase decreased from 95% to 90% after long term leaching test.
朱雪涛, 杜兵, 阿曼角, 康媞, 陈登美, 石建华, 刘建国. 半水磷石膏地下充填材料的磷和氟浸出特性及地球化学模拟[J]. 中国环境科学, 2022, 42(2): 680-687.
ZHU Xue-tao, DU Bing, A Man-jiao, KANG Ti, CHEN Deng-mei, SHI Jian-hua, LIU Jian-guo. Leaching properties of phosphorus and fluorine in hemihydrate phosphogypsum as underground filiing materials and geochemical simulation. CHINA ENVIRONMENTAL SCIENCECE, 2022, 42(2): 680-687.
Rashad A M. Phosphogypsum as a construction material[J]. Journal of Cleaner Production, 2017,166:732-743.
[2]
Zhou J, Sheng Z, Li T, et al. Preparation of hardened tiles from waste phosphogypsum by a new intermittent pressing hydration[J]. Ceramics International, 2012,42:7237-7245.
[3]
Tayibi H, Choura M, López F A, et al. Environmental impact and management of phosphogypsum[J]. Journal of Environmental Management, 2009,90:2377-2386.
[4]
Pérez-López R, Macías F, Cánovas C R, et al. Pollutant flows from a phosphogypsum disposal area to an estuarine environment:An insight from geochemical signatures[J]. Science of the Total Environment, 2016,553:42-51.
[5]
Contreras M, Pérez-López R, Gázouez M J, et al. Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum wastes applied to mineral CO2 sequestration[J]. Waste Management, 2015,45:412-419.
[6]
Pérez-López R, Nieto J M, De La Rosaj D, et al. Environmental tracers for elucidating the weathering process in a phosphogypsum disposal site:Implications for restoration[J]. Journal of Hydrology, 2015,529:1313-1323.
[7]
那华,吕国诚,张丹,等.矿区典型环境污染及其充填胶凝固定化研究进展[J]. 黄金科学技术, 2020,28(5):646-657. Na H, Lv G C, Zhang D, et al. Research progress of typical environmental pollution in polymetallic mining area and its filling and gel immobilization[J]. Gold Science and Technology, 2020,28(5):646-657.
[8]
杨培发,陈军民,陈志华.我国湿法磷酸生产技术对比[J]. 磷肥与复肥, 2020,35(1):24-26. Pei F Y, Chen J M, Chen Z H. Comparison of WPA production technology in China[J]. Phosphate & Compound Fertilizer, 2020, 35(1):24-26.
[9]
贵州省人民政府.省人民政府关于加快磷石膏资源综合利用的意见[Z]. 贵阳, 2018. People's Government of Guizhou Province. Opinions of provincial people's government on speeding up comprehensive utilization of phosphogypsum resources[Z]. Guiyang, 2018.
[10]
孙志立,车建青.磷石膏资源化利用的发展方向[J]. 化肥工业, 2014, 41(4):1-3,22. Sun Z L, Che J Q. Development direction of resource utilization of phosphogypsum[J]. Fertilizer industry, 2014, 41(4):1-3,22.
[11]
Jiang G Z, Wu A X, Wang Y M, et al. Low cost and high efficiency utilization of hemihydrate phosphogypsum:Used as binder to prepare filling material[J]. Construction and Building Materials, 2018,167:263-270.
[12]
杨成军,杨敏,曹建新.半水/无水磷石膏复相胶凝材料水化硬化特性研究[J]. 非金属矿, 2014,37(6):22-25. Yang C J, Yang M, Cao J X. Study on hydration and hardening of duplex gypsum binder of hemihydrite phosphogypsum and anhydrite phosphogypsum[J]. Non-Metallic Mines, 2014,37(6):22-25.
[13]
李剑秋,李子军,王佳才,等.磷石膏充填材料与技术发展现状及展望[J]. 现代矿业, 2018,34(10):1-4,8. Li J Q, Li Z J, Wang J C, et al. Development statues and prospect of phoshpogypsum filling material and technique[J]. Modern Mining, 2018,34(10):1-4,8.
[14]
王佳才,吴爱祥,李剑秋,等.半水磷石膏充填材料及其制备方法:中国, 2017107310661[P]. 2018-01-09. Wang J C, Wu A X, Li J Q, et al. Filling material of hemihydrate phosphogypsum and its preparation method:China, 2017107310661[P]. 2018-01-09.
[15]
张政,李金娟,郭兴强等.磷石膏渗滤液对碳酸盐岩的溶蚀试验[J]. 贵州大学学报(自然科学版), 2020,37(4):118-124. Zhang Z, Li J J, Guo X Q, et al. Dissolution experiment of phosphogypsum leachate on carbonatite[J]. Journal of Guizhou University(Natural Sciences), 2020,37(4):118-124.
[16]
蔡保德,李金娟,郭兴强,等.多种介质修复磷石膏堆场渗滤液污染岩溶地下水[J]. 贵州大学学报(自然科学版), 2019,36(2):118-124. Cai B D, Li J J, Guo X Q, et al. Remediation of karst groundwater by percolation of phosphogypsum yard with various media[J]. Journal of Guizhou University(Natural Sciences), 2019,36(2):118-124.
[17]
姜利国,尹成薇,梁冰.环境pH对香溪河流域磷矿废石释磷特性的影响[J]. 环境工程学报, 2016,10(5):2674-2680. Jiang L G, Ying C Z, Liang B. Effects of environmental pH on phosphorus leaching characteristics of phosphate waste rock deposited within Xiangxi River watershed[J]. Chinese Journal of Environmental Engineering, 2016,10(5):2674-2680.
[18]
HJ557-2010固体废物浸出毒性浸出方法-水平振荡法[S]. HJ557-2010 Test method standard for leaching toxicity of solid wastes——Horizontal vibration extraction procedure[S].
[19]
EPA Method 1313 Liquid-solid partitioning as a function of extract pH using a parallel batch extraction procedure[S].
[20]
EPA Method 1315 Mass transfer rates of constituents in monolithic or compacted granular materials using a semi-dynamic tank leaching procedure[S].
[21]
Xue X, Ke Y, Kang Q, et al. Cost-effective treatment of hemihydrate phosphogypsum and phosphorous slag as cemented paste backfill material for underground mine[J]. Advances in Materials Science and Engineering, 2019,(2019):1-11.
[22]
杨林,曹建新,刘亚明.半水磷石膏的晶型、形貌及胶凝性能的影响因素研究[J]. 人工晶体学报, 2015,44(9):2460-2467. Yang L, Cao J X, Liu Y M. Study on the influence factor of the crystalline,morphology and cementitious properties of hemi-hydrate phosphogypsum[J]. Journal of Synthetic Crystals, 2015,44(9):2460-2467.
[23]
GB3838-2002地表水环境质量标准[S]. GB3838-2002 Environmental quality standards for surface water[S].
杨敏.杂质对不同相磷石膏性能的影响[D]. 重庆:重庆大学, 2008. Yang M. Effect of impurities on the properties of phosphogypsum with different forms[D]. Chongqing:Chongqing University, 2008.
[27]
谢正苗,吴卫红,徐建民.环境中氟化物的迁移和转化及其生态效应[J]. 环境科学进展, 1999,7(2):41-54. Xie Z M, Wu W H, Xu J M. Translocation and transformation of fluorides in the environment and their biological effects[J]. Advances in Environmental Science, 1999,7(2):41-54.
[28]
Kiminami K, Matsuoka K, Konishi T, et al. Effects of addition of α-tricalcium phosphate powders on material properties of the chelate-setting hydroxyapatite cement[J]. Phosphorus Research Bulletin, 2017, 33:7-13.
[29]
孙占学.氟的水文地球化学[J]. 华东地质学院学报, 1992,15(3):288-295. Sun Z X. Hydrogeochemistry of fluorine[J]. East China Institute of Geology, 1992,15(3):288-295.
[30]
彭家惠,万体智,汤玲,等.磷石膏中杂质组成、形态、分布及其对性能的影响[J]. 中国建材科技, 2000,(6):31-35. Peng J H, Wan T Z, Tang L, et al. Morphology distribution of impurities in phosphogypsum and its influence on properties[J]. China Building Materials Science & Technology, 2000,(6):31-35.
[31]
朱其顺,许光泉.中国地下水氟污染的现状及研究进展[J]. 环境科学与管理, 2009,34(1):42-44,51. Zhu Q S, Xu G Q. The current situation and research progress of groundwater fluorine pollution, in China[J]. Environmental Science and Management. 2009,34(1):42-44,51.
[32]
兰文涛,吴爱祥,王贻明,等.半水磷石膏充填体离子固化与尺寸效应[J]. 中国环境科学, 2019,39(1):210-218. Lan W T, Wu A X, Wang Y M, et al. Ionic solidification and size effect of hemihydrate phosphogypsum backfill[J]. China Environmental Science, 2019,39(1):210-218.
[33]
巩文信.铝氟形态相互作用与混凝/吸附除氟机制研究[D]. 北京:中国科学院研究生院, 2012. Gong W X. Species interactions between aluminium and fluoride and the mechanism of fluoride removal by coagulation and adsorption[D]. Beijing:Graduate University of Chinese Academy of Sciences, 2012.
[34]
张梦舟,徐曾和,梁冰.三峡库区香溪河流域磷矿废石磷素释放特性研究[J]. 中国环境科学, 2016,36(3):840-848. Zhang M Z, Xu Z H, Liang B. Phosphorus release from phosphate waste rocks deposited in Xiangxi River watershed of Three Gorges Reservoir[J]. China Environmental Science, 2016,36(3):840-848.