2024年 06期

摘要(Abstract)：

针对中国华北地区某氟化工企业制冷剂废水中氟离子超标现象，在实验室小试的基础上开展制冷剂废水的流化床深度除氟中试试验，确定流化床除氟工艺的最佳工况，并与传统除氟剂的药剂成本进行技术经济对比。结果表明：当氯化钙与氟化物(以氟离子计)物质的量比为3∶1、投加聚合氯化铝质量浓度为550 mg/L、酸碱度pH约为6.7、搅拌时间为43 min时工况最佳，氟化物质量浓度由9 mg/L左右减至1 mg/L左右，去除率约为89%;相对于传统除氟剂，流化床除氟工艺能实现制冷剂废水中氟化物的深度去除，是一种新型、低成本的深度除氟工艺。

关键词(KeyWords)： 废水处理;深度除氟;中试试验;制冷剂废水;流化床;氟化物

基金项目(Foundation): 山东省自然科学基金项目(ZR2017MEE061)

作者(Author): 张明辉,周福伟,盖文革,张刚

DOI: 10.13349/j.cnki.jdxbn.20240318.003

参考文献(References)：

[1] TU B Y,YU K F,FU D J,et al.Amino-rich Ag-NWs/NH2-MIL-125(Ti) hybrid heterostructure via LSPR effect for photo-assist uranium extraction from fluorine-containing uranium wastewater without sacrificial agents[J].Applied Catalysis:B:Environmental,2023,337:122965.

[2] ZHOU G,MENG Q Z,LI S L,et al.Novel magnetic metal-organic framework derivative:an adsorbent for efficient removal of fluorine-containing wastewater in mines[J].Journal of Environmental Chemical Engineering,2022,10(5):108421.

[3] 王欣新.氟化物污染的危害及其治理[J].农家参谋，2019(16):191.

[4] LINHARES D,CAMARINHO R,GARCIA P V,et al.Mus musculus bone fluoride concentration as a useful biomarker for risk assessment of skeletal fluorosis in volcanic areas[J].Chemosphere,2018,205:540.

[5] 国家环境保护局.污水综合排放标准：GB 8978—1996[S].北京：中国标准出版社，1998:274-275.

[6] 北京市环境保护局.城镇污水处理厂水污染物排放标准：DB11/890—2012[S].北京：北京市环境保护局，2012:5.

[7] 天津市环境保护局.城镇污水处理厂水污染物排放标准：DB12599—2015[S].天津：天津市环境保护局，2015:11.

[8] 江苏省生态环境厅.城镇污水处理厂污染物排放标准：DB32/4440—2022[S].江苏：江苏省生态环境厅，2022:11.

[9] 山东省环境保护厅.流域水污染物综合排放标准：第3部分：小清河流域：DB37/3416.3—2018[S].山东：山东省环境保护厅，2018:11.

[10] ACHOUR S,YOUCEF L.Defluoridation of Algerian drinking water by precipitation and adsorption methods[J].Applied Mechanics and Materials,2014,641/642:365.

[11] GOMORO K,ZEWGE F,HUNDHAMMER B,et al.Fluoride removal by adsorption on thermally treated lateritic soils[J].Bulletin of the Chemical Society of Ethiopia,2012,26(3):361.

[12] LIU J R,SU J F,ALI A,et al.Potential of a novel facultative anaerobic denitrifying Cupriavidus sp.W12 to remove fluoride and calcium through calcium bioprecipitation[J].Journal of Hazardous Materials,2022,423:126976.

[13] SINGH S,CHAUDHARI S.Fluoride mitigation by co-precipitation in calcium phosphate systems:effect of process parameters and presence of synthetic non-calcined hydroxyapatite[J].Journal of Water Process Engineering,2023,53:103765.

[14] 段作山，王向举，马小蕾，等.反渗透除氟除氨氮技术在饮用水中的应用[J].净水技术，2021,40(3):139.

[15] XU Y L,SUN W,MIAO C M,et al.Ablation properties of C/C-UHTCs and their preparation by reactive infiltration of K2MeF6 (Me=Zr,Ti) molten salt[J].Journal of the European Ceramic Society,2021,41(11):5405.

[16] 陈益.电渗析法除氟处理[J].建筑技术通讯(给水排水),1981(2):45.

[17] ZHANG W,ZHAN G P,LI F K,et al.From MOF to Al/N-doped porous carbon:creating multiple capture sites for efficient capacitive deionization defluorination[J].Desalination,2022,543:116090.

[18] HE Y J,HUANG L,SONG B C,et al.Defluorination by ion exchange of SO■ on alumina surface:adsorption mechanism and kinetics[J].Chemosphere,2021,273:129678.

[19] 张小东，赵飞燕，王永旺，等.废水除氟技术研究现状[J].无机盐工业，2019,51(12):6.

[20] FORSTER A L B,ZHANG Y,WESTERMAN D C,et al.Improved total organic fluorine methods for more comprehensive measurement of PFAS in industrial wastewater,river water,and air[J].Water Research,2023,235:119859.

[21] 周福伟.流化床-诱导结晶工业水深度除氟技术研究[D].济南：济南大学，2021:13-14.