| 123 | 0 | 11 |
| 下载次数 | 被引频次 | 阅读次数 |
针对半导体生产企业治理含氟废水过程中产生的含氟渣资源化利用问题，采用氟化物化学转型法使含氟渣转变为氟化钙，从而实现含氟渣的资源化利用。研究了氟化铵、氢氟酸-氟化铵、乙酸、乙酸-氟化铵等不同转型剂的转型效果，重点考察了转型剂种类、溶液pH、溶液氟浓度等对转型渣中氟化钙含量的影响。结果表明：采用乙酸-氟化铵转型剂将含氟渣转型为氟化钙的转型率最高；在液固体积质量比10 mL/1 g、乙酸用量为n(CH3COOH)/[2×n(CaCO3)]=1.2和氟化铵用量为n(NH4F)/[2×n(Ca)+4×n(Al)+6×n(Si)-n(F-)含氟渣]=1.1、搅拌时间1 h、溶液pH=3.5～4.0条件下，氟化钙质量分数为88.72%,氟化钙转型率为38.11%。通过乙酸-氟化铵分步转型，能够消除CaCO3表层生成的CaF2对内层CaCO3进一步酸解的抑制作用，提高CaF2含量和含氟渣的转型率，可为含氟渣的资源化利用提供技术参考。
Abstract：To address the issue of resource utilization of fluoride-containing waste residues generated during the treatment of fluoride-containing wastewater from semiconductor manufacturing enterprises, a chemical transformation method is employed to convert fluoride residues into calcium fluoride, thereby achieving resource utilization of these residues.The transformation effects of different agents, including ammonium fluoride, hydrofluoric acid-ammonium fluoride, and acetic acid-ammonium fluoride were studied, focusing on the effects of the type of transformation agent, solution pH and fluoride concentration on the calcium fluoride content in the transformed residue.The results indicate that transformation rate is the highest for converting fluoride residues into calcium fluoride using acetic acid-ammonium fluoride as the transformation agent yields.Under conditions of liquid volume to solid mass ratio of 10 mL/1 g, acetic acid dosage of n(CH3COOH)/[2×n(CaCO3)]=1.2,ammonium fluoride dosage of n(NH4F)/[2×n(Ca)+4×n(Al)+6×n(Si)-n(F-)fluoride residue)]=1.1,stirring time of 1 h and solution pH between 3.5 and 4.0,the calcium fluoride content can reach 88.72%,with transformation rate of 38.11%.The stepwise transformation using acetic acid-ammonium fluoride can eliminate the inhibiting effect of calcium fluoride formed on the surface of calcium carbonate on the further acid dissolution of the inner layer of CaCO3,thereby increasing the content of CaF2 and the transformation rate of the fluoride-containing residues.It can provide a technical reference for the resource utilization ot fluorine-containing slag.
[1] 王彩红.浅谈含氟废水的来源及氟化物执行标准和深度除氟方法[J].皮革制作与环保科技，2023,4(3):16-18.WANG Caihong.On fluoride wastewater source and fluoride implementation standard and deep fluoride removal method[J].Leather Manufacture and Environmental Technology,2023,4(3):16-18.
[2] 吴俊楠，周晶.高标准排放背景下的含氟废水深度处理技术研究及应用[J].广东化工，2023,50(20):112-113.WU Junnan,ZHOU Jing.Analysis of advanced treatment technology for fluoride wastewater under the background of high emission standard[J].Guangzhou Chemical Industry,2023,50(20):112-113.
[3] 张丹丹.含氟废水污泥资源化回收利用[J].山东化工，2024,53(12):247-249.ZHANG Dandan.Study on the recycling and utilization of fluorine-containing wastewater sludge[J].Shandong Chemical Industry,2024,53(12):247-249.
[4] 朱萍，夏斌，刘强，等.氟化钙污泥提纯及资源化利用的研究现状[J].中国资源综合利用，2022,40(10):104-111.ZHU Ping,XIA Bin,LIU Qiang,et al.Research status of purification and resource utilization of calcium fluoride sludge [J].China Resources Comprehensive Utilization,2022,40(10):104-111.
[5] 王俊杰，赵娇娇，孟旭超，等.光伏光电行业含氟废水及污泥利用处置研究现状及展望[J].环境工程技术学报，2018,8(3):333-342.WANG Junjie,ZHAO Jiaojiao,MENG Xuchao,et al.Research status and prospect of fluorinated wastewater and sludge utilization in photovoltaic industry [J].Journal of Environmental Engineering Technology,2018,8(3):333-342.
[6] 谢顺昕，李育彪，薛浩，等.氟化钙污泥性质分析及浮选提纯工艺研究[J/OL].矿产综合利用，1-9[2024-10-24].http://kns.cnki.net/kcms/detail/51.1251.TD.20231118.1440.002.html.XIE Shunxin,LI Yubiao,XUE Hao,et al.Study on mineralogy and flotation purification of calcium fluoride sludge[J].Multipurpose Utilization of Mineral Resources,1-9[2024-10-24].http://kns.cnki.net/kcms/detail/51.1251.TD.20231118.1440.002.html.
[7] 吉栋梁，赵泽华，程俊华，等.四步法含氟污泥制备酸级氟化钙及其中试研究[J].四川环境，2022,41(6):18-25.JI Dongliang,ZHAO Zehua,CHENG Junhua,et al.Preparation of acid grade calcium fluoride by fluoride containing sludge using four step method and its pilot study [J].Sichuan Environment,2022,41(6):18-25.
[8] 仇雅丽，郑宇，刘勇奇，等.湿法冶炼氟化钙渣资源化利用实验研究[J].广东化工，2022,49(3):133-134.QIU Yali,ZHENG Yu,LIU Yongqi,et al.Experimental study on resource utilization of sodium fluoride calcium removal slag in hydrometallurgy [J].Guangdong Chemical Industry,2022,49(3):133-134.
[9] 陈献桃.以Na2SiF6固相形式回收钙镁磷肥厂含氟废水中的氟[J].岳阳师范学院学报(自然科学版),2000(3):43-44.CHEN Xiaotao.Retrieving fluorine from waste water in factory which produces calaium magesium phosphate through Na2SiF6 which is in solid state[J].Journal of Hunan Institute of Science and Technology(Natural Sciences),2000(3):43-44.
[10] 汤鸿霄.无机高分子絮凝剂的基础研究[J].环境化学，1990(3):1-12.TANG Hongxiao.Basic research on inorganic polymer flocculant[J].Environmental Chemistry,1990(3):1-12.
[11] 蒯杰，赵宇.含氟工业废水处理技术现状[J].资源节约与环保，2020(6):105-106.KUAI Jie,ZHAO Yu.Present situation of fluorine-containing industrial wastewater treatment technology[J].Resources Economization & Environmental Protection,2020(6):105-106.
[12] 程浩铭，张翠玲，任昊晔，等.化学沉淀法处理高氟废水的工艺条件优化[J].兰州交通大学学报，2018,37(5):80-84.CHENG Haoming,ZHANG Cuiling,REM Haoye,et al.Optimization of the technological conditions for the treatment of high fluoride wastewater by the chemical precipitation method[J].Journal of Lanzhou Jiaotong University,2018,37(5):80-84.
基本信息:
DOI：10.13355/j.cnki.sfyj.2025.03.009
中图分类号:X76;TQ132.32
引用信息:
[1]马红周,党煜博,王耀宁等.含氟渣转型制备氟化钙试验研究[J].湿法冶金,2025,44(03):353-360.DOI:10.13355/j.cnki.sfyj.2025.03.009.
基金信息: