混凝沉淀法处理冶金含氟废水工艺研究

doi:10.19964/j.issn.1006-4990.2023-0261

Abstract

Abstract:

The excessive fluorine content in water will cause great damage to the environment.At present，coagulant sedimentation method is widely used to treat fluorine-containing wastewater in metallurgical industry.Therefore，in view of the many influencing factors and the lack of comprehensive evaluation of the defluorination effect in coagulant sedimentation process，the fluorine-containing wastewater produced in the production process of a steel company was studied.Orthogonal experiments were designed to investigate the effects of pH，polyaluminum chloride（PAC） dosage，polyacrylamide（PAM） dosage，PAC stirring time and PAM stirring time on the defluorination efficiency of fluorine-containing wastewater.The research results indicated that the primary and secondary factors affecting defluorination efficiency were as follows：pH＞PAC stirring time＞PAC dosage＞PAM stirring time＞PAM dosage.In addition，the influence of the above factors and single factor changes such as temperature on the fluoride removal efficiency was studied.The results showed that defluorination efficiency under experimental conditions in this study was up to 99.3% when pH was 7，PAC dosage was 70 mL，PAM dosage was 2.5 mL，PAC stirring time was 15 min，PAM stirring time was 30 min，temperature was 30 ℃.In practical engineering applications，the total removal rate of fluoride ion by the coagulant sedimentation method was about 80%~90%，and the concentration of fluoride ion was about 7 mg/L.The results illustrated that the coagulant sedimentation method could satisfy the fluoride discharge standard.

Key words: coagulant sedimentation method, fluorine-containing wastewater, PAC, PAM

CLC Number:

X703

ZHU Zuoqiao, SHI Mengyuan, MAO Rui, GUO Haining, SU Yuao. Study on treatment process of metallurgical fluorine-containing wastewater by coagulant sedimentation method[J]. Inorganic Chemicals Industry, 2024, 56(4): 118-124.

Figures/Tables 10

Table 1

Table 2

Table 3

Calculation results of orthogonal experiment and range analysis of each parameter"

序号	pH	5%PAC投加量/mL	0.1%PAM投加量/mL	PAC搅拌时间/min	PAM搅拌时间/min	余氟含量/（mg·L^-1）
1	6	20	0.5	5	5	0.92
2	6	30	1.5	20	25	0.19
3	6	40	2.5	10	20	0.17
4	6	50	1	25	15	0.08
5	6	60	2	15	10	1.9
6	7	20	2.5	20	15	1.35
7	7	30	1	10	10	0.94
8	7	40	2	25	5	0.56
9	7	50	0.5	15	25	0.31
10	7	60	1.5	5	20	0.8
11	8	20	2	10	25	1.9
12	8	30	0.5	25	20	2.9
13	8	40	1.5	15	15	2.8
14	8	50	2.5	5	10	3.5
15	8	60	1	20	5	0.41
16	9	20	1.5	25	10	8.22
17	9	30	2.5	15	5	6.83
18	9	40	1	5	25	5
19	9	50	2	20	20	2.42
20	9	60	0.5	10	15	3.53
21	10	20	1	15	20	12
22	10	30	2	5	15	8.13
23	10	40	0.5	20	10	8.33
24	10	50	1.5	10	5	8.37
25	10	60	2.5	25	25	7.95
K-₁	0.65	4.88	3.20	3.67	3.42
K-₂	0.79	3.80	3.69	2.98	4.58
K-₃	2.30	3.37	4.08	4.77	3.18
K-₄	5.20	2.94	2.98	2.54	3.66
K-₅	8.96	2.92	3.96	3.94	3.07
$R$	8.31	1.96	1.1	2.23	1.51
影响主次：pH、PAC搅拌时间、PAC投加量、PAM搅拌时间、PAM投加量

Table 3

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

References 28

1	国家市场监督管理总局，国家标准化管理委员会. 生活饮用水卫生标准：GB 5749—2022［S］. 北京：中国标准出版社， 2022.
2	程秀绵. 含氟废水处理工艺的技术改进［J］. 工业水处理， 2007， 27（6）：84-86. doi: 10.11894/1005-829x.2007.27(6).84
	CHENG Xiumian. Technical reform in the fluorine-containing wa-stewater treatment［J］. Industrial Water Treatment， 2007， 27（6）：84-86. doi: 10.11894/1005-829x.2007.27(6).84
3	郑文茹，张付宝，汪仲权，等. 国内含氟废水处理技术研究进展［J］. 有机氟工业， 2019（3）：32-35.
	ZHENG Wenru， ZHANG Fubao， WANG Zhongquan， et al. Research progress in treatment of fluorine-containing wastewater in China［J］. Organo-Fluorine Industry， 2019（3）：32-35.
4	AMOR Z， BARIOU B， MAMERI N， et al. Fluoride removal from brackish water by electrodialysis［J］. Desalination， 2001， 133（3）：215-223. doi: 10.1016/S0011-9164(01)00102-3
5	OUYANG Zhuanxu， YANG Bijing， YI Jiangnan， et al. Exposure to fluoride induces apoptosis in liver of ducks by regulating Cyt-C/Caspase 3/9 signaling pathway［J］. Ecotoxicology and Environmental Safety， 2021， 224：112662. doi: 10.1016/j.ecoenv.2021.112662
6	李雪玲，刘俊峰，李培元. 石灰沉淀法除氟的应用［J］. 水处理技术， 2000， 26（6）：359-361.
	LI Xueling， LIU Junfeng， LI Peiyuan. Principle and application of fluoride removal by lime sedimentation method［J］. Technology of Water Treatment， 2000， 26（6）：359-361.
7	蔺亚青，刘帆，徐龙贵，等. 工业污水处理厂含氟废水处理技术［J］. 清洗世界， 2023， 39（5）：131-133.
	LIN Yaqing， LIU Fan， XU Longgui， et al. Treatment technology of fluorine-containing wastewater in industrial sewage treatment pla-nt［J］. Cleaning World， 2023， 39（5）：131-133.
8	李丽梅. 光伏含氟废水处理方法试验研究［J］. 山西化工， 2023， 43（4）：221-223.
	LI Limei. Experimental study on the treatment method of photovoltaic fluorine containing wastewater［J］. Shanxi Chemical Industry， 2023， 43（4）：221-223.
9	金月清，曾旭. 两级沉淀法处理液晶面板生产中含氟废水的研究［J］. 中国给水排水， 2019， 35（21）：109-112.
	JIN Yueqing， ZENG Xu. Treatment of fluoride wastewater in liquid crystal panel production by two-stage precipitation method［J］. China Water & Wastewater， 2019， 35（21）：109-112.
10	苏双青，赵焰，徐志清，等. 我国煤矿矿井水氟污染现状及除氟技术研究［J］. 能源与环保， 2020， 42（11）：5-10.
	SU Shuangqing， ZHAO Yan， XU Zhiqing， et al. Status quo of fluoride pollution of coal mine water in China and research on fluoride removal technology［J］. China Energy and Environmental Pro-ection， 2020， 42（11）：5-10.
11	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）：6-9，19.
	ZHANG Xiaodong， ZHAO Feiyan， WANG Yongwang， et al. Research status of wastewater defluoridation technology［J］. Inorganic Chemicals Industry， 2019， 51（12）：6-9，19.
12	王洪涛，季峻峰，刘连文. 蒙脱石降氟作用的实验研究［J］. 岩石矿物学杂志， 2003， 22（1）：71-73，76.
	WANG Hongtao， JI Junfeng， LIU Lianwen. An experimental study on defluoridation of drinking water with montmorillonite［J］. Acta Petrologica et Mineralogica， 2003， 22（1）：71-73，76.
13	赵艳锋，林罡明，李东泽. 粉煤灰处理含氟废水的研究［J］. 科学技术与工程， 2011， 11（10）：2389-2391.
	ZHAO Yanfeng， LIN Gangming， LI Dongze. Study on removal of fluoride wastewater by fly ash［J］. Science Technology and Engineering， 2011， 11（10）：2389-2391.
14	王绍文，李惊涛，王海东. 冶金废水处理回用新技术手册［M］. 北京：化学工业出版社， 2019：78.
15	刘宏江，李鹏，贺军四，等. 含氟废水处理的机理和工艺流程的研究［J］. 铜业工程， 2012（6）：81-84.
	LIU Hongjiang， LI Peng， HE Junsi， et al. Brief analysis on industrial security & protection system［J］. Copper Engineering， 2012（6）：81-84.
16	余琴芳，镇祥华，邹磊，等. 含氟工业废水深度处理工艺方案［J］. 净水技术， 2020， 39（5）：140-146.
	YU Qinfang， ZHEN Xianghua， ZOU Lei， et al. Solutions of advanced treatment process for industrial fluoride wastewater［J］. Water Purification Technology， 2020， 39（5）：140-146.
17	崔兵，金怡，杨泽坤. 钙盐-混凝法处理高氟废水的实验研究［J］. 工业水处理， 2023， 43（6）：150-155.
	CUI Bing， JIN Yi， YANG Zekun. Research on the treatment of high fluoride wastewater by calcium salt-coagulation method［J］. Industrial Water Treatment， 2023， 43（6）：150-155.
18	韩秀丽，赵凯，刘磊，等. 无氟连铸保护渣冶金性能的研究进展［J］. 材料导报， 2022， 36（11）：187-193.
	HAN Xiuli， ZHAO Kai， LIU Lei， et al. Research progress of metallurgical properties of fluorine-free continuous casting mold flux-es［J］. Materials Reports， 2022， 36（11）：187-193.
19	赵春宝，李晓阳，徐金岩，等. 包晶钢方坯连铸用无氟保护渣的研制与应用［J］. 宽厚板， 2020， 26（3）：15-20.
	ZHAO Chunbao， LI Xiaoyang， XU Jinyan， et al. Development and application of fluorine-free mould fluxes for peritectic steel billet continuous casting［J］. Wide and Heavy Plate， 2020， 26（3）：15- 20.
20	何本贵，高谦，刘芳. 公路路堑边坡稳定性影响因素正交分析与数值模拟［J］. 岩土工程学报， 2005， 27（6）：716-719.
	HE Bengui， GAO Qian， LIU Fang. Orthogonal analysis and numerical simulation on influential factors of freeway slope stabili-ty［J］. Chinese Journal of Geotechnical Engineering， 2005， 27（6）：716-719.
21	周玉珠. 正交试验设计的矩阵分析方法［J］. 数学的实践与认识， 2009， 39（2）：202-207.
	ZHOU Yuzhu. A matrix analysis of orthogonal design［J］. Mathematics in Practice and Theory， 2009， 39（2）：202-207.
22	刘斌，孙红梅，陈山，等. 顶空固相微萃取-气相色谱-串联质谱法测定水中2，4，6-三氯酚［J］. 环境监控与预警， 2019， 11（3）：36-39.
	LIU Bin， SUN Hongmei， CHEN Shan， et al. Determination of 2，4，6-trichlorophenol in water by HS-SPME-GC-MS-MS［J］. Environmental Monitoring and Forewarning， 2019， 11（3）：36-39.
23	叶康，张翠玲，程浩铭，等. 响应面优化PAC絮凝除氟工艺条件研究［J］. 环境科学与管理， 2021， 46（1）：68-72.
	YE Kang， ZHANG Cuiling， CHENG Haoming， et al. Optimization of defluoridation process of PAC by response surface［J］. Environmental Science and Management， 2021， 46（1）：68-72.
24	杨作清，李素芹，熊国宏. 钢铁工业水处理实用技术与应用［M］. 北京：冶金工业出版社， 2015：43.
25	申粤. 锆盐混凝剂的混凝行为及机理研究［D］. 重庆：重庆工商大学， 2021.
	SHEN Yue. Esearch on coggulation behavior and coagulation mechanism of zirconium salt coagulant［D］. Chongqing： Chongqing Technology and Business University， 2021.
26	侯郊，何翠萍，侯彦青，等. 高盐废水脱除氟离子实验研究［J］. 世界有色金属， 2022（12）：142-145.
	HOU Jiao， HE Cuiping， HOU Yanqing， et al. Research on F removal experiment of high-salt wastewater［J］. World Nonferrous Metals， 2022（12）：142-145.
27	贺建栋. 强化混凝工艺对微污染水体中多氯联苯的处理效能研究［D］. 兰州：兰州交通大学， 2017.
	HE Jiandong. Study on the processing efficiency of PCBs from micro-polluted water by enhanced coagulation［D］. Lanzhou： Lanzhou Jiaotong University， 2017.
28	韩军，石宇，谭炳卿，等. 南水北调东线工程水质仿真系统的研制开发［J］. 系统仿真学报， 2002， 14（12）：1579-1583.
	HAN Jun， SHI Yu， TAN Bingqing， et al. R & D of the water quality simulation system of east route of south-to-north water transfer project［J］. Acta Simulata Systematica Sinica， 2002， 14（12）：1579-1583.

[1]	ZHANG Feigang, LIU Zhongli. Study on application of CuO/g-C₃N₄ composites in organic dye degradation and supercapacitors [J]. Inorganic Chemicals Industry, 2025, 57(1): 129-136.
[2]	WU Qingqing, XU Xuetang, WANG Fan. Study on capacitor performance of high⁃mass⁃loading ZnCo-based carbonate hydroxide electrode materials [J]. Inorganic Chemicals Industry, 2024, 56(7): 46-54.
[3]	LIU Dexin, MA Tengyue, AN Jinling, LIU Jinrong, HE Weiyan. Study on cathode material design and electrochemical properties of manganese-based sodium ion battery [J]. Inorganic Chemicals Industry, 2024, 56(3): 51-55.
[4]	WANG Yizhou, HU Xiaomei, WANG Yongxiang, ZHANG Weimin. Study on preparation of nickel-iron-manganate sodium layered oxides and their properties [J]. Inorganic Chemicals Industry, 2024, 56(2): 57-64.
[5]	HAN Hongjing, ZHANG Jingze, LAMAO Zhuoma, HAN Jizhe, WU Yongmin, TANG Weiping. Preparation of Al-Co co-doped lithium manganese oxide and its adsorption performance of lithium [J]. Inorganic Chemicals Industry, 2023, 55(7): 38-44.
[6]	WANG Jianfang, YANG Heping, LI Kaibin, CONG Shiqiang, ZHANG Bojie, GUO Shan. Study on preparation of C₃N₄/MnCo₂S₄ composites and their capacitive properties [J]. Inorganic Chemicals Industry, 2023, 55(7): 70-74.
[7]	XU Xuetang, WANG Xukai, ZHANG Shenhe, HUANG Meixiang, NONG Shuliu, XU Nuo. Study on preparation and properties of vanadate doped NiCo-LDH electrode [J]. Inorganic Chemicals Industry, 2023, 55(5): 52-58.
[8]	WANG Lijuan, YAN Kezhou, GUO Zhiqiang, ZHAO Zhonghe, GUO Yanxia, CHENG Fangqin. Preparation of poly-aluminum chloride from acid leaching liquor of red mud-coal gangue activated by sodium salt [J]. Inorganic Chemicals Industry, 2023, 55(4): 76-83.
[9]	HU Yue, MO Hengliang, LI Tianyu, PENG Wenjuan, SUN Guangdong, XIAO Hongkang, CHEN Yili, LI Suoding, TANG Yang. Study on spinning molding and performance of Ti-based lithium ion sieve powder and PVDF resin [J]. Inorganic Chemicals Industry, 2023, 55(11): 58-63.
[10]	LI Sen, WANG Jin, WANG Yingying, CAI Mingfang. Synthesis and modification of NaA zeolite and its application in polyurethane system [J]. Inorganic Chemicals Industry, 2023, 55(10): 78-85.
[11]	JIANG Tiantian,XU Xuetang,WANG Fan. Research on growth and supercapacitance of NiCo based electrode materials regulated by halogen ions [J]. Inorganic Chemicals Industry, 2022, 54(8): 66-73.
[12]	HOU Shunli,ZHAO Duan,ZHOU Geng,WEI Shishi,LI Jian,WANG Jiatai. Research progress on doping modification of high nickel ternary nickel-cobalt-aluminum cathode material [J]. Inorganic Chemicals Industry, 2022, 54(8): 40-46.
[13]	DONG Peng,ZHOU Yingjie,HOU Minjie,YANG Dongrong,DAI Yongnian,LIANG Feng. Research progress on Na3V₂（PO₄）₃ cathode materials for sodium ion batteries [J]. Inorganic Chemicals Industry, 2022, 54(5): 1-10.
[14]	ZHANG Yue,WANG Min,LI Jinli,ZHAO Youjing,WANG Huaiyou. Study on thermophysical properties of solar salt composites doped with nanoparticles [J]. Inorganic Chemicals Industry, 2022, 54(5): 54-60.
[15]	Zhang Tianliang,Li Jun,Xiong Wei,Zhang Haiyan,Tao Xiaoqiu. Study on one-step preparation of activated carbon with high specific surface by K₂CO₃ activation and its capacitance performance [J]. Inorganic Chemicals Industry, 2022, 54(4): 159-164.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on treatment process of metallurgical fluorine-containing wastewater by coagulant sedimentation method

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 28

Related Articles 15

Metrics

Comments

Recommended 0

水平	pH	5%PAC投加量/mL	0.1%PAM 投加量/mL	PAC搅拌时间/min	PAM搅拌时间/min
水平1	6	20	0.5	5	5
水平2	7	30	1	10	10
水平3	8	40	1.5	15	15
水平4	9	50	2	20	20
水平5	10	60	2.5	25	25