含氟废液资源化制备氟化钠的工艺研究

doi:10.19964/j.issn.1006-4990.2023-0353

Abstract

Abstract:

The shortage of fluorite resources leads to the shortage of fluorine resources.In order to relieve the pressure of fluorine resources，it is necessary to fully improve the effective utilization rate of fluorine resources.The free fluorine in the waste liquid containing fluorine was recycled to prepare sodium fluoride by precipitation method with ammonium fluoride or hydrofluoric acid waste water as raw materials.The effects of reaction time，temperature，pH，and sodium salts on the quality of sodium fluoride products during the preparation process were studied，and the reuse frequency and effect of the filtrate after the reaction were explored.The results showed that when the reaction time of ammonium fluoride waste liquid was 120 min，the reaction temperature was 85 ℃ and the molar ratio of fluoride ions to sodium ions in sodium chloride was 1∶1，the quality of prepared sodium fluoride was best（98.30%） and the yield was 67.92%.After the reaction，the filtrate was evaporated after defluorination，and the nitrogen content of ammonium chloride reached 24.47%，which was met the requirements of agricultural ammonium chloride qualified products.The pH of the waste liquid containing hydrofluoric acid was adjusted to 6 by neutralization and sodium hydroxide.The mass fraction of sodium fluoride was 98.15%，and the filtrate could be reused at least 5 times.The process of preparing sodium fluoride from waste liquid containing fluorine with different components was realized in this work，which greatly reduced the waste of fluorine resources and made the fluorine resources fully and effectively utilized.

Key words: sodium fluoride, ammonium fluoride wastewater, hydrofluoric acid wastewater, reclamation

CLC Number:

TQ124.3

DENG Guoping, WU Yong, DUAN Lizhong, REN Zhi, WU Lixin. Research on process of preparing sodium fluoride from waste liquid containing fluorine as resource[J]. Inorganic Chemicals Industry, 2024, 56(6): 133-138.

Figures/Tables 8

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References 17

1	YOU Shaowei， CAO Shaotao， MO Chunyang，et al.Synthesis of high purity calcium fluoride from fluoride-containing wastewat-er［J］.Chemical Engineering Journal，2023，453：139733.
2	WU Shouyan， WANG Yajing， IQBAL M，et al.Challenges of fluoride pollution in environment：Mechanisms and pathological significance of toxicity：A review［J］.Environmental Pollution，2022，304：119241.
3	李育彪，杨旭.我国萤石资源及选矿技术进展［J］.矿产保护与利用，2022，42（2）：49-58.
	LI Yubiao， YANG Xu.Overview of fluorite resources and processing technology in China［J］.Conservation and Utilization of Mineral Resources，2022，42（2）：49-58.
4	杨勇，陈海洋，李煜坤，等.无水氟化氢和氟化铝工艺研发及工业应用进展［J］.无机盐工业，2023，55（9）：17-25，120.
	YANG Yong， CHEN Haiyang， LI Yukun，et al.Progress of process development and industrial application for anhydrous hydrogen fluoride and aluminum fluoride［J］.Inorganic Chemicals Industry，2023，55（9）：17-25，120.
5	蔡志明.电子厂含磷含氟废水处理工艺设计与应用［J］.中国高新科技，2021（10）：136-137.
	CAI Zhiming.Design and application of phosphorus and fluoride wastewater treatment process in electronic factory［J］.China High and New Technology，2021（10）：136-137.
6	段利中，苏贝贝，范相虎，等.电子行业含氟废液资源化的研究进展与展望［J］.广州化工，2022，50（19）：23-25.
	DUAN Lizhong， SU Beibei， FAN Xianghu，et al.Research progress and prospects of recycling fluorine-containing waste liquid in electronics industry［J］.Guangzhou Chemical Industry，2022，50（19）：23-25.
7	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.
8	刘亮强，冯永山.含氟废水处理工艺综述［J］.铜业工程，2022（2）：92-95，100.
	LIU Liangqiang， FENG Yongshan.Overview of fluorine-containing wastewater treatment process［J］.Copper Engineering，2022（2）：92-95，100.
9	吕智爽，蔡梦阳，杜春霖.利用生产氢氟酸的废酸制备氟化钠的研究［J］.辽宁化工，2020，49（4）：367-369，373.
	Zhishuang LÜ， CAI Mengyang， DU Chunlin.Study on the preparation of sodium fluoride with the waste liquid of hydrofluoric acid production［J］.Liaoning Chemical Industry，2020，49（4）：367-369，373.
10	万志鹏.含氟废水处理技术研究进展［J］.云南化工，2019，46（5）：24-25.
	WAN Zhipeng.Research progress on treatment of fluorine-containing sewage［J］.Yunnan Chemical Technology，2019，46（5）：24-25.
11	ZENG Guisheng， LING Bo， LI Zhongjun，et al.Fluorine removal and calcium fluoride recovery from rare-earth smelting wastewater using fluidized bed crystallization process［J］.Journal of Hazardous Materials，2019，373：313-320.
12	李凯华，晏乃强，徐亚玲，等.玻璃减薄蚀刻液中氟硅酸的选择性脱除方法［J］.环境工程学报，2014，8（3）：1079-1085.
	LI Kaihua， YAN Naiqiang， XU Yaling，et al.Method of selective removal of fluosilicic acid from used glass thinning solution［J］.Chinese Journal of Environmental Engineering，2014，8（3）：1079-1085.
13	晁夫奎.高浓度含氟工业废水综合处理及资源化利用研究［D］.徐州：中国矿业大学，2020.
	CHAO Fukui.Study on the comprehensive treatment and resource utilization of industrial wastewater with high concentration of fluorine［D］.Xuzhou：China University of Mining and Technology，2020.
14	温爱鹏.工业级氟硅酸钠制备白炭黑与氟化钠的新工艺研究［D］.南昌：南昌大学，2016.
	WEN Aipeng.Study on the new preparation technology of silica and sodium fluoride from industrial grade sodium hexafluorosilicate［D］.Nanchang：Nanchang University，2016.
15	于波，任桐，都兴红，等.含氟废水处理工艺研究［J］.中国资源综合利用，2020，38（11）：192-195.
	YU Bo， REN Tong， DU Xinghong，et al.Study on the treatment process of fluorine-containing wastewater［J］.China Resources Comprehensive Utilization，2020，38（11）：192-195.
16	张方.我国萤石资源与氟化工产业发展形势分析［J］.化学工业，2008，26（7）：6-9.
	ZHANG Fang.Fluorite resource and the development of China fluorine chemical industry［J］.Chemical Industry，2008，26（7）：6-9.
17	韩朝应，石秀明.氟硅酸钠制氟化钠联产氢氟酸的工艺研究［J］.硫磷设计与粉体工程，2019（2）：16-19，5.
	HAN Chaoying， SHI Xiuming.Process study for production of sodium fluoride and hydrofluoric acid from sodium fluorosilica-te［J］.Sulphur Phosphorus & Bulk Materials Handling Related Engineering，2019（2）：16-19，5.

等级	化学成分的质量分数/%
等级	NaF	SiO₂	碳酸盐（CO₃^2-）	硫酸盐（SO₄^2-）	酸度（HF）	水中不溶物	H₂O
一级	≥98	≤0.5	≤0.37	≤0.3	≤0.1	≤0.7	≤0.5
二级	≥95	≤1.0	≤0.74	≤0.5	≤0.1	≤3	≤1.0
三级	≥84		≤1.49	≤2.0	≤0.1	≤10	≤1.5

原料	w（氟化钠）/%	氟化钠产率/%	w（硫酸根）/%	w（碳酸根）/%
氯化钠+氟废液	98.30	67.92	≤0.01	≤0.01
硫酸钠+氟废液	88.42	51.51	10.21	≤0.01
碳酸钠+氟废液	90.36	71.33	≤0.01	4.55

处理方法	w（N）/%	w（Na）/%	w（F）/%
GB/T 2946—2018《氯化铵》农业用标准（合格品）	≥23.5	≤1.6	—
1^#	21.38	9.71	8.19
2^#	22.84	5.82	5.06
3^#	25.65	2.57	2.38
4^#	24.47	1.02	0.25
5^#	24.15	0.19	0.10

反应pH	w（氟化钠）/%	w［游离酸（HF）］/%	产率/%
3	75.88	22.35	30.52
4	88.92	10.53	53.82
5	95.23	4.82	72.73
6	98.15	0.06	80.31
7	93.85	0.03	83.45
8	91.32	0.01	84.29
9	88.42	0.01	84.79

样品	回用率/%	m（氟化钠）/g	w（NaF）/%	w（游离酸）/%	w（水不溶物）/%	氟利用率/%
氟化钠	66.45	32.82	97.66	0.017	0.30	85.29
氟化钠-回用1	66.77	34.54	97.53	0.024	0.22	89.64
氟化钠-回用2	63.31	34.81	97.88	0.008 4	0.21	90.66
氟化钠-回用3	68.58	35.22	98.35	0.004 2	0.25	92.17
氟化钠-回用4	65.36	33.94	96.53	0.008 0	0.05	87.18
氟化钠-回用5	62.96	34.56	95.58	0.007 9	0.08	87.90
氟化钠-蒸发		8.39	96.73	0.58	0.07

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Inorganic Acid-Base-Salt Committee of CIESC

Research on process of preparing sodium fluoride from waste liquid containing fluorine as resource

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样品	杂质元素含量
样品	Al	Mg	K	Ca	Cr	Fe
氟化铵废液	10.76	0.26	1.06	1.60	0.02	0.43
氢氟酸废液	82.14	5.01	22.61	18.47	0.16	28.49
氟化钠（氟化铵废液）	6.42	0.08	0.11	0.20	0.00	0.11
氯化铵-蒸发	37.60	1.25	11.41	1.21	0.41	6.67
氯化铵-冷凝	8.06	1.23	14.63	16.98	0.03	0.80
氟化钠（氢氟酸废液）	0.05	0.21	24.88	0.34	0.17	1.01

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[3]	Xie Tangfeng,Chen Ruokui,Gong Qinxue,Cai Luorong. Determination of silicon dioxide in crude sodium fluoride by potassium fluosilicate titrimetric method with microwave digestion [J]. Inorganic Chemicals Industry, 2021, 53(9): 92-96.
[4]	HUANG Feng-Ming. Production technology of sodium fluorosilicate by thermal decomposition method [J]. INORGANICCHEMICALSINDUSTRY, 2013, 45(12): 31-.
[5]	HE Hong-Liang-, MING Da-Zeng-, LI Zhi-Xiang. Separation method in producing sodium fluoride with soda method [J]. INORGANICCHEMICALSINDUSTRY, 2012, 44(1): 10-.
[6]	HU Zhen. Preparation of sodium fluoride by recovering fluorine from waste liquid in phosphate chemical industry [J]. INORGANICCHEMICALSINDUSTRY, 2011, 43(6): 53-.
[7]	Li Jin;Zuo Guangling;Li Rulin. Preparation of sodium fluoride and white carbon black from sodium flurosilicate and natural brine [J]. INORGANICCHEMICALSINDUSTRY, 2010, 0(7): 0-0.
[8]	Zhang Mei. Research on production process of cryolite and by-product silica white by sodium hydroxide-sodium fluosilicate method [J]. INORGANICCHEMICALSINDUSTRY, 2010, 0(4): 0-0.
[9]	Zhou Xiumei;Luo Yunhong;Yang Bin;Chen Wailiu;Hu Jinrong. Study on preparation of cryolite from solid sodium fluoride [J]. INORGANICCHEMICALSINDUSTRY, 2010, 0(11): 0-0.
[10]	Zhou Xiumei. Control and transformation for sodium fluosilicate production process [J]. INORGANICCHEMICALSINDUSTRY, 2009, 0(10): 0-0.