铝电解含氟固废处理技术研究进展

doi:10.19964/j.issn.1006-4990.2024-0170

Abstract

Abstract:

The current applications of hydrometallurgical and pyrometallurgical technologies in the treatment of fluorine-containing solid wastes such as carbon slag，spent pot lining and aluminum electrolytes were reviewed.The advantages and disadvantages of these two technologies were outlined.Hydrometallurgical treatment involved selecting appropriate reagents to leach fluorine，aluminum，and other elements into the liquid phase under specific conditions，and then preparing aluminum fluoride products through steps such as precipitation and calcination.However，the quality and properties of the products still needed further improvement.Pyrometallurgical treatment focused on converting fluorine into fluorides under high-temperature conditions to achieve fluorine recovery.However，the corrosion of equipment under high-temperature conditions limited its large-scale application.It was of great significance for the continuous development of safe，effective，and high-value utilization technologies for fluorine-containing solid wastes in China's aluminum electrolysis industry.Current work was mainly concentrated on using chemical methods to extract and utilize valuable elements from fluorine-containing solid wastes.In the future，it was necessary to explore other new treatment methods，develop a wider variety of products，and achieve low-cost and large-scale utilization of fluorine-containing solid wastes.

Key words: aluminum electrolysis, fluorine-containing, solid waste, treatment

CLC Number:

TQ124.3

WANG Danqin, LIAN Yicheng, DU Xin, YAN Feifei, LIU Wanchao, REN Wurong. Research progress on treatment technology for fluorine-containing solid wastes of electrolytic aluminum[J]. Inorganic Chemicals Industry, 2025, 57(6): 9-17.

Figures/Tables 4

Table 1

Fig.1

Table 2

Hydrometallurgy methods to treat fluorine-containing solid wastes"

处理方法	浸出剂	反应条件	最优结果	焙烧温度及成本
酸法处理	H₂SO₄^［14］	电解质、氧化铝和硫酸的质量比为1∶1∶5，反应温度为275 ℃，焙烧时间为4 h	有Al₂O₃时，反应产物为NaAl（SO₄）₂，F提取率为99.76%（生成HF气体）	低温焙烧（<300 ℃），成本较低
	H₂SO₄^［15］	硫酸与大修渣质量比为1.4，焙烧温度为360 ℃，焙烧时间为2 h，浸出温度为80 ℃，浸出时间为2 h	Li转化为NaLiSO₄，Al转化为NaAl（SO₄）₂，Li和Al的浸出率分别为99.50%和72.57%，F气化率为99.34%（生成HF气体）	低温焙烧（360 ℃），成本较低
	H₂SO₄^［16］	硫酸与大修渣质量比为1.4，焙烧温度为750 ℃，焙烧时间为2 h，浸出温度为80 ℃，浸出时间为2 h	Al在高温下先转化为NaAl（SO₄）₂，后转化为Al₂O₃，Li和Al的浸出率分别为95.6%和0.9%，F生成HF气体	高温焙烧（750 ℃），成本较高
碱法处理	Na₂CO₃^［19］	碳酸钠与炭渣质量比为2.5，焙烧温度为950 ℃，保温时间为2 h，含氟废水氟铝物质的量比为6，pH为6.2，结晶温度为20 ℃	焙烧产物C、Na₂CO₃、NaF和NaAlO₂，回收C粉纯度为89%，F的回收率大于98%	高温焙烧（950 ℃），成本较高
	Na₂CO₃^［20］	Na₂CO₃溶液浓度为3.8 mol/L，液固质量比为4.5，反应温度为180 ℃，反应时间为1 h	Li的浸出率为99.12%，Al的浸出率小于1.00%，选择性提锂	低温反应（180 ℃），成本较低
	NaOH^［21］	NaOH溶液浓度为2 mol/L，温度为70 ℃，pH为4.0	可溶性F回收率为92%（生成AlF₂OH·1.4H₂O ）	低温反应（<100 ℃），成本较低
铝盐处理	H₂SO₄- Al₂（SO₄）₃^［13］	浸出温度为95 ℃，浸出时间为4 h，初始pH为3，液固质量比为8，氟铝物质的量比为3	冰晶石完全溶解，反应产物为碱式氟化铝，浸出率为62.3%	低温反应（<100 ℃），成本较低
	AlCl₃^［28］	AlCl₃浓度为0.85 mol/L，液固质量比为3，浸出温度为95 ℃，浸出pH为0.5	Li浸出率为88.3%，浸出剂中的Al³⁺进入渣相参与形成Na₅Al₃F₁₄和 AlF_1.5（OH）_1.5·（H₂O）_0.375	低温反应（<100 ℃），成本较低
	Al（NO₃）₃^［29］	1）焙烧配料Al（NO₃）₃与Na₃AlF₆物质的量比为1∶2~2∶1，温度为85~135 ℃；2）水洗温度为25 ℃，液固质量比为10；3）与NH₄HF₂焙烧温度为200、400、600 ℃各2 h；4）去除Na₅Al₃F₁₄：Al（NO₃）₃质量分数为20%，液固质量比为10，温度为80 ℃，搅拌时间为2 h	冰晶石中Na的转化率为97.03%，产品中AlF₃的纯度高于98.8%，AlF₃的平均粒径为14.9 μm	低温反应（<150 ℃），成本较低

Table 2

Table 3

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处理方法	处理对象	反应条件	最优结果	成本
高温热处理	废阴极^［37］	1）焙烧温度为1 700 ℃，焙烧时间为60 min；2）焙烧温度为2 400 ℃，焙烧时间为60 min	1）氟化物脱除率为88.54%（烟气回收氟化盐）；2）氟化物脱除率为96.89%（烟气回收氟化盐）	高温焙烧（>2 000 ℃），成本高
高温热处理	炭渣^［40］	焙烧温度为650~800 ℃，焙烧时间为60~150 min	焙烧产物为电解质（Na₃AlF₆、NaF和Al₂O₃），质量分数大于98%	焙烧温度较高（800 ℃），成本较高
氟化物转化技术	废阴极（CaF₂ 转化技术）^［43］	焙烧温度为700~950 ℃，保温时间为2 h，白云石添加量为40%	焙烧产物为CaF₂、MgO、Ca₁₂Al₁₄O₃₃、Na₂CO₃、CaO和MgAl₂O₄，浸出毒性试验F^-的质量浓度为47.53 mg/L	高温焙烧（850 ℃），成本较高
	炭渣（AlF₃ 转化技术）^［48］	1）除碳：焙烧温度为670 ℃，反应时间为80 min，O₂流速为7 g/min；2）铝盐焙烧：Al₂（SO₄）₃质量分数为50%，焙烧温度为670 ℃，反应时间为10 min；3）水浸去除硫酸根：温度为35 ℃，时间为15 min，液固体积质量比（mL/g）为6	1）C的去除率为99.95%，F损失率为0.48%；2）F转化率为99.76%（生成AlF₃）；3）F损失率为3.98%，AlF₃纯度为94.3%；整个流程中F回收率为94.56%	高温焙烧（670 ℃），成本较高
	铝电解质（HF 转化技术）^［50］	加热温度为180~350 ℃，时间为1~4 h，负压反应器压力为-400~-100 Pa	F全量化回收（生成HF ）	低温负压反应（<350 ℃），成本较低

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Research progress on treatment technology for fluorine-containing solid wastes of electrolytic aluminum

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