硝酸型废退锡水的分离特性与蒸馏强化偏锡酸回收

doi:10.19964/j.issn.1006-4990.2021-0603

摘要/Abstract

摘要：

针对电路板硝酸型废退锡液再生和锡提取技术的改进，对硝酸型废退锡水的物理化学特征、氧化还原与沉淀反应规律、真空蒸馏特性进行了理论分析和实验研究。结果表明：硝酸溶液中三价铁离子的存在可以将锡离子氧化为四价；硝酸浓度的提高可促进β型偏锡酸沉淀的形成；蒸馏是硝酸的浓缩过程，当水的蒸出率达到67.75%时，硝酸质量分数提高到40.04%，锡的质量分数降到了0.04%。废退锡水中锡以β型偏锡酸形式析出，析出率达到97.36%。经过蒸馏强化所获得沉淀物具有更好的沉淀特性；蒸馏底液保留了退锡水的有效成分，可作为再生退锡水。

关键词: 废退锡水, β型偏锡酸, 退锡水再生, 沉淀反应, 蒸馏

Abstract:

Aiming at the improvements of regeneration technology and tin extraction mothed of nitric acid type tin stripping waste solution for PCB industries，the physical and chemical characteristics，the behaviors of redox and precipitation reactions，and vacuum distillation characteristics of waste tin stripping solution were theoretically analyzed and experimentally studied.The results showed that Fe³⁺ in nitric acid solution could oxidize tin ion to tetravalent.The increase of nitric acid concentration promoted the precipitation formation of β-type meta stannic acid.Vacuum distillation was the concentration process of nitric acid.When the evaporation rate of water reached 67.75%，the mass ratio of nitric acid increased to 40.04% and the mass ratio of tin decreased to 0.04%.Tin in the waste tin stripping water was precipitated in the form of β-metastannic acid，and the precipitation rate reached 97.36%.The precipitate β-metastannic acid obtained by distillation had better precipitation characteristics.The distillation bottom liquid retained the effective components of tin stripping liquid and could be used to mix tin stripping liquid.

Key words: tin stripped waste liquid, β-metastannic acid, tin stripping solution regeneration, precipitation reaction, vacuum distillation

中图分类号:

TQ134.32

金分丽,查正炯,王永成,周桓. 硝酸型废退锡水的分离特性与蒸馏强化偏锡酸回收[J]. 无机盐工业, 2022, 54(8): 101-106.

JIN Fenli,ZHA Zhengjiong,WANG Yongcheng,ZHOU Huan. Separation characteristics of nitric acid type tin stripping waste solution and distillation enhanced recovery of meta stannic acid[J]. Inorganic Chemicals Industry, 2022, 54(8): 101-106.

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参考文献 11

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项目	pH	密度/（g·L^-1）	w（SnO₂）/%	w［Fe（NO₃）₃］/%	w［Cu（NO₃）₂］/%	w（HNO₃）/%	w（H₂O）/%
悬浊液	-0.49	1 368.2	9.763	3.920	1.600	21.318	63.399
澄清液	-0.49	1 190.0	0.948	3.583	1.386	23.617	70.467
湿固相	—	—	33.130	4.810	2.170	15.220	44.660

序号	氧化还原反应	ΔG^{（298 K）}/ （kJ·mol^-1）	反应判断
1	Sn+HNO₃+5H₂O=［Sn（H₂O）₆］²⁺+HNO₂	-186.79	自发
2	［Sn（H₂O）₆］²⁺→［Sn（H₂O）₆］⁴⁺	29.70	不自发
3	Sn²⁺+2HNO₃+2H⁺→Sn⁴⁺+2NO₂+2H₂O	114.67	不自发
4	Cu + HNO₃+H⁺=Cu⁺+ NO₂+H₂O	-27.10	自发
5	Cu⁺+HNO₃+H⁺→Cu²⁺+NO₂+H₂O	-61.57	自发
6	Sn²⁺+2 Cu^{2 +}→Sn⁴⁺+2 Cu⁺	-1.32	自发
7	Fe²⁺+NO₃^-+2H⁺→Fe³⁺+NO₂+H₂O	-1.879	自发
8	Sn²⁺+2Fe³⁺→Sn⁴⁺+2Fe²⁺	-118.70	自发
9	2Sn²⁺+O₂+4H⁺→2Sn⁴⁺+2H₂O	-175.73	自发
10	Sn²⁺+H₂O₂+2H⁺→Sn⁴⁺+2H₂O	-71.40	自发

序号	沉淀反应	ΔG^（298K）/ （kJ·mol^-1）	沉淀终点计算值*（pH）	沉淀终点测定值* 实测pH
11	Sn⁴⁺+2H₂O→SnO₂ +4H⁺	-47.84	>-1.60	—
12	Sn ²⁺+2OH^-→Sn（OH）₂	-149.91	>1.86	1.8
13	Fe³⁺ +3OH^-→Fe（OH）₃	-182.87	>3.98	3.5
14	Cu²⁺ +2OH^-→Cu（OH）₂	-112.20	>5.16	10.0
15	Fe²⁺ +2OH^-→Fe（OH）₂	-93.11	>6.83	—

m（废退锡水）/g	通氧气时间/h	m（H₂O₂）/ g	m（硝酸）/ g	pH	w（Sn⁴⁺）/ %
33.53	3	5	—	-0.66	0.717
33.03	—	—	1.43	-0.66	0.594
32.69	—	—	2.75	-0.71	0.523
32.80	—	—	5.50	-0.75	0.249
32.75	—	—	10.97	-0.85	0.137
32.68	—	—	16.44	-0.91	0.113

溶液质量/g	总蒸失率/%	水蒸出率/ %	pH	w（Sn⁴⁺）/ %	w（Fe³⁺）/ %	w（Cu²⁺）/ %	w（HNO₃）/ %	w（H₂O）/ %	w（馏出液的硝酸）/%	锡的析出率/%
1 005.71	0.00	0.00	-0.66	0.75	1.08	0.71	23.62	68.90	—	0.000
1 005.71	0.00	0.00	-0.55	0.64	1.05	0.74	25.33	67.75	—	0.00
1 030.83	2.02	2.52	-0.56	0.46	1.16	0.80	25.45	67.01	13.86	15.16
932.49	8.82	11.76	-0.57	0.39	1.16	0.81	27.97	64.50	8.21	44.15
933.23	11.43	15.32	-0.58	0.36	1.20	0.81	27.63	64.68	7.59	52.76
906.75	12.50	16.79	-0.59	0.33	1.21	0.82	26.67	65.56	7.43	57.38
894.68	12.40	16.57	-0.60	0.28	1.28	0.85	30.64	61.24	7.88	60.68
849.21	18.61	25.44	-0.61	0.25	1.27	0.83	31.94	60.05	5.82	68.08
856.45	18.99	25.92	-0.62	0.23	1.30	0.87	30.21	61.51	5.95	71.43
833.75	19.72	26.88	-0.63	0.24	1.30	0.88	33.10	58.58	6.08	74.85
832.22	22.38	30.77	-0.65	0.24	1.40	0.90	31.63	59.59	5.28	73.38
776.80	23.91	32.98	-0.68	0.21	1.41	0.93	36.02	55.05	4.96	75.51
766.73	28.26	39.22	-0.71	0.18	1.50	0.99	36.17	54.38	4.38	78.23
724.27	31.25	43.46	-0.74	0.18	1.55	1.02	36.45	53.78	4.18	82.28
698.91	32.92	45.86	-0.77	0.17	1.61	1.06	36.64	53.22	4.00	83.30
673.75	34.72	48.44	-0.80	0.16	1.70	1.13	37.00	52.27	3.87	84.75
638.25	37.32	52.16	-0.83	0.15	1.79	1.16	38.58	50.21	3.69	86.68
604.82	39.95	55.98	-0.86	0.13	1.86	1.21	39.11	49.24	3.45	87.82
583.64	41.75	58.54	-0.89	0.11	1.90	1.24	40.72	47.36	3.40	89.86
569.74	43.51	61.05	-0.94	0.11	1.96	1.25	40.63	47.21	3.32	91.62

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