粉煤灰酸法提取氧化铝蒸发母液回收氯化铝工艺研究

doi:10.11962/1006-4990.2020-0278

摘要/Abstract

摘要：

在粉煤灰盐酸法提取氧化铝蒸发结晶工序中,由于氯化铝溶液多次循环蒸发,引起蒸发母液中钙、镁、硅、磷等杂质离子的富集,当母液中杂质离子的浓度达到一定程度时需将部分氯化铝蒸发母液外排,这将会造成15%~20%原料铝的损失。利用氯化氢气体盐析结晶技术对蒸发母液进行处理,通过两级盐析结晶和浓盐酸洗涤,不仅实现了回收蒸发母液中氯化铝的目的,还提高了六水氯化铝晶体的纯度,使回收的氧化铝纯度达到99.38%,同时氧化铝中氧化钙、氧化镁、五氧化二磷的质量分数分别降低至2.680×10^-5、2.849×10^-4、2.051×10^-4。提出了蒸发母液回收氯化铝工艺路线,此流程可完全并入现有粉煤灰盐酸法提取氧化铝工艺的主流程。

关键词: 粉煤灰, 蒸发母液, 氯化铝, 氯化氢, 盐析结晶

Abstract:

In the evaporation and crystallization process of extracting alumina from fly ash by hydrochloric acid method,the aluminum chloride solution was repeatedly evaporated,which caused the enrichment of impurity ions such as calcium,magne-sium,silicon and phosphorus in the evaporation mother liquor.When the impurity ions in the mother liquor reached a certain degree,part of the aluminum chloride evaporation mother liquor needs to be discharged,which will cause the loss of 15%~20% of the raw aluminum.The technology of HCl gas salting-out crystallization was used to treat the evaporation mother liquor.After two-stage salting-out crystallization and concentrated hydrochloric acid washing,not only the purpose of recovering aluminum chloride in the evaporation mother liquor was realized,but also the purity of aluminum chloride crystal hexahydrate was increased,so that the purity of alumina recovered reached to 99.38%. Meanwhile,the contents of CaO,MgO and P₂O₅ in alumina were reduced to 2.680×10^-5,2.849×10^-4 and 2.051×10^-4 respectively.In addition,the process of recovering aluminum chloride from mother liquor was put forward,which can be completely incorporated into the existing main process of extracting aluminum oxide by hydrochloric acid method from fly ash.

Key words: fly ash, evaporation mother liquor, aluminum chloride, HCl, salting-out crystallization

中图分类号:

TQ133.1

钞晓光,王宏宾,曹坤,戴崟,松丽涛,邹萍,贾敏,高桂梅. 粉煤灰酸法提取氧化铝蒸发母液回收氯化铝工艺研究[J]. 无机盐工业, 2020, 52(12): 64-68.

Chao Xiaoguang,Wang Hongbin,Cao Kun,Dai Yin,Song Litao,Zou Ping,Jia Min,Gao Guimei. Study on technology of recovering aluminum chloride from evaporation mother liquor in extraction of alumina from fly ash by hydrochloric acid method[J]. Inorganic Chemicals Industry, 2020, 52(12): 64-68.

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参考文献 23

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主要成分	质量浓度/（g·L^-1）	主要成分	质量浓度/（g·L^-1）
Al₂O₃	179.924	SiO₂	0.584
CaO	9.686	ZnO	0.053
Fe₂O₃	0.088	Cr₂O₃	0.168
MgO	8.516	CuO	0.036
P₂O₅	5.717	V₂O₅	0.364
TiO₂	0.060	MnO₂	0.845
Li₂O	0.528

样品编号	Al		Ca		Fe		Mg		P		Ti		Li
样品编号	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %
盐析原液	52 389.6	—	3 805.3	—	33.8	—	2 810.4	—	1 372.8	—	19.90	—	135.6	—
盐析产品-1	41 285.9	78.81	15.1	0.40	0.7	1.99	169.2	6.02	57.9	4.22	0.05	0.24	2.6	1.93
盐析产品-2	43 003.7	82.08	145.2	3.82	0.5	1.55	179.8	6.40	103.4	7.53	1.00	5.01	27.3	20.16
盐析产品-3	49 643.9	94.76	160.4	4.22	1.5	4.33	281.9	10.03	118.5	8.63	0.80	3.96	24.0	17.70
样品编号	Si		Zn		Cr		Cu		V		Mn
样品编号	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %	质量/ g	析出率/ %
盐析原液	150.0	—	23.2	—	63.1	—	16.0	—	170.4	—	293.8	—
盐析产品-1	12.3	8.22	0.2	0.74	3.9	6.14	0.2	0.97	0.2	0.09	2.8	0.95
盐析产品-2	12.6	8.39	0.4	1.62	6.7	10.69	0.5	3.06	3.1	1.82	10.2	3.48
盐析产品-3	12.5	8.32	0.4	1.61	9.1	14.48	0.5	3.39	1.6	0.94	13.7	4.65

样品名称	CaO			Fe₂O₃			MgO			P₂O₅
样品名称	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%
盐析产品-1	1 248	270	78	140	12	91	9 047	3 605	60	3 557	1 696	52
盐析产品-2	13 666	2 496	82	117	9	92	13 669	3 677	73	9 281	2 905	69
盐析产品-3	9 521	2 388	75	85	22	74	15 213	4 996	67	7 106	2 885	59
样品名称	TiO₂			Li₂O			SiO₂			ZnO
样品名称	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%
盐析产品-1	8	1	87	978	72	93	441	338	23	13	3	79
盐析产品-2	101	20	80	4 093	719	82	562	331	41	53	6	89
盐析产品-3	67	14	79	1 677	547	67	624	284	54	32	5	85
样品名称	Cr₂O₃			CuO			V₂O₅			MnO₂
样品名称	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%	洗前 w/10^-6	洗后 w/10^-6	洗涤效率/%
盐析产品-1	131	72	45	23	2	89	27	2	91	397	56	86
盐析产品-2	283	121	57	46	8	84	519	45	91	1 241	198	84
盐析产品-3	249	142	43	11	7	32	372	20	95	869	230	74

样品名称		质量分数/%													烧失量/%
样品名称		Al₂O₃	CaO	Fe₂O₃	MgO	P₂O₅	TiO₂	Li₂O	SiO₂	ZnO	Cr₂O₃	CuO	V₂O₅	MnO₂	烧失量/%
盐析产品-1	洗前	95.07	1.367	0.012	1.367	0.928	0.010	0.409	0.056	0.005	0.028	0.005	0.052	0.124	0.562
盐析产品-1	洗后	98.40	0.250	0.001	0.368	0.291	0.002	0.072	0.033	0.001	0.012	0.001	0.004	0.020	0.543
盐析产品-2	洗前	95.87	0.952	0.008	1.521	0.711	0.007	0.168	0.062	0.003	0.025	0.001	0.037	0.087	0.551
盐析产品-2	洗后	98.29	0.239	0.002	0.500	0.289	0.001	0.055	0.028	0.000	0.014	0.001	0.002	0.023	0.553
盐析产品-3	洗前	97.87	0.125	0.014	0.905	0.356	0.001	0.098	0.044	0.001	0.013	0.002	0.003	0.040	0.526
盐析产品-3	洗后	98.86	0.027	0.001	0.361	0.170	0.000	0.007	0.034	0.000	0.007	0.000	0.000	0.006	0.531

主要成分	质量浓度/（g·L^-1）	主要成分	质量浓度/（g·L^-1）
Al₂O₃	149.808	SiO₂	0.019
CaO	0.263	ZnO	0.000
Fe₂O₃	0.004	Cr₂O₃	0.019
MgO	0.502	CuO	0.001
P₂O₅	0.330	V₂O₅	0.012
TiO₂	0.002	MnO₂	0.024
Li₂O	0.111

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