高杂质氟硅酸制备氟化铵联产氟化镁工艺技术研究

doi:10.11962/1006-4990.2019-0609

Abstract

Abstract:

An Efficient utilization process of high impurity fluosilicic acid was designed and researched to produce NH₄F with co-production of MgF₂.On the basis of characteristics of high impurity fluosilicic acid and mother liquor of NH₄F,a series of key factors were deeply studied to make up for the lack of related researches,including pH,reaction temperature,free ammonia,feeding method,exothermic curve,concentration curve and material balance,etc..Optimized process conditions were obtained,under which,the yield of primary crystallization of NH₄F was about 25%,which meet the requirements of first-class products in GB/T 28653—2012;the yield of MgF₂ reached more than 95%,which meet the MF-2 requirements of YS/T 691—2009.Research on concentration revealed that there was a good linear relationship between the concentration and density of NH₄F（y=3.9778x-4.0017;y：the concentration;x：the density）,and the critical crystallization density was 1.14 g/cm³.Material balance research showed that the studied process had a high raw material utilization and important industrial application value.

Key words: high impurity fluosilicic acid, ammonium fluoride, magnesium fluoride, material balance

CLC Number:

TQ124.3

Huang Zhong,Yu Shuangqiang,Gao Kaiyuan,He Jun,Huang He,Zhang Xianfeng,Chen Xizhen. Study on process technology of preparing NH₄F and co-producing MgF₂ with high impurity fluosilicic acid[J]. Inorganic Chemicals Industry, 2020, 52(10): 110-116.

实验序号	pH	SiO₂理论质量/ g	反应生成硅胶质量/g	过滤情况	硅胶含固量/%	灼烧后的SiO₂质量/g	转化率/%
1	3.0	46.8	—	无法过滤	—	—	—
2	6.0	46.8	152.4	很难（1 h）	11.60	17.7	34.8
3	7.0	46.8	245.3	较难（30 min）	12.50	30.6	58.1
4	7.5	46.8	353.6	一般（20 min）	12.90	42.4	90.7
5	9.0	46.8	120.3	容易（5 min）	31.24	46.4	99.1

序号	反应温度/℃	过滤速度/ （mL·min^-1）	过滤速度平均值/（mL·min^-1）	滤液中 w（F）/%	滤液中w（F）平均值/%	硅胶中 w（F）/%	硅胶中w（F）平均值/%	硅胶含水量/%	硅胶含水量平均值/%
1	40	5.8	5.9	77	74	23	26	68	68
2	40	5.8		73		27		66
3	40	5.9		72		28		68
4	60	7.2	7.4	78	79	22	22	66	66
5	60	7.6		78		22		64
6	60	7.5		79		21		67
7	70	9.1	9.8	81	80	19	20	65	63
8	70	9.8		79		21		62
9	70	10.5		81		19		63
10	80	12.9	14.0	85	85	15	15	62	61
11	80	18.2		86		14		59
12	80	11.0		84		16		62

实验序号	滤液	滤液中w（氟硅酸盐）/%	滤液 w（F）/%	氟硅物质的量比/%	转化率/ %
1	脱氨前	0.11	6.98	389.97	99.1
1	脱氨后	1.36	9.00	41.97	87.8
2	脱氨前	0.22	8.71	247.53	98.6
2	脱氨后	2.12	8.79	26.39	86.4
3	脱氨前	0.23	9.14	257.33	98.4
3	脱氨后	3.46	15.90	29.20	84.0

序号	洗涤方式	硅胶 w（F）/%	一次洗涤 w（F）/%	一次洗涤率/%	二次洗涤 w（F）/%	二次洗涤率/%	三次洗涤 w（F）/%	三次洗涤率/%	四次洗涤 w（F）/%	四次洗涤率/%	洗涤率合计/%
1	再浆	3.94	1.34	68.02	0.34	17.26	0.08	4.06	0.02	1.01	90.35
1	置换	3.94	1.30	65.99	0.19	9.64	0.07	3.55	0.04	2.03	81.21
2	再浆	3.91	1.20	61.38	0.33	16.88	0.08	4.09	0.02	1.02	83.37
2	置换	3.91	1.33	68.03	0.13	6.65	0.07	3.58	0.04	2.05	80.31
3	再浆	3.91	1.30	66.50	0.31	15.86	0.08	4.09	0.03	1.53	87.98
3	置换	3.91	1.24	63.43	0.17	8.70	0.07	3.58	0.04	2.05	77.76
4	再浆	3.90	1.24	63.59	0.26	13.33	0.09	4.62	0.05	2.56	84.10
4	置换	3.90	1.17	60.00	0.12	6.15	0.06	3.08	0.05	2.56	71.79
平均值	再浆			64.87		15.83		4.22		1.53	86.45
平均值	置换			64.36		7.79		3.45		2.17	77.77

		w（氟化铵）	w[游离酸（以HF计）]	w[氟硅酸盐（以氟硅酸铵计）]
GB/T 28653— 2012指标	一等品	≥95.0	≤1.0	≤0.5
GB/T 28653— 2012指标	合格品	≥93.0	≤1.0	≤1.0
产品	一次结晶	95.6	0.30	0.39
产品	二次结晶	89.4	0.78	1.48

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on process technology of preparing NH₄F and co-producing MgF₂ with high impurity fluosilicic acid

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样品名称	w （SO₄^2-）	w （P₂O₅）	w （CaO）	w （MgO）	w （Fe₂O₃）	w （Al₂O₃）	w （SiO₂）	w （F^-）
母液	1.50	0.54	0.01	0.03	0.02	0.11	0.7	26.8
氟化铵	1.11	0.82	0.01	0.02	未测出	0.09	0.5	45.9

检测指标		w（SO₄^2-）	w（P₂O₅）
一次结晶合格品洗涤	洗涤前	0.27	0.22
一次结晶合格品洗涤	洗涤后	0.03	未测出
二次结晶非合格品洗涤	洗涤前	1.11	0.82
二次结晶非合格品洗涤	洗涤后	0.06	0.05

实验序号	氟化铵母液质量分数/%	氟收率/ %	过滤情况
1	20	94.6	速度快
2	30	96.2	速度快
3	35	95.0	速度快
4	40	95.3	速度快
5	44	93.2	速度较慢,呈细流状
6	53	92.4	速度较慢,呈细流状

实验序号	加料方式	氟收率/%	过滤情况
1	氟化铵溶液滴加到硫酸镁溶液	—	无法过滤
2	硫酸镁溶液滴加到氟化铵溶液	87.8	难过滤
3	两种溶液同时滴加,同时结束	95.4	过滤速度快
4	两种溶液同时滴加,氟化铵溶液先滴加完成	95.0	过滤速度快

实验序号	反应温度/℃	氟化铵母液质量分数/%	氟收率/ %	过滤情况
1	80	35	87.0	速度较慢,呈细流状
2	70	35	95.3	速度较慢,呈细流状
3	60	35	95.7	过滤速度快
4	60	44	93.8	速度较慢,呈细流状
5	60	53	93.6	速度较慢,呈细流状
6	常温	35	96.2	过滤速度快

项目	w （F）	w （Mg）	w （Ca）	w （SiO₂）	w （P₂O₅）	w （SO₄^2-）	w （H₂O）
YS/T 691—2009：MF-2	≥45	≥28	—	≤0.9	≤1.1	≤1.3	≤1.0
样品1	49.28	33.59	0.50	0.016	未测出	1.12	0.17
样品2	49.35	33.62	0.47	0.015	未测出	1.06	0.13
样品3	49.32	33.68	0.56	0.011	未测出	1.14	0.16

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Study on process technology of preparing NH4F and co-producing MgF2 with high impurity fluosilicic acid