氟硅酸、氧化镁制无水氟化氢联产优质硫酸镁工艺研究

doi:10.11962/1006-4990.2018-0579

Abstract

Abstract:

Anhydrous hydrogen fluoride,a basic material in fluorine chemical industry,is traditionally prepared by fluorite-sulfuric acid method.With the increasing scarcity of fluorite resources and the limited exploitation of fluorite resources by the state,it is of crucial importance for fluorine chemical industry to develop highly-efficient recycling of low-grade fluorine resources.The process of preparing high-value-added anhydrous hydrogen fluoride and combined production of high-quality magnesium sulfate by fluorosilicic acid which was the by-product in the phosphate fertilizer industry was studied.The effects of various key control parameters in the experimental process,including raw material concentration,raw material ratio,reaction temperature and the reaction time etc.,were analyzed.The highly-efficient recycling development of low-grade fluorosilicon resources by-products had been completed,and the bottleneck problem that restricted the development of related industries had been solved.Its economic benefits,environmental protection benefits and social benefits were remarkable.

Key words: phosphate fertilizer by-product, fluorosilicic acid, anhydrous hydrogen fluoride, high quality magnesium sulfate, efficient recycling

CLC Number:

TQ124.3

Hao Jiantang. Study on producing anhydrous hydrogen fluoride by fluorosilicic acid and magnesium oxide and combined production of high quality magnesium sulfate[J]. Inorganic Chemicals Industry, 2019, 51(8): 40-43.

实验编号	n（H₂SiF₆）: n（MgO）	氟硅酸用量（100%）/g	氧化镁用量（100%）/g	得到的氟硅酸镁量（MgSiF₆·6H₂O）/g	氟硅酸镁分析结果		原料利用率/%
实验编号	n（H₂SiF₆）: n（MgO）	氟硅酸用量（100%）/g	氧化镁用量（100%）/g	得到的氟硅酸镁量（MgSiF₆·6H₂O）/g	MgSiF₆·6H₂O主含量（质量分数）/%	w（MgSO₄·7H₂O）/%	氟硅酸	氧化镁
1^#	1:1	298.8	83.0	537.3	97.81	0.27	85.21	85.21
2^#	1:1	149.4	41.5	261.2	98.02	0.22	84.50	84.51
3^#	1.1:1	164.3	41.5	300.9	98.42	0.19	88.51	95.80
4^#	1.1:1	164.3	41.5	300.2	98.37	0.20	88.30	95.25
5^#	1.2:1	358.6	83.0	608.5	98.65	0.23	82.01	93.83
6^#	1.2:1	179.3	41.5	300.1	98.27	0.26	80.86	92.43

实验编号	反应温度/℃	氟硅酸镁收率/%	氟硅酸镁溶液过滤速度	氟硅酸镁分析结果
实验编号	反应温度/℃	氟硅酸镁收率/%	氟硅酸镁溶液过滤速度	MgSiF₆·6H₂O 主含量（质量分数）/%	w（MgSO₄·7H₂O）/%
1^#	55~65	94.98	快	98.27	0.51
2^#	55~65	95.12	快	98.01	0.55
3^#	75	95.48	快	98.42	0.39
4^#	75	95.25	快	98.37	0.47
5^#	85	95.01	较慢	98.21	0.52
6^#	85	95.10	较慢	98.19	0.57

实验编号	反应时间/min	氟硅酸镁收率/%	氟硅酸镁溶液过滤速度	氟硅酸镁分析结果
实验编号	反应时间/min	氟硅酸镁收率/%	氟硅酸镁溶液过滤速度	MgSiF₆·6H₂O 主含量（质量分数）/%	w（MgSO₄·7H₂O）/%
1^#	15	95.38	快	98.27	0.41
2^#	15	94.77	快	98.34	0.45
3^#	30	95.48	快	98.42	0.39
4^#	30	95.25	快	98.37	0.47
5^#	60	95.24	快	97.89	0.55
6^#	60	95.18	快	98.01	0.49

编号	煅烧温度/℃	煅烧前质量/g	煅烧1 h后质量/g	煅烧 2 h后质量/g	煅烧3 h后质量/g	理论煅烧后质量/g
1^#	120	30	24.1	19.2	16.3	11.2
2^#	150		20.1	15.6	12.6
3^#	200		16.5	12.1	11.3
4^#	250		13.8	11.8	11.2
5^#	300		11.3	11.2	11.2
6^#	350		11.2	11.2	11.2

反应温度/℃	反应率/%	反应温度/℃	反应率/%
常温	3.1	250	78.5
150	19.5	300	100.0
200	38.1	350	100.0

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on producing anhydrous hydrogen fluoride by fluorosilicic acid and magnesium oxide and combined production of high quality magnesium sulfate

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编号	n（MgO）: n（H₂SO₄）	未提纯硫酸镁		提纯后硫酸镁
编号	n（MgO）: n（H₂SO₄）	w（MgSO₄·7H₂O）/%	w（水不溶物)/%	w（MgSO₄·7H₂O）/%	w（水不溶物）/%
1^#	1:1	86.19	8.13	—	—
2^#	1:1.05	96.38	2.25	99.41	0.08
3^#	1:1.1	97.94	1.38	99.66	0.02
4^#	1:1.2	97.68	1.58	99.68	0.01

项目	w（氟化氢）/%	w（水）/ %	w（氟硅酸）/%	w（二氧化硫）/%	w[不挥发酸（以H₂SO₄计）]/%
GB 7746—2011Ⅰ类	≥99.98	≤0.005	≤0.005	≤0.003	≤0.005
本工艺无水氟化氢产品	99.99	0.003	0.003	0.002	0.003

项目	w[硫酸镁（以MgSO₄·7H₂O计）]/%	w[氯化物（以Cl计）]/%	w（铁）/ %	w（水不溶物）/%
Ⅰ类（MgSO₄· 7H₂O）优等品	≥99.5	≤0.10	≤0.002	≤0.02
本工艺产品	99.65	0.07	0.001	0.016

项目	单耗/ （t·t^-1）	单价（不含税）/ （元·t^-1）	单位成本/ 元
氟硅酸100%	1.42	1 800	2 556
浓硫酸98%	2.75	300	825
氧化镁 85%	1.22	600	732
天然气	500 m³/t	2.0	1 000
蒸汽	10	178	1 780
电	500 kW·h/t	0.58	290
人工	—	—	100
修理费	—	—	50
其他费用	—	—	30
总计			7 363
副产硫酸镁 99%	3	1 800	5 400
小计			1 963

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