脱除磷石膏中水溶磷、水溶氟的实验研究

doi:10.19964/j.issn.1006-4990.2021-0394

Abstract

Abstract:

The comprehensive utilization of phosphogypsum is of great significance to the sustainable development of phosphor-chemical enterprise and the eco-environmental protection of the Yangtze River Valley.However,the phosphogypsum contains a small amount of phosphorus,fluorine,organic compounds,and so on.The harmful impurities impact its application performance,which can′t be used directly.So,the distribution and removal of water-soluble phosphorus and water-soluble fluorine in phosphogypsum from a company in Anning were studied by lime neutralization,water washing and flotation.The results showed that the water-soluble phosphorus and water-soluble fluorine in phosphogypsum could be removed effectively by gypsum mixing,adding lime and mother solution cyclic utilization technique.The removal rates of them were 74.95% and 76.20% respectively,and their contents were 0.090% and 0.043% separately,which could meet the limit requirements of secondary indicators in GB/T 23456—2018《phosphogypsum》 standard.The water-soluble phosphorus and water-soluble fluorine could also be removed effectively by the three-stage countercurrent washing process.The removal rates of them were 78.81% and 89.94% respectively,and their contents were 0.087% and 0.018% separately.The quality of the pretreated phosphogypsum also could meet the secondary grade index requirements of GB/T 23456—2018《phosphogypsum》 standard.The efficiency separation of CaSO₄·2H₂O and SiO₂ was successfully achieved by the direct flotation process of one-stage roughing and two-stage cleaning.Simultaneously,the water-soluble phosphorus and the water-soluble fluorine in phosphogypsum were also effectively removed.Thus the quality of phosphogypsum was improved and reached the first-grade index requirements of GB/T 23456—2018《phosphogypsum》.From the perspective of economic feasibility and the analysis of the current low value utilization of phosphogypsum,the gypsum slurry mixing lime mother liquor circulating phosphogypsum pretreatment process formed by research is more applicable.

Key words: phosphogypsum, water-soluble phosphorus, water-soluble fluorine, removal

CLC Number:

TQ126.3

ZHANG Lizhen,ZHANG Yongxing,WU Zhaoyang,ZHANG Xiufeng,TAN Xiumin. Experimental study on removal of water-soluble phosphorus and water-soluble fluorine from phosphogypsum[J]. Inorganic Chemicals Industry, 2022, 54(4): 40-45.

Figures/Tables 11

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References 11

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化学成分	质量分数/%	化学成分	质量分数/%
CaO	28.19	P₂O_5总	0.920
SO₃	36.42	P₂O_5水溶	0.330
SiO₂	12.03	F_总	0.320
Al₂O₃	0.74	F_水溶	0.250
Fe₂O₃	0.14	MgO	0.062
结晶水	16.00	Na₂O	0.081

陈化时间/h	质量分数/%		脱除率/%
陈化时间/h	P₂O_5水溶	F_水溶	P₂O_5水溶	F_水溶
0	0.097	0.044	75.80	74.81
4	0.100	0.040	74.43	76.54
8	0.093	0.042	76.47	75.62
16	0.089	0.036	77.23	78.87
24	0.097	0.038	75.35	77.85

编号	产出磷石膏
	P₂O_5水溶		F_水溶
	质量分数/%	脱除率/%	质量分数/%	脱除率/%
A-循-5	0.075		0.034
A-循-10	0.085		0.046
A-循-15	0.082		0.045
A-循-20	0.100		0.057
B-循-5	0.085		0.039
B-循-10	0.100		0.045
B-循-15	0.096		0.041
B-循-20	0.099		0.041
平均	0.090	74.95	0.043	76.20

项目	液固比为2						液固比为3
	磷石膏					水洗液 pH	磷石膏					水洗液 pH
	w（水溶 P₂O₅）/%	脱除率/ %	w（水溶 F）/%	脱除率/ %	pH	水洗液 pH	w（水溶 P₂O₅）/%	脱除率/ %	w（水溶 F）/%	脱除率/ %	pH	水洗液 pH
洗1	—		—		—	2.75	0.140		0.065		—	2.90
洗2	—		—		—	3.01	0.099		0.026		—	3.23
洗3	0.087	78.810	0.018	89.940	5.58	4.06	0.087	78.330	0.011	93.710	5.89	4.25

项目		w（CaSO₄· 2H₂O,干基）/%	w（P₂O₅, 干基）/%	w（F^-, 干基）/%	w（MgO, 干基）/%	w（NaO, 干基）/%	w（Cl^-, 干基）/%	w（SiO₂, 干基）/%
指标	一级	≥90	≤0.20	≤0.10	≤0.10	≤0.06	≤0.02
指标	二级	≥80	≤0.30	≤0.20	≤0.30	≤0.10	≤0.04
石灰-1		82.74	0.065	0.023	0.004	0.011	0.004	14.71
石灰-2		83.36	0.10	0.057	0.007	0.023	0.005	14.47
水洗		83.49	0.087	0.018	0.005	0.008	0.007	14.29
正浮选		97.50	0.08	0.02	0.024	0.009	0.000 2	1.17

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Experimental study on removal of water-soluble phosphorus and water-soluble fluorine from phosphogypsum

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工艺	项目	数量	单价	消耗额/元	备注
水洗	水	2.04 t	6.50 元/t	13.26	每生产1 t合格磷石膏需原料1.02 t
	电	7 kW·h	0.80元/kW·h	5.60	每生产1 t合格磷石膏需原料1.02 t
	合计			18.86
石灰中和	石灰	3.06×10^-3 t	600元/t	1.836	每生产1 t合格磷石膏需原料1.02 t
	水	0.034 t	6.50元/t	0.221
	电	3.5 kW·h	0.80元/kW·h	2.80
	合计			4.86
浮选	十二胺	0.36×10^-3t	23 000元/t	8.28	每生产1 t合格磷石膏需原料1.19 t
	水	0.60 t	6.50元/t	3.90
	电	4 kW·h	0.80元/kW·h	3.20
	硫酸				磷化工企业自产
	合计			15.38

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