Effect of K-B-Al ternary system on the melting characteristics and glass structure of tailings

doi:10.11949/0438-1157.20240833

Abstract

Abstract:

To solve the problem of phosphate tailings accumulation, this study uses phosphate tailings and low-grade phosphate rock as the main raw materials, B₂O₃, Al₂O₃, KCl and other additives, to activate phosphate tailings and low-grade phosphate ore through thermal processing and prepare glass fertilizer. The influence of K-B-Al system on the melting characteristics of phosphorus tailings system was investigated by single factor and response surface experiments. The influence of additives on the activation effect of elements and slag phase structure of molten products was discussed by combining X-ray diffraction (XRD), Fourier infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that when the ratio of phosphorus tailings, low-grade phosphate rock, serpentine, KCl, B₂O₃ and Al₂O₃ is 55∶25∶20∶7∶10∶1.5, the lowest melt flow temperature T_F of the system is 1135℃, which is 335℃ lower than that of the conventional system. The activation rates of P₂O₅, CaO, and MgO in the glass fertilizer melted at 1350℃ are all about 95%. The effects of melting temperature and additives on the glass network structure of the material are analyzed. Under the selected process conditions, B₂O₃ mainly breaks the silicon oxygen network, while Al₂O₃ participates in the network composition and also destroys the silicon oxygen network.

Key words: phosphate tailings, glass ferilizer, silicon oxide structure, activation, waste treatment, optimal design

摘要：

为解决磷尾矿的堆积问题，以磷尾矿和低品位磷矿为主要原料，以B₂O₃、Al₂O₃、KCl等为助剂，通过热法加工实现磷尾矿及中低品位磷矿的活化并制备玻璃肥料。通过单因素和响应曲面实验探究了K-B-Al体系对磷尾矿体系熔融特性的影响，结合X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱仪（XPS）探讨了助剂添加对熔融产物元素活化效果和渣相结构的影响。结果表明，在磷尾矿、低品位磷矿、蛇纹石、KCl、B₂O₃、Al₂O₃配比为55∶25∶20∶7∶10∶1.5时，体系熔融流动温度T_F最低为1135℃，较常规体系降低335℃。在1350℃时熔融所得玻璃肥料P₂O₅、CaO、MgO活化率均达到95%左右。分析了熔融温度和助剂对物料玻璃网络结构的影响。在所选工艺条件下B₂O₃以断裂硅氧网络为主，Al₂O₃既参与网络组成，也破坏硅氧网络。

关键词: 磷尾矿, 玻璃肥料, 硅氧结构, 活化, 废物处理, 优化设计

CLC Number:

TQ 126.3

Zhongqing CHEN, Jiaxu LIU, Yanyu WANG, Hongquan JING, Cuihong HOU, Lingbo QU. Effect of K-B-Al ternary system on the melting characteristics and glass structure of tailings[J]. CIESC Journal, 2025, 76(3): 1323-1333.

陈仲卿, 刘家旭, 王艳语, 井红权, 侯翠红, 屈凌波. K-B-Al体系对磷矿熔融特性及玻璃结构的影响[J]. 化工学报, 2025, 76(3): 1323-1333.

Figures/Tables 17

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原料	元素组成/%（质量分数）								灼烧失量/%(质量分数)
原料	P₂O₅	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	K₂O	B₂O₃	灼烧失量/%(质量分数)
磷尾矿	9.22	26.81	8.67	5.74	0.62	0.80	0	0.65	44.73
低品位磷矿	18.33	43.05	0.95	6.51	0.35	0.58	0.07	0.29	29.60
蛇纹石	1.08	2.64	39.80	37.94	0	1.05	1.08	0	14.54

原料	元素组成/%（质量分数）								灼烧失量/%(质量分数)
原料	P₂O₅	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	K₂O	B₂O₃	灼烧失量/%(质量分数)
磷尾矿	9.22	26.81	8.67	5.74	0.62	0.80	0	0.65	44.73
低品位磷矿	18.33	43.05	0.95	6.51	0.35	0.58	0.07	0.29	29.60
蛇纹石	1.08	2.64	39.80	37.94	0	1.05	1.08	0	14.54

元素种类	分析方法
P₂O₅、SiO₂、CaO、MgO	《钙镁磷肥》（GB/T 20412—2021）
K₂O	《钙镁磷钾肥》（HG/T 2598—1994）
Al₂O₃	《磷矿石和磷精矿中氧化铝含量的测定》（GB/T 1871.3—1995）
Fe₂O₃	《复混肥料中铜、铁、锰、锌、硼、钼含量的测定》（GB/T 14540—2003）
B₂O₃	《地下水质分析方法第44部分：硼量的测定H酸-甲亚胺分光光度法》（DZ/T 0064.44—2021）

元素种类	分析方法
P₂O₅、SiO₂、CaO、MgO	《钙镁磷肥》（GB/T 20412—2021）
K₂O	《钙镁磷钾肥》（HG/T 2598—1994）
Al₂O₃	《磷矿石和磷精矿中氧化铝含量的测定》（GB/T 1871.3—1995）
Fe₂O₃	《复混肥料中铜、铁、锰、锌、硼、钼含量的测定》（GB/T 14540—2003）
B₂O₃	《地下水质分析方法第44部分：硼量的测定H酸-甲亚胺分光光度法》（DZ/T 0064.44—2021）

CaO/SiO₂	原料矿用量/%（质量分数）			T_S/℃
CaO/SiO₂	磷尾矿	低品位磷矿	蛇纹石	T_S/℃
1.8	80	0	20	1490
1.9	72	8	20	1482
2.0	64	16	20	1478
2.1	55	25	20	1455
2.2	47	33	20	1465
2.3	38	42	20	1467
2.4	30	50	20	1474
2.5	21	59	20	1482
2.6	12	68	20	1490
2.7	0	80	20	1494