K-B-Al体系对磷矿熔融特性及玻璃结构的影响

doi:10.11949/0438-1157.20240833

摘要/Abstract

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

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

中图分类号:

TQ 126.3

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.

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.

图/表 17

表1 原料矿主要元素组成

Table 1 Composition of main elements in raw ore

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

图1 磷尾矿热法活化流程

Fig.1 Thermal activation process of phosphate tailings

表2 各元素含量分析方法

Table 2 Analysis method of each element content

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）

表3 不同CaO/SiO2对原料矿流动温度TS的影响

Table 3 Effect of different CaO/SiO2 on TS of raw ore

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

表4 单因素实验结果

Table 4 Results of single factor experiment

用量/%（质量分数）			流动温度T_F/℃
KCl	B₂O₃	Al₂O₃	流动温度T_F/℃
3	6	0	1286
7	6	0	1252
11	6	0	1221
15	6	0	1201
19	6	0	1210
11	2	0	1306
11	6	0	1221
11	10	0	1141
11	15	0	1143
11	8	0	1172
11	8	1.5	1163
11	8	3	1147
11	8	5	1144

表5 参数编码和取值

Table 5 Parameter coding and value selection

自变量	单位	编码变量和级别
自变量	单位	-1	0	1
KCl	%（质量分数）	7	11	15
B₂O₃	%（质量分数）	6	8	10
Al₂O₃	%（质量分数）	0	1.5	3

表6 不同助剂添加量对流动温度的影响

Table 6 Effect of different flux addition on flow temperature

KCl/% （质量分数）	B₂O₃/% （质量分数）	Al₂O₃/% （质量分数）	T_F/℃
11	10	3.0	1129
11	8	1.5	1160
7	10	1.5	1135
11	8	1.5	1162
15	8	0	1167
15	10	1.5	1144
7	8	3.0	1176
15	6	1.5	1222
11	6	0	1221
11	10	0	1141
11	8	1.5	1169
11	8	1.5	1162
7	8	0	1180
15	8	3.0	1146
11	8	1.5	1160
11	6	3.0	1189
7	6	1.5	1232

图2 K-B-Al三元体系对流动温度（TF）的影响

Fig.2 Influence of K-B-Al ternary system on flow temperature (TF)

表7 K-B-Al对流动温度影响的方差分析结果

Table 7 ANOVA results of influence of K-B-Al on flowing temperature

Source	Sum of squares	F-value	P-value
model	14507.58	23.81	0.0002
A-KCl	242.00	3.57	0.1006
B-B₂O₃	12403.12	183.19	<0.0001
C-Al₂O₃	595.13	8.79	0.0210
AB	90.25	1.33	0.2862
AC	72.25	1.07	0.3360
BC	100.00	1.48	0.2636
A²	337.27	4.98	0.0608
B²	576.38	8.51	0.0224
C²	77.85	1.15	0.3192
residual	473.95	—	—
lack of fit	418.75	10.11	0.0244
pure error	55.20	—	—
cor total	14981.53	—	—

图3 熔融时间对四种配料磷活化率的影响GF1—K∶B∶Al=11∶10∶3; GF2—K∶B∶Al=11∶10∶0; GF3—K∶B∶Al=7∶10∶1.5; GF4—K∶B∶Al=15∶10∶1.5

Fig.3 Effect of melting time on phosphorus activation rate of four schemes

图4 熔融时间为5 min时四种配料主要营养元素的活化效果

Fig.4 Activation effect of main nutrient elements of four schemes when melting time is 5 min

图5 四种熔融温度下水淬玻璃肥料的XRD谱图

Fig.5 XRD patterns of water-quenched glass fertilizer at four melting temperatures

表8 四种硅氧四面体Q n 在红外光谱图中对应峰位［29］

Table 8 Peak positions and shapes of four silicon-oxygen tetrahedrons Q n in infrared spectra［29］

结构单元	Q ⁿ	振动峰位置/cm^-1
[SiO₄]	Q⁰	850~875
[Si₂O₇]	Q¹	920~950
[Si₂O₆]	Q²	980~1020
[Si₂O₅]	Q³	1050~1080

图6 温度对硅氧结构数量的影响

Fig.6 Effect of temperature on the number of silica-oxygen structures

图7 B2O3添加量对硅氧结构数量的影响

Fig.7 Effect of B2O3 on the number of silica-oxygen structures

图 8 Al2O3含量为0~3%的Gaussian拟合结果和红外谱图

Fig.8 FTIR spectra and Gaussian fitting results for Al2O3 content of 0~3%

图9 K-B-Al体系添加前后活化产物的元素摩尔含量和XPS图谱比较

Fig.9 Comparison of elemental molar content and XPS spectra of activation products before and after addition of K-B-Al system

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