不同活化方式下硅质铁尾矿的粉磨特性与胶凝活性

doi:10.12068/j.issn.1005-3026.2024.07.015

摘要/Abstract

摘要：

机械活化是提高尾矿活性的常用方法，将化学活化剂加入粉磨体系中的机械-化学活化方式是更为有效的手段.使用5种活化剂，采用了单掺和复配的方式对硅质铁尾矿（iron ore tailings，IOTs）粉磨特性及早期胶凝活性的影响进行对比分析.通过机械活化、机械-化学活化2种方式制备铁尾矿粉，测定2种活化方式磨细后IOTs的粉磨特性——比表面积、颗粒粒径分布（PSD）及3，7，28 d胶凝活性，利用XRD和SEM分析水化产物.结果表明：在相同的粉磨时间内，各活化剂的加入均能提高IOTs比表面积，粉磨90 min时添加复合活化剂的机械-化学活化与机械活化相比最多提高30.43%；活化剂的加入提高IOTs粉磨效率使PSD区间更窄；水化早期胶凝体系的强度提高主要是活化剂可促进钙矾石形成，后期强度提高是因为尾矿活性提高.本研究对硅质铁尾矿的高效利用具有重要意义.

关键词: 硅质铁尾矿, 机械-化学活化, 粉磨特性, 胶凝活性, 水化产物

Abstract:

Mechanical activation is a commonly used method to improve the activity of tailings， and adding chemical activators to the grinding system is a more effective method. Five types of activators were used to compare and analyze the grinding characteristics and early gelation activity of siliceous iron ore tailings （IOTs） using single and composite methods. Iron ore tailings powder was prepared by mechanical activation and mechanochemical activation， and the grinding characteristics of IOTs after grinding were measured， including specific surface area， particle size distribution （PSD）， and gelation activity at 3， 7， 28 d. The hydration products were analyzed by using XRD and SEM. The conclusion shows that the addition of various activators can increase the specific surface area of IOTs within the same grinding time， and the mechanical chemical activation with the addition of composite activators at 90 minutes of grinding can increase by up to 30.43% compared with mechanical activation. The addition of activators improves the grinding efficiency of IOTs， resulting in a narrower PSD range. The strength increase of cementitious system in the early stage of hydration is mainly due to the fact that activator can promote the formation of ettringite， while the strength increase in the later stage is due to the improvement of tailings activity. This study is of great significance for the efficient utilization of siliceous iron ore tailings.

Key words: siliceous iron ore tailings, mechanical?chemical activation, grinding characteristics, gelling activity, hydration products

中图分类号:

TU 528

王述红, 刘长宇, 侯钦宽, 曹莹. 不同活化方式下硅质铁尾矿的粉磨特性与胶凝活性[J]. 东北大学学报（自然科学版）, 2024, 45(7): 1028-1036.

Shu-hong WANG, Chang-yu LIU, Qin-kuan HOU, Ying CAO. Grinding Characteristics and Gelling Activity of Siliceous Iron Ore Tailings Under Different Activation Modes[J]. Journal of Northeastern University(Natural Science), 2024, 45(7): 1028-1036.

图/表 20

表1 P.I 42.5水泥性能

Table 1 P.I 42.5 cement performance

比表面积/(m²·kg^-1)	凝结时间/min		抗压强度/MPa
比表面积/(m²·kg^-1)	初凝	终凝	3 d	7 d	28 d
358	172	234	26.45	33.09	46.85

表2 水泥和铁尾矿的化学组成（质量分数） (%)

Table 2 Chemical composition of cement and iron tailings （mass fraction）

材料	SiO₂	Al₂O₃	CaO	Fe₂O₃	MgO	SO₃	Na₂O
水泥	20.60	4.57	63.27	2.59	3.29	2.11	0.55
铁尾矿	74.89	4.39	4.28	9.78	4.52	0.47	0.59

图1 原状IOTs颗粒形貌

Fig.1 Morphology of undisturbed IOTs particles

图2 不同粉磨时间下的IOTs比表面积

Fig.2 IOTs specific surface area under different grinding time

图3 粉磨180 min的IOTs球磨罐

Fig.3 IOTs ball mill jar for 180 min grinding

图4 掺机械活化IOTs水泥胶砂抗压强度及活性指数

Fig.4 Compressive strength and activity index of cement mortar mixed with mechanically activated IOTs

图5 单一活化剂剂量对IOTs比表面积的影响

Fig.5 Effect of single activator dosage on specific surface area of IOTs

图6 单一活化剂对IOTs胶凝活性的影响

Fig.6 Effect of single activator on IOTs gelling activity

图7 复合活化剂掺量对IOTs比表面积的影响

Fig.7 Effect of composite activators dosage on specific surface area of IOTs

图8 复合活化剂掺量对IOTs胶凝活性的影响

Fig.8 Effect of composite activators dosage on IOTs gelling activity

图9 粉磨时间对IOTs比表面积的影响

Fig.9 Effects of grinding time on IOTs specific surface area

图10 粉磨时间对IOTs胶凝活性的影响

Fig.10 Effects of grinding time on IOTs gelling activity

图11 不同活化方式的粒径分布曲线（a）—机械活化；（b）—机械-化学活化.

Fig.11 Particle size distribution curves of different activation modes

表3 不同活化方式下IOTs的颗粒粒径分布 (%)

Table 3 The particle size of IOTs under different activation modes

编号	体积分数
编号	<1.13 μm	1.13~4.03 μm	4.04~9.86 μm	9.87~21.2 μm	21.3~40.1 μm	40.2~58.9 μm	>58.9 μm
A1	4.50	13.99	15.37	17.79	18.26	11.93	18.14
A2	7.51	21.16	19.27	20.92	19.50	7.88	3.72
A3	9.56	23.65	19.43	20.91	17.83	6.18	2.43
A4	11.48	24.9	19.28	20.24	16.27	5.35	2.49
A5	12.24	25.69	19.35	20.33	15.64	4.89	1.85
A6	5.14	28.54	20.19	16.01	9.42	1.97	18.72
D1	2.82	16.99	18.79	19.01	21.18	14.11	7.10
D2	4.58	24.35	23.51	24.17	16.55	3.74	3.09
D3	6.95	29.66	23.59	22.96	12.83	2.30	1.39
D4	8.68	31.79	23.21	21.70	11.18	2.27	1.92
D5	8.09	33.30	23.77	21.41	9.80	2.26	1.38

图12 IOTs颗粒分布（a）—机械活化；（b）—机械-化学活化.

Fig.12 Particle distribution of IOTs

图13 活化尾矿RRB方程（a）—机械活化；（b）—机械-化学活化.

Fig.13 RRB equation of activated tailings

表4 铁尾矿在不同粉磨方式下RRB方程参数 (under different grinding methods)

Table 4 RRB equation parameters of iron tailings

编号	相关系数	$d e$ /μm	n
A1	0.992	27.4	0.88
A2	0.990	16.4	0.93
A3	0.988	14.5	0.91
A4	0.992	12.7	0.82
A5	0.989	11.2	0.86
A6	0.849	14.5	0.69
D1	0.972	24.1	1.05
D2	0.965	12.7	0.95
D3	0.972	9.86	0.91
D4	0.978	8.68	0.92
D5	0.970	7.64	0.93

表4 铁尾矿在不同粉磨方式下RRB方程参数 (under different grinding methods)

Table 4 RRB equation parameters of iron tailings

编号	相关系数	$d e$ /μm	n
A1	0.992	27.4	0.88
A2	0.990	16.4	0.93
A3	0.988	14.5	0.91
A4	0.992	12.7	0.82
A5	0.989	11.2	0.86
A6	0.849	14.5	0.69
D1	0.972	24.1	1.05
D2	0.965	12.7	0.95
D3	0.972	9.86	0.91
D4	0.978	8.68	0.92
D5	0.970	7.64	0.93

图14 复合胶凝体系3 d的XRD图谱

Fig.14 XRD pattern of composite cementitious system 3 d

图15 复合胶凝体系28 d的XRD图谱

Fig.15 XRD pattern of composite cementitious system 28 d

图16 水化产物微观形貌（a），（b）—A5试样3 d；（c），（d）—D3试样3 d；（e），（f）—A5试样28 d；（g），（h）—D3试样28 d.

Fig.16 The micromorphology of hydration products

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