钒钛铁尾矿复合胶凝材料的制备及性能

王长龙; 马锦涛; 杨丰豪; 张高青; 陈敬亮; 荊牮霖; 李鑫; 翟玉新; 刘枫

doi:10.7513/j.issn.1004-7638.2023.01.017

钒钛铁尾矿复合胶凝材料的制备及性能

doi: 10.7513/j.issn.1004-7638.2023.01.017

1.
河北工程大学土木工程学院, 河北邯郸 056038
2.
江西理工大学资源与环境工程学院, 江西赣州 341000
3.
中铁建设集团有限公司, 北京 100040
4.
中铁建设集团建筑发展有限公司, 河北保定 074207

基金项目: 国家重点研发计划（2018YFC1903602-01）；河北省自然科学基金（E2020402079, E2022402103）；河北省科技重大专项项目（21283804Z）；固废资源化利用与节能国家重点实验室开放基金（SWR-2020-004）；中铁建设集团有限公司科技研发计划（22-14b, 22-11b），邯郸市科学技术研究与发展计划项目（21422111260）。

详细信息

作者简介:
王长龙，1977年出生，汉，男，黑龙江七台河人，教授，博导，主要从事固废资源化利用，E-mail: baistuwong@139.com

通讯作者:
张高青，1981年出生，汉，男，河北邢台人，讲师，硕士，主要从事固废基混凝土研究，E-mail: jngczg@163.com

中图分类号: X757,TU528
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出版历程
- 收稿日期: 2022-08-31
- 刊出日期: 2023-02-28

Preparation and properties of composite cementitious materials containing vanadium-titanium iron ore tailings

1.
School of Civil Engineering, Hebei University of Engineering, Handan 056038, Hebei, China
2.
School of Resources and Environmental Engineering , Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
3.
China Railway Construction Group Co., Ltd., Beijing 100040, China
4.
Construction Development Co., Ltd., China Railway Construction Group, Baoding 074207, Hebei, China

摘要

摘要: 为促进钒钛铁尾矿高质量、规模化地有效利用，以钒钛铁尾矿为主要原料制备复合胶凝材料，采用粒度分析、力学性能测试、X 射线衍射（XRD）及扫描电镜（SEM）测试等手段，研究了钒钛铁尾矿粉磨特性、掺量对复合胶凝材料性能影响及复合胶凝材料的水化机理。结果表明：粉磨30 min的钒钛铁尾矿比表面积达到400 m²/kg，其 28 d 活性指数接近70%；当钒钛铁尾矿掺量为27%，胶砂比为 1∶3，水胶比为0.4时，所制备的复合胶凝材料3 d和28 d 抗压强度分别为14.9 MPa和 32.6 MPa，标准稠度为32.6%，凝结时间为125 min（初凝）和396 min（终凝），复合胶凝材料净浆试样14 d的收缩值较同龄期P·O 42.5水泥净浆试样收缩值低51.8%；在标准养护条件下，复合胶凝材料的水化产物主要为C-S-H凝胶、Ca(OH)₂、Mg(OH)₂和钙矾石（AFt），钒钛铁尾矿水化反应后残余矿物相石英和透辉石颗粒与水化产物的凝聚效应为复合胶凝材料的强度提供了保障，透辉石水化生成Mg(OH)₂对胶凝体系早期自收缩起到抑制作用。
- 钒钛铁尾矿 /
- 复合胶凝材料 /
- 掺量 /
- 透辉石 /
- 凝聚效应
Abstract: In order to improve the high-quality and large-scale effective utilization of vanadium-titanium iron ore tailings (VIOTs), composite cementitious materials (CCM) were prepared with VIOTs as the main raw materials. The effects of grinding characteristics of VIOTs, content of VIOTs on the properties of CCM and hydration mechanism of CCM were investigated via means of particle size analysis, mechanical property test, X-ray diffraction (XRD) and scanning electron microscope (SEM). The results show that the specific surface area of VIOTs grinding for 30 minutes reaches 400 m²/kg, and its 28-day activity index is close to 70%. When the content of VIOTs is 27%, the cement-sand ratio is 1∶3 and the water-binder ratio is 0.4, the 3-day and 28-day compressive strength of the CCM are 14.9 MPa and 32.6 MPa respectively, the standard consistency is 32.6%, the initial setting time is 125 min and the final setting time is 396 min. The 14-day shrinkage value of CCM paste is 51.8% lower than that of P·O 42.5 cement paste at the same age. The hydration products of the CCM are mainly C-S-H gel, Ca(OH)₂, Mg(OH)₂ and ettringite (AFt) under standard curing conditions, and the coagulation effect of quartz and diopside particles and hydration products after the hydration reaction of vanadium-titanium iron ore tailings is the guarantee for the strength of the CCM. The hydration of diopside to form Mg(OH)₂ can inhibit the early self-shrinkage of the cementitious system.
- vanadium-titanium iron ore tailings (VIOTs) /
- composite cementitious materials (CCM) /
- content /
- diopside /
- coagulation effect

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图 1 原料的XRD图谱

（a）钒钛铁尾矿；（b）粉煤灰；（c）矿渣粉；（d）水泥

Figure 1. XRD patterns of raw materials

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图 2 不同粉磨时间钒钛铁矿尾矿粒度累积分布

Figure 2. Cumulative distribution of VIOTs with different fineness

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图 3 不同粉磨时间钒钛铁矿尾矿活性指数

Figure 3. Activity index of VIOTs with different grinding time

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图 4 水泥和复合胶凝材料净浆试样体积稳定性比较

Figure 4. Volume stability comparison between pure cement and CCM paste

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图 5 复合胶凝材料净浆的XRD图谱

Figure 5. XRD patterns of CCM paste

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图 6 养护3 d和28 d龄期水化产物的SEM形貌

（a）水泥，养护3d；（a1）水泥，养护28d；（b）复合胶凝材料，养护3d；（b1）复合胶凝材料，养护28d

Figure 6. SEM images of hydration produces after curing 3 d and 28 d

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表 1 原料的化学成分

Table 1. Chemical compositions of raw materials %

原料	CaO	SiO₂	Fe₂O₃	MgO	Al₂O₃	TiO₂	Na₂O	K₂O	SO₃	烧失量	其他
钒钛铁尾矿	21.62	44.47	10.78	11.21	7.39	0.86	0.55	0.23	0.09	2.08	0.72
粉煤灰	3.25	45.94	4.36	0.40	35.17	1.35		0.42	0.31	7.86	0.94
矿渣粉	39.12	29.88	0.78	9.06	14.77	2.19	0.53	0.41	1.81	0.62	0.83
水泥	56.10	23.26	2.69	3.96	6.89	0.40	0.46	0.67	2.12	3.02	0.43

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表 2 水泥的主要理化性质

Table 2. Main physical and chemical properties of cement

表观密度/(kg·m⁻³)	细度/(m²·kg⁻¹)	凝结时间/min		28 d强度/MPa
表观密度/(kg·m⁻³)	细度/(m²·kg⁻¹)	初凝	终凝	抗折	抗压
3.08×10³	356	55	365	7.2	60.7

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表 3 不同粉磨时间钒钛铁尾矿的特征粒径及比表面积

Table 3. Characteristic particle size and specific surface area of VIOTs at different grinding times

磨矿时间/min	特征粒径/μm			比表面积/(m²·kg⁻¹）
磨矿时间/min	D₁₀	D₅₀	D₉₀	比表面积/(m²·kg⁻¹）
10	6.839	99.462	277.966	158
20	2.733	35.251	135.541	354
30	1.822	18.245	79.059	400
40	1.417	13.395	65.356	485
50	1.120	10.408	58.900	566

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表 4 复合胶凝材料配合比

Table 4. Mix proportion of CCM

编号	原材料配比/%				抗压强度/MPa
编号	水泥	钒钛铁尾矿粉	矿渣粉	粉煤灰	3 d	28 d
A0	100				25.4	52.6
B1	30		35	35	15.1	32.6
B2	30	35	35		14.6	31.1
B3	30	35		35	9.7	21.7
C1	30	15	39	16	16.4	34.9
C2	30	27	27	16	14.9	32.6
C3	30	39	15	16	13.5	28.4

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表 5 复合胶凝材料的工作性能

Table 5. Working property of CCM

标准稠度/%	凝结时间/min		安定性/mm
标准稠度/%	初凝	终凝	试件1	试件2	均值
32.6	125	396	2.0	2.5	2.25

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