煤系固废基绿色充填材料制备及其性能研究

董猛; 李江山; 陈新; 金佳旭; 鲁龙钊

doi:10.12363/issn.1001-1986.22.05.0384

煤系固废基绿色充填材料制备及其性能研究

董猛^{1, 2,},
李江山^2,*, ,,
陈新²,
金佳旭¹,
鲁龙钊²

1.
辽宁工程技术大学土木工程学院，辽宁阜新 123000
2.
中国科学院武汉岩土力学研究所岩土力学与工程国家重点实验室，湖北武汉 430071

基金项目: 中国科学院国际合作重点项目(115242KYSB20200002)

详细信息

作者简介:
董猛，1997年生，男，辽宁铁岭人，博士研究生，从事固废资源化方面研究. E-mail：cjdpzdm@163.com

通讯作者:
李江山，1987年生，男，四川巴中人，博士，研究员，从事污染场地工程修复和固废资源化方面研究. E-mail：jsli@whrsm.ac.cn

中图分类号: TD823
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出版历程
- 收稿日期: 2022-05-18
- 修回日期: 2022-10-13
- 网络出版日期: 2022-11-27
- 刊出日期: 2022-12-24

Preparation of coal-series solid-waste-based green filling materials and their performance

DONG Meng^{1, 2,},
LI Jiangshan^2,*, ,,
CHEN Xin²,
JIN Jiaxu¹,
LU Longzhao²

1.
School of Civil Engineering, Liaoning Technical University, Fuxin 123000, China
2.
State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Science, Wuhan 430071, China

摘要

摘要:
充填技术是绿色开采的重要组成部分，研发成本低廉、性能可靠、低碳环保的充填材料，是发展充填技术的关键。采用煤矸石(CG)和煤系偏高岭土(MK)为原材料制备煤系固废基绿色充填材料，探讨配合比和碱激发剂对充填材料强度以及流动度的影响，并结合X射线衍射(XRD)、傅里叶变换红外吸收光谱仪(FTIR)、热重分析(TG)和扫描电镜能谱分析(SEM-EDS)等表征手段，揭示充填强度发展机理。综合强度、流动性和环境指标，优化充填材料配比。研究结果表明：绿色充填材料体系中，煤系偏高岭土通过碱激发水化反应起到胶凝作用，体系强度随偏高岭土的增加呈线性增长，磨细的煤矸石充当惰性填料，协同Na₂SiO₃改善流动性。该充填材料主要水化产物为N―A―S―H和沸石，Si―O―Si发生聚解，随即四面体Al―O键部分取代Si―O键，由(SiO₄)⁴⁻变成(AlO₄)⁴⁻，进一步聚合形成Si―O―Al基团。当碱激发剂中Na₂SiO₃与NaOH比例为1∶1时，聚合程度最高。水化产物填充了煤矸石颗粒间孔隙，使基质致密，提高充填材料强度。综合指标评价推荐偏高岭土与煤矸石的配比为3∶7，此时不仅满足强度和流动性的要求，而且碳排放指数仅有0.257。本研究为开发成本低廉、性能可靠、低碳环保的充填材料提供新的思路，具有较好的实用性和经济性。
- 煤矸石 /
- 煤系偏高岭土 /
- 碱激发 /
- 绿色充填材料 /
- 性能研究
Abstract:
The filling technology is an important part of green mining. The low-carbon environmental-friendly filling materials with low costs in research and development and reliable performance are critical for the development of filling technologies. The coal gangue (CG) and coal-series metakaolin (MK) were adopted as the raw materials to prepare coal-series solid-waste-base green filling materials, and the effect of the mixing proportion and alkali activator on the strength and fluidity of filling materials was discussed. In combination with the X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric (TG) analysis and scanning electron microscopy/energy dispersive x-ray spectroscopy (SEM-EDS) and other characterization measures, the filling strength development mechanism was revealed. Considering the strength, fluidity and environmental indexes, the mixing proportion of filling materials was optimized. As indicated by the research results, in the green filling material system, the coal-series metakaolin generates gelatinization effects through alkali-activated hydration reaction. The system strength is increased in a linear mode with the increase of metakaolin. The finely-grounded coal gangue is used as the inert filler that coordinates with Na₂SiO₃ to improve fluidity. The main hydration products of this filling material are N ― A ― S ― H and zeolites. Right after Si ― O ― Si depolymerization, the tetrahedral Al ― O bond takes the place of Si ― O bond, resulting in the change of (SiO₄)⁴⁻ into (AlO₄)⁴⁻. Through further polymerization, the Si ― O ― Al group is generated. When the ratio between Na₂SiO₃ and NaOH is 1∶1 in the alkali activator, the polymerization degree is the highest. The hydration products are filled into the pores of coal gangue particles, leading to dense matrix and stronger filling materials. As recommended based on the comprehensive index evaluation, the mixing ratio between metakaolin and coal gangue shall be 3∶7, which does not only meet the requirements of strength and fluidity but also provides the carbon emission index as low as 0.257. This research provides new approaches for developing the low-carbon environmental-friendly filling materials with low costs and reliable performance, and is highly practical and economically efficient.
- coal gangue /
- coal-series metakaolin /
- alkali activation /
- green filling material /
- performance research

HTML全文

图 1 原材料颗粒粒径级配曲线

Fig. 1 Particle size distribution curves of raw material particles

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图 2 原材料矿物组成

2θ—衍射角

Fig. 2 Mineral composition of raw materials

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图 3 抗压强度实验样品制备

Fig. 3 Preparation of samples used for compressive strength experiment

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图 4 不同龄期下试样的抗压强度

Fig. 4 Compressive strength of samples at different ages

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图 5 试样的流动度

Fig. 5 Fluidity of samples

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图 6 3 d和28 d龄期试样的XRD谱

Fig. 6 XRD graph of samples at the ages of 3 d and 28 d

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图 7 不同偏高岭土掺量在不同减激发剂下的FTIR谱

Fig. 7 FTIR graph of different mixing amounts of metakaolin under different alkali activators

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图 8 3 d龄期下试样的TG和DTG曲线

Fig. 8 TG and DTG curves of samples at the age of 3 d

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图 9 28 d龄期下试样的TG和DTG曲线

Fig. 9 TG and DTG curves of samples at the age of 28 d

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图 10 28 d龄期下试样的SEM-EDS图

Fig. 10 SEM-EDS diagram of samples at the age of 28 d

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图 11 流动度和3 d龄期强度指标

Fig. 11 Fluidity and strength indexes at the age of 3 d

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图 12 碳排放指标

Fig. 12 Carbon emission index

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表 1 原材料的化学组成

Table 1 Chemical composition of raw materials

原材料	各组成质量分数/%
原材料	SiO₂	Al₂O₃	Fe₂O₃	CaO	Na₂O	SO₃	Loss
偏高岭土	54.29	41.52	0.63	0.35	0.31	0.04	1.09
煤矸石	47.35	21.85	3.22	4.86	0.71	5.69	3.09

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表 2 原材料配比设计

Table 2 Mix proportion design of raw materials

编号	各成分质量分数/%			碱类型
编号	煤矸石	偏高岭土	碱外掺量	Na₂SiO₃∶NaOH
A1	30	70	10	1∶2
A2	40	60	10	1∶2
A3	50	50	10	1∶2
A4	60	40	10	1∶2
A5	70	30	10	1∶2
A6	80	20	10	1∶2
B1	30	70	10	1∶1
B2	40	60	10	1∶1
B3	50	50	10	1∶1
B4	60	40	10	1∶1
B5	70	30	10	1∶1
B6	80	20	10	1∶1
C1	30	70	10	2∶1
C2	40	60	10	2∶1
C3	50	50	10	2∶1
C4	60	40	10	2∶1
C5	70	30	10	2∶1
C6	80	20	10	2∶1
D1	30	70	10	3∶1
D2	40	60	10	3∶1
D3	50	50	10	3∶1
D4	60	40	10	3∶1
D5	70	30	10	3∶1
D6	80	20	10	3∶1

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表 3 原材料二氧化碳排放量

Table 3 Carbon dioxide emissions of raw materials

原材料	MK	CG	NaOH	Na₂SiO₃
CO₂排放量/(kg·m⁻³)	0.400	0.079	1.30	1.86

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