2.Jiangxi Copper Technology Institute Co.,Ltd.,Nanchang330001,China
Citations
CHEN Zhihua,YU Hu,WANG Quanyong. Preparation of roadbed materials using copper tailings[J]. Copper Engineering,2025(6):129-137.
Abstract
Copper tailings pose a critical challenge to sustainable mining development due to their massive production volume, difficulties in large-scale disposal, and high safety risks associated with tailings pond storage. This study developed subgrade materials using copper tailings as the primary raw material, supplemented with plastic clay and cement. Comprehensive experimental characterization was conducted, including compaction tests, unconfined compressive strength (UCS) tests, California Bearing Ratio (CBR) tests, freeze-thaw cycle tests, wet-dry cycle tests, leaching toxicity analysis, and microstructural characterization. Key findings demonstrated that the compressive strength increased significantly with higher cement content. At 5% cement content (by mass), the 7-day UCS reached 5.23 MPa. After 5 freeze-thaw cycles, the compressive strength ratio (BDR) exceeded 80%. Following 25 wet-dry cycles, the retained strength remained above 3 MPa. Heavy metal ion concentrations in leachates complied fully with GB/T 5749—2022 Standards for Drinking Water Quality limits. This research comprehensively validated the favorable mechanical properties, durability, and environmental compatibility of copper tailings-based subgrade materials. The results confirmed the technical feasibility of utilizing copper tailings as the principal raw material for subgrade construction, providing a novel pathway for large-scale disposal and resource utilization of copper tailings. This approach held significant promise for advancing tailings-free mining initiatives and promoting sustainable green mining practices.
Keywords
copper tailing;roadbed material;mechanical property;durability;comprehensive utilization of resource;
铜是我国重要的战略性矿产资源,在国民经济发展和基础设施建设中具有举足轻重的意义[ 杨航,李伟光,申士富,等. 江西某铜尾矿制备发泡陶瓷的正交试验研究[J]. 铜业工程,2019(2):78-86. 1]。铜矿开采是重要的基础性产业之一,而铜尾矿是铜矿开采、破碎、粉磨、选别后剩余的固体废弃物。随着铜矿开采力度的加大和矿石品位的下降,铜尾矿的产量逐渐增加[ 王国彬,肖庆飞,田厚源,等. 我国铜尾矿规模化消纳的研究进展[J]. 有色金属工程,2024,14(9):169-183. 2]。据统计,2023年我国尾矿的总产生量超过14亿吨,其中铜尾矿产生量超过3.6亿吨,而综合利用率仅为30.13%,大部分尾矿仍以堆存于尾矿库的形式进行处理[ 张鸽,张弛,林星杰,等. 双碳背景下铜尾矿综合利用方向探讨[J]. 矿冶,2024,33(4):600-606. 陈玉芳,朱灿. 铜尾矿库尾矿全粒径规模化低碳消纳研究[J]. 铜业工程,2022(5):31-37. 3-4]。尾矿的堆存不仅占用了大量的土地,而且还会对土壤、地表水和地下水造成潜在的环境安全风险[ XU R S,TONG H,KONG F H,et al. Potential of copper tailings as supplementary siliceous materials in the preparation of autoclaved aerated concrete[J]. Journal of Building Engineering,2024,98:111250-111250. 5]。
近年来,针对铜尾矿的综合利用已开展了较多研究[ 李炳蓉,于虎,林清泉,等. 循环经济模式下铜尾矿资源综合利用研究进展[J]. 铜业工程,2025(3):93-105. YI Y R,JAABAY D,LI C H,et al. Study on the gelation performance of mechanically wet-activated copper tailings[J]. Environmental Science and Pollution Research International,2025,32(9):5320-5331. 6-7]。主要包括:①有价金属再回收,采用浮选、浸出(酸浸/生物浸出)及选冶联合工艺回收残余铜、铁、金、银等元素[ BAKALARZ A,DUCHNOWSKA M. Analysis of the possibility of copper recovery from flotation stratiform copper ore tailings[J]. Mineral Processing and Extractive Metallurgy Review,2024,45(8):943-949. CONIĆ V,JANOŠEVIĆ M,BOŽIĆ D S,et al. Copper,zinc,and lead recovery from jarosite Pb–Ag tailings waste (part 2)[J]. Minerals,2024,14(8):791. 8-9];②环境修复材料应用,利用其吸附性、碱性或矿物组成,处理废水或修复酸性土壤及矿区环境[ 叶燕飞. 铜尾矿对模拟黑臭水中COD的净化实验研究[J]. 广东化工,2025,52(7):113-115. 毛喆,杨涛涛,张金桃,等. 基于铜尾矿生态化利用的矿山修复技术试验研究[J]. 地球环境学报,2024,15(5):790-798. 10-11];③用于烧结建材的制备,将尾矿作为原料或掺合料用于生产砖、瓦、陶粒、微晶玻璃等烧结制品[ 徐伟,鲁亚,刘松柏,等. 碱激发-碳养护对铜尾矿固化砖的作用机理研究[J]. 硅酸盐通报,2023,42(1):188-195,221. 李伟光,林荣琪,宋厚彬,等. 高硫铜尾矿制备多孔陶瓷材料及其孔结构性能研究[J]. 矿产保护与利用,2024,44(2):91-98. CHENG Y,LI J R,QIN C,et al. Template-free route to fabricate extra-lightweight ceramsite with a single large pore structure[J]. Ceramics International,2023,49(22):36446-36457. 12-14];④用于矿山充填材料,通过胶凝材料固化尾矿,形成膏体或高浓度尾砂胶结充填体,用于回填井下采空区[ 陈贤树,何勤,曲生华,等. 高硫超细铜尾矿充填胶凝材料的研究与应用[J]. 新型建筑材料,2020,47(9):107-110,150. 郭万进,吴明海,王阳,等. 我国铜矿尾矿资源化利用技术现状及进展[J]. 矿产综合利用,2023(5):127-134. 15-16]。尽管这些技术为铜尾矿资源化提供了多元途径,但其规模化消纳能力仍面临显著瓶颈,难以消纳历史堆存的巨量尾矿[ 石孟利. 铜尾矿的稳定固化及安全处置工艺研究[D]. 昆明:昆明理工大学,2024. 李亚民,黄凌云,李汶交,等. 有色金属矿山尾矿资源化利用研究进展[J]. 矿冶,2023,32(4):93-103. 17-18]。因此,探索能够大规模、高效消纳历史堆存及新增铜尾矿的新型技术路径,已成为当前行业亟待解决的关键问题。本研究提出的铜尾矿基路基材料制备技术,正是面向这一重大需求的有益探索。
铜尾矿由江西铜业集团有限公司提供,塑性土取自九江市某取土场,水泥为强度等级为42.5的普通水泥。分别利用X射线荧光光谱(XRF)和X射线衍射光谱(XRD)对铜尾矿进行化学成分和物相组成分析,结果见表1和图1。由表1可知,铜尾矿的主要化学成分包括Si,Al,K,Ca,Fe。由图1可知,铜尾矿的主要物相组成为石英、长石、云母以及透长石,铜尾矿的成分稳定,可作为路基材料的原材料使用[ PEI T R,ZHENG Y,WANG Y L,et al. Utilization of copper tailings in the preparation of low-calcium Portland cement clinker and carbonation-hardening mechanism[J]. Construction and Building Materials,2024,457:139362. 21]。利用马尔文粒度分析仪对铜尾矿和塑性土的粒度分布情况进行了分析,结果见图2。由图2可知:铜尾矿粒度按Dv(10)为2.87 μm、Dv(50)为11.1 μm、Dv(90)为48.4 μm;塑性土粒度Dv(10)为0.886 μm、Dv(50)为6.98 μm、Dv(90)为62.2 μm。利用液塑限联合测定法对铜尾矿和塑性土的液塑限指数进行测定,结果见表2。铜尾矿的液限为17.43,塑限为11.79;塑性土的液限为31.17,塑限为14.53;塑性指数为16.64。通过向铜尾矿中复配适量塑性土可以改善铜尾矿的塑性指数。
表1 铜尾矿的主要化学成分
Table 1 Chemical components of copper tailings (%)
成分
F
Na2O
MgO
SO3
Al2O3
质量分数
0.251
0.146
0.759
2.222
18.187
成分
K2O
CaO
TiO2
Fe2O3
SiO2
质量分数
6.710
2.506
0.435
4.918
62.967
成分
ZnO
CuO
MnO
P2O5
其他
质量分数
0.154
0.152
0.132
0.256
0.205
图1 铜尾矿的XRD图谱
Fig. 1 XRD spectrum of copper tailings
图2 铜尾矿和塑性土的粒度分布图
Fig. 2 Malvern particle size distribution of copper tailings
表2 铜尾矿与塑性土的塑性指数
Table 2 Plasticity index of copper tailings and plastic soil (%)
Fig. 9 Effects of wet-dry cycle times on compressive strength of roadbed materials
2.7 微观结构分析
2.7.1 FTIR分析
为探究路基材料微观结构演变,对水泥掺量为5%、养护28 d的基准样品,以及经历不同冻融循环和干湿循环周期的样品进行了傅里叶变换红外光谱(FTIR)分析,结果见图10。其中,图10(a)展示了养护28 d样品及经1次、5次冻融循环样品的FTIR谱图;图10(b)展示了养护28 d样品及经5次、10次干湿循环样品的FTIR谱图。由图10可知,通过不同波数下的吸收带,可以对分子基团进行分析和鉴定。3597 cm−1处的吸收带与Ca(OH)2中的Ca-OH有关,这在养护28 d后的样品中强度最高,说明养护28 d后样品中仍含有较多的Ca(OH)2;冻融循环和干湿循环样品对应的吸收带相对较弱,证明冻融循环和干湿循环过程促进了样品中二次水化反应的持续进行[ KUCHARCZYK S,SITARZ M,ZAJAC M,et al. The effect of CaO/SiO2 molar ratio of CaO-Al2O3-SiO2 glasses on their structure and reactivity in alkali activated system[J]. Spectrochimica Acta Part A:Molecularand Biomolecular Spectroscopy,2018,194:163-171. 26],消耗了Ca(OH)2,提升了强度。3402 cm−1处的吸收带与样品中Si-OH的伸缩振动有关。1621 cm−1处的吸收带与H-O-H的弯曲振动有关。873 cm−1和1479 cm−1处O-C-O键的不对称伸缩振动吸收带与CO32−有关,这与样品中碳酸盐的存在有关[ LIU X M,ZHAO X B,YIN H F,et al. Intermediate-calcium based cementitious materials prepared by MSWI fly ash and other solid wastes:hydration characteristics and heavy metals solidification behavior[J]. Journal of Hazardous Materials,2018,349:262-271. 27]。值得注意的是,998 cm−1和1124 cm−1处的吸收带与Si-O-T(T=Si,Al)硅氧键和铝硅氧桥以及Si-O断裂硅氧桥的不对称拉伸振动有关[ KUCHARCZYK S,SITARZ M,ZAJAC M,et al. The effect of CaO/SiO2 molar ratio of CaO-Al2O3-SiO2 glasses on their structure and reactivity in alkali activated system[J]. Spectrochimica Acta Part A:Molecularand Biomolecular Spectroscopy,2018,194:163-171. 26],这代表了水泥水化产生的凝胶[ BRZEZIŃSKA-MIECZNIK J,JELEŃ P,HABERKO K,et al. The effect of NaOH and KOH treatment on the behavior of CO32− and OH− groups in natural origin hydroxyapatite[J]. Ceramics International,2017,43(15):12540-12545. 28]。在691 cm−1处的吸收带代表SO42−的伸缩振动带。474 cm−1的吸收带与Si-O-Si的弯曲振动有关。这代表了硅酸盐,包括晶体和非晶态[ SHI Z G,SHI C J,WAN S,et al. Effect of alkali dosage and silicate modulus on carbonation of alkali-activated slag mortars[J]. Cement and Concrete Research,2018,113:55-64. 29]。
为了揭示微观结构演变与宏观性能的关联,对水泥掺量为5%、养护28 d的基准样品,以及经历不同冻融循环和干湿循环周期的样品进行了扫描电子显微镜(SEM)分析,结果见图11。图11(a~e)分别为养护28 d,1次、5次冻融循环,以及5次、10次干湿循环试验样品的SEM图像。由图11(a~c)可知:相较于养护28 d的样品[图11(a)],经1次冻融循环后的样品[图11(b)]表面产生了更丰富的絮状胶凝产物,这些产物填充了孔隙,紧密包裹并桥接骨料颗粒,形成更为致密的整体结构,这与其宏观强度的提升相吻合[ XU Y T,LIU X M,ZHANG Y L,et al. Investigation on sulfate activation of electrolytic manganese residue on early activity of blast furnace slag in cement-based cementitious material[J]. Construction and Building Materials,2019,229:116831. 30];然而,经5次冻融循环后[图11(c)],在低温和饱水环境的反复作用下,前期水化形成的絮状胶凝产物发生劣化,使得材料致密性降低、孔隙率增加,从而导致路基材料强度下降。通过对比图11(a,d,e)可知,经5次干湿循环后的样品[图11(d)]同样产生了更加丰富的絮状胶凝产物,水化产物的增加及其对内部孔隙结构的优化,是该阶段抗压强度得以提高的微观基础[ WANG Y G,GAO S,LIU X M,et al. Preparation of non-sintered permeable bricks using electrolytic manganese residue:Environmental and NH3-N recovery benefits[J]. Journal of Hazardous Materials,2019,378:120768. 31]。相较于冻融样品[图11(b)],干湿循环样品表面的致密性明显提高,主要是由于干湿循环过程具备的饱水和烘干阶段高于室温的条件,共同营造了更有利于持续水化和结构致密化的环境,从而使强度得到更显著提升。
Fig. 11 SEM images of road base materials:(a) Cured for 28 days;(b) After 1 freeze-thaw cycle;(c) After 5 freeze-thaw cycles;(d) After 5 wet-dry cycles;(e) After 10 wet-dry cycles
XUR S,TONGH,KONGF H,et al. Potential of copper tailings as supplementary siliceous materials in the preparation of autoclaved aerated concrete[J]. Journal of Building Engineering,2024,98:111250-111250.
YIY R,JAABAYD,LIC H,et al. Study on the gelation performance of mechanically wet-activated copper tailings[J]. Environmental Science and Pollution Research International,2025,32(9):5320-5331.
[8]
BAKALARZA,DUCHNOWSKAM. Analysis of the possibility of copper recovery from flotation stratiform copper ore tailings[J]. Mineral Processing and Extractive Metallurgy Review,2024,45(8):943-949.
[9]
CONIĆV,JANOŠEVIĆM,BOŽIĆD S,et al. Copper,zinc,and lead recovery from jarosite Pb–Ag tailings waste (part 2)[J]. Minerals,2024,14(8):791.
CHENGY,LIJ R,QINC,et al. Template-free route to fabricate extra-lightweight ceramsite with a single large pore structure[J]. Ceramics International,2023,49(22):36446-36457.
PEIT R,ZHENGY,WANGY L,et al. Utilization of copper tailings in the preparation of low-calcium Portland cement clinker and carbonation-hardening mechanism[J]. Construction and Building Materials,2024,457:139362.
KUCHARCZYKS,SITARZM,ZAJACM,et al. The effect of CaO/SiO2 molar ratio of CaO-Al2O3-SiO2 glasses on their structure and reactivity in alkali activated system[J]. Spectrochimica Acta Part A:Molecularand Biomolecular Spectroscopy,2018,194:163-171.
[27]
LIUX M,ZHAOX B,YINH F,et al. Intermediate-calcium based cementitious materials prepared by MSWI fly ash and other solid wastes:hydration characteristics and heavy metals solidification behavior[J]. Journal of Hazardous Materials,2018,349:262-271.
[28]
BRZEZIŃSKA-MIECZNIKJ,JELEŃP,HABERKOK,et al. The effect of NaOH and KOH treatment on the behavior of CO32− and OH− groups in natural origin hydroxyapatite[J]. Ceramics International,2017,43(15):12540-12545.
[29]
SHIZ G,SHIC J,WANS,et al. Effect of alkali dosage and silicate modulus on carbonation of alkali-activated slag mortars[J]. Cement and Concrete Research,2018,113:55-64.
[30]
XUY T,LIUX M,ZHANGY L,et al. Investigation on sulfate activation of electrolytic manganese residue on early activity of blast furnace slag in cement-based cementitious material[J]. Construction and Building Materials,2019,229:116831.
[31]
WANGY G,GAOS,LIUX M,et al. Preparation of non-sintered permeable bricks using electrolytic manganese residue:Environmental and NH3-N recovery benefits[J]. Journal of Hazardous Materials,2019,378:120768.