掺杂锂渣的硅酸盐水泥熟料的烧成特性及水化性能研究

doi:10.19964/j.issn.1006-4990.2024-0421

摘要/Abstract

摘要：

锂渣是金属锂在冶炼过程中产生的工业固体废弃物，综合利用锂渣具有十分重要的现实意义。以锂渣为添加剂，研究了其掺入量对生料易烧性的影响规律，使用XRD与SEM等测试技术表征了不同熟料的相组成与微观结构，并结合水泥胶砂试样抗压强度及孔隙结构特征的变化规律，揭示了锂渣改善硅酸盐水泥熟料质量的机理。结果表明：当锂渣掺入量为5%（质量分数）时，水泥熟料具有最佳的水化性能；胶砂试样养护3、28、90 d后，抗压强度分别为38.16、58.35、75.61 MPa。锂渣的掺入丰富了生料中K₂O、Na₂O与TiO₂等氧化物的含量，降低了液相的黏度，这不仅显著促进了CaO的溶解，加速了水泥熟料的烧成，而且有助于C₃S和C₃A的生成。此外，锂渣中的Al³⁺通过置换C₃S和C₂S中的Si⁴⁺提高物相的水化活性。故锂渣的掺入显著改善了胶砂制品的致密度，减少了胶砂试样中的多害孔与有害孔数量，进而赋予试样理想的抗压强度。研究结果为锂渣的综合利用提供了理论基础和技术支持。

关键词: 锂渣, 易烧性, 水泥熟料, 结构与性能, 水化特性

Abstract:

Lithium slag is an industrial solid waste generated during the smelting process of metallic lithium，of which comprehensive utilization has received significant practical significance.Based on this，the effect of lithium slag additive on the burnability of raw materials was investigated.XRD and SEM techniques were applied to characterize the phase composition and microstructure of different clinkers.Meanwhile the changes in compressive strength and pore structure characteristics of cement mortar samples were analyzed.Base on the above results，the improving mechanism of the Portland cement clinker quality were revealed.Experiments showed that when the amount of lithium slag added reached 5%，cement clinker exhibited the best hydration performance.After curing for 3，28 d，and 90 d，the compressive strengths of the adhesive sand samples were as high as 38.16 MPa，58.35 MPa，and 75.61 MPa，respectively.The content of oxides including K₂O，Na₂O，and TiO₂ in the raw material was increased in accompany with a reduction in liquid phase viscosity，after adding lithium slag.This result significantly promoted the dissolution of CaO，accelerates the burning of cement clinker，and contributed to C₃S and C₃A generation.In addition，Al³⁺distributed in lithium slag could enhance its hydration activity by replacing Si⁴⁺ in C₃S and C₂S.Therefore，increasing the addition of lithium slag significantly improved the density of mortar products，and resulted to a decrease in the less multi harmful holes and harmful ones，thus endowing the mortar sample with ideal compressive strength.The research provided the theory basis and technology support for the comprehensive utilization of lithium slag

Key words: lithium slag, burnability, cement clinker, microstructure and performance, hydration characteristics

中图分类号:

TQ131.11

司斌, 薛苗苗, 赵亚莉. 掺杂锂渣的硅酸盐水泥熟料的烧成特性及水化性能研究[J]. 无机盐工业, 2025, 57(7): 120-126.

SI Bin, XUE Miaomiao, ZHAO Yali. Study on burning characteristics and hydration properties of portland cement clinker doped with lithium slag[J]. Inorganic Chemicals Industry, 2025, 57(7): 120-126.

图/表 12

表1

图1

图2

图3

图4

图5

图6

图7

图8

图9

表2

图10

参考文献 16

[1]	刘大锐，许立军，李世春，等.粉煤灰中战略金属锂的回收研究进展［J］.无机盐工业，2023，55（1）：56-63.
	LIU Darui， XU Lijun， LI Shichun，et al.Research progress of recovery of strategic metal lithium from fly ash［J］.Inorganic Chemicals Industry，2023，55（1）：56-63.
[2]	张苏江，张彦文，张立伟，等.中国锂矿资源现状及其可持续发展策略［J］.无机盐工业，2020，52（7）：1-7.
	ZHANG Sujiang， ZHANG Yanwen， ZHANG Liwei，et al.Present situation and sustainable development strategy of China′s lithium resources［J］.Inorganic Chemicals Industry，2020，52（7）：1-7.
[3]	WU Houqin， YANG Jie， XUE Kai，et al.Effects of spodumene flotation tailings as aggregates on mechanical properties of cement mortar［J］.Colloids and Surfaces A：Physicochemical and Engineering Aspects，2022，640：128346.
[4]	TAN Hongbo， ZHANG Xun， HE Xingyang，et al.Utilization of lithium slag by wet-grinding process to improve the early strength of sulphoaluminate cement paste［J］.Journal of Cleaner Production，2018，205：536-551.
[5]	董双快，吴福飞，王红，等.工业废渣替代砂浆细集料的可行性研究［J］.贵州师范大学学报（自然科学版），2020，38（2）：101- 107.
	DONG Shuangkuai， WU Fufei， WANG Hong，et al.Feasibility study of mortar with waste industrial slag as fine aggregate［J］.Journal of Guizhou Normal University（Natural Sciences），2020，38（2）：101-107.
[6]	刘晓莉，肖永贞，谢幸福，等.锂渣在陶瓷釉面砖中的应用研究［J］.陶瓷，1998（2）：37-38.
	LIU Xiaoli， XIAO Yongzhen， XIE Xingfu，et al.Research on the application of lithium slag in ceramic glazed tile［J］.Ceramics，1998（2）：37-38.
[7]	任雪红.离子固溶对阿利特介稳结构及性能的影响［D］.北京：中国建筑材料科学研究总院，2012.
	REN Xuehong.The effect of ionic solid solution on alite mesostable structure and properties［D］.Beijing：China Building Materials Research Institute，2012.
[8]	MANZANO H， DURGUN E， ABDOLHOSSEINE QOMI M J，et al.Impact of chemical impurities on the crystalline cement clinker phases determined by atomistic simulations［J］.Crystal Growth & Design，2011，11（7）：2964-2972.
[9]	李春红，费文斌.锂渣在水泥工业中的应用研究［J］.水泥技术，2001（5）：57-58.
	LI Chunhong， FEI Wenbin.Research on the application of lithium slag in the cement industry［J］.Cement Technology，2001（5）：57-58.
[10]	TRAMONTIN SOUZA M， DE MATOS P R， SILVA ANDRADE NETO J DA，et al.Single-burn clinkering of endodontic calcium silicate-based cements：Effects of ZnO in the C₃S phase formation and hydration rate［J］.Materials Letters，2022，311：131556.
[11]	GIMINEZ-MOLINA S， BLANCO M T， MARR J，et al.Phase relations in the system Ca₂SiO₄-CaO-CaSO₄-CaF₂ relevant to cement clinkering［J］.Advances in Cement Research，1992，4（14）：81-86.
[12]	LV Yang， LI Xiangguo， MA Baoguo，et al.Managing Zn wastes in C₃S：Comparison of two incorporation methods［J］.Materials and Structures，2015，48（8）：2659-2669.
[13]	商得辰.重金属离子在水泥熟料中的固化行为及作用机理研究［D］.武汉：武汉理工大学，2017.
	SHANG Dechen.Study on the solidification behavior and mechanism of heavy metal ions in cement clinker［D］.Wuhan：Wuhan University of Technology，2017.
[14]	CHABAYASHI T，OTA M， KATO H，et al.Influence of balium oxide on mineral composition of the low burning-temperature type clinker and properties of the cement［J］.Cement Science and Concrete Technology，2023，76（1）：53-59.
[15]	YANG Qingchun， WU Jiaming， JIANG Jun，et al.Study on the composition and hydration properties at early stages of high-sodium Portland cement clinker under the synergistic effects of SO₃ ［J］.Construction and Building Materials，2023，400：132696.
[16]	TURKOGLU M， BAYRAKTAR O Y， BENLI A，et al.Effect of cement clinker type，curing regime and activator dosage on the performance of one-part alkali-activated hybrid slag/clinker composites［J］.Journal of Building Engineering，2023，68：106164.

样品	w（SiO₂）	w（Al₂O₃）	w（CaO）	w（MgO）	w（Fe₂O₃）	w（K₂O）	w（Na₂O）	w（BaO）	w（TiO₂）	烧失量
锂渣	44.25	25.29	8.56	0.16	0.14	2.50	6.14	0.25	2.56	10.15
生料	12.56	4.22	37.56	2.67	2.57	0.10	0.15	0.10	0.02	40.05

锂渣掺入量/%	气孔率/%	气孔尺寸分布/%
锂渣掺入量/%	气孔率/%	< 20 nm	20~< 50 nm	50~<200 nm	200~1 000 nm	> 1 000 nm
未掺入	22.23	10.26	19.55	15.54	34.61	20.04
1	20.96	18.55	20.66	18.98	30.13	15.68
2	18.23	20.81	19.26	19.32	27.01	13.60
3	17.11	15.72	17.03	15.69	39.20	12.36
4	16.39	14.86	18.02	14.87	40.35	11.90
5	15.26	22.61	16.99	18.00	30.80	11.60

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会