铜渣/电解锰渣基磷酸盐胶凝材料的制备及其形成机理探讨  

Preparation and mechanism of copper slag/electrolytic manganese residue-based phosphate cementitious materials

作　　者：母维宏 和森 周新涛[1] 黄静 罗中秋[1,4] 马越 王路星 邵周军 MU Wei-hong;HE Sen;ZHOU Xin-tao;HUANG Jing;LUO Zhong-qiu;MA Yue;WANG Lu-xing;SHAO Zhou-jun(Faculty of Chemical Engineering,Kunming University of Science and Technology,Kunming 650500,Yunnan Province,China;Shenzhen Qianhai Dongjiang Environmental Protection Technology Service Co.,Ltd.,Shenzhen 518000,Guangdong Province,China;Faculty of Mechanical and Electrical Engineering,Xichang University,Xichang 615000,Sichuan Province,China;The Higher Educational Key Laboratory for Phosphorus Chemical Engineering of Yunnan Province,Kunming University of Science and Technology,Kunming 650500,Yunnan Province,China)

机构地区：[1]昆明理工大学化学工程学院,云南昆明650500 [2]深圳市前海东江环保科技服务有限公司,广东深圳518000 [3]西昌学院机械与电气工程学院,四川西昌615000 [4]昆明理工大学云南省高校磷化工重点实验室,云南昆明650500

出　　处：《化学工程》2020年第10期23-28,51,共7页Chemical Engineering(China)

基　　金：国家自然科学基金地区基金(51662024,21866018);昆明理工大学引进人才科研启动基金资助项目(KKSY201605021);昆明理工大学分析测试基金(2016T20160009);云南科技厅青年基金(2017FD093);云南教育厅资助性项目(2017ZZX147)。

摘　　要：为提高铜渣(CS)的综合利用率和拓展电解锰渣(EMR)的处理途径,采用富含铁氧化物的CS和含Mn、NH 3-N的EMR与磷酸二氢钠(P)制备铜渣/电解锰渣基磷酸盐胶凝材料,考察CS∶P质量比、EMR掺量对胶凝材料力学性能及毒性浸出的影响,并采用SEM/EDS和XRD表征材料的微观结构和物相组成,揭示其形成机理。实验结果表明:随着CS∶P的增加,材料的抗压强度先增大后减小;当EMR掺量为15%—40%时,材料中Mn和NH3-N浸出质量浓度均满足GB—8978标准限值(Mn:2.0 mg/L;NH3-N:15.0 mg/L)。SEM/EDS和XRD分析结果表明,材料可水化生成Fe(H2PO4)3,Fe3(PO4)2,Mg(H2PO4)2等磷酸盐黏结相,而EMR中的Mn和NH3-N可转化形成Mn3(PO4)2,MnPO4·1.5H2O,Mn3(PO4)2·1.5H2O、NH4FePO4·H2O和NH4MgPO4·6H2O等低溶解度的磷酸盐化学沉淀,这些磷酸盐化合物间相互粘接形成密实整体,最终不仅使材料高强,同时还可有效固定/稳定Mn和NH 3-N。In order to improve the comprehensive utilization rate of copper slag(CS)and expand the treatment of electrolytic manganese slag(EMR),copper slag/electrolytic manganese residue-based phosphate cementing material was prepared by using rich-iron oxide in CS and EMR containing Mn and NH 3-N to react with sodium dihydrogen phosphate(P).The effects of m(CS)∶m(P)mass ratio and EMR content on the mechanical properties and toxicity leaching of cementitious materials were investigated,and the microstructure and phase compositions of the materials were characterized by SEM/EDS and XRD to reveal the formation mechanism.The experimental results showed that the compressive strength of samples increased first and then decreased with an increase of m(CS)∶m(P);when EMR content was 15%-40%,Mn and NH3-N leaching mass concentrations in the samples both meet GB-8978 standard limits(Mn 2.0 mg/L;NH3-N 15.0 mg/L).SEM/EDS and XRD analyses results show that the material could be hydrated to form phosphate bonding phases such as Fe(H2PO4)3,Fe3(PO4)2,Mg(H2PO4)2,and Mn and NH3-N in EMR could be converted into low solubility phosphate chemical precipitation such as Mn3(PO4)2,MnPO4·1.5H2O,Mn3(PO4)2·1.5H2O,NH4FePO4·H2O and NH4MgPO4·6H2O.These phosphate compounds adhered to each other to form a dense whole,which not only made the material high in strength,but also effectively solidified/stabilized Mn and NH3-N.

关 键 词：铜渣 电解锰渣 磷酸盐胶凝材料 形成机理 

分 类 号：X781[环境科学与工程—环境工程]