工程科学学报，第39卷，第9期：1305-1312,2017年9月 Chinese Journal of Engineering,Vol.39,No.9:1305-1312,September 2017 D0l:10.13374/j.issn2095-9389.2017.09.002;htp:/journals..usth.edu.cn 复合激发剂对铜炉渣活性影响及充填材料制备 姜关照2)，吴爱祥2)，王贻明2)，王洪江12)，兰文涛12)，刘超2) 1)北京科技大学土木与资源工程学院，北京1000832)金属矿山高效开采与安全教育部重点试验室，北京100083 ☒通信作者，E-mail:wuaixiang@(126.com 摘要为了实现铜炉渣的废物利用，以碱激发方式为主研究铜炉渣制备矿用胶凝材料的可能性.选取生石灰、NOH和早 强剂组成的混合物作为复合激发剂，开展铜炉渣活性激发和充填材料制备试验，并采用X射线衍射和扫描电子显微镜对铜炉 渣水化产物进行分析.试验结果表明，各激发剂对铜炉渣活性的影响顺序依次为生石灰>早强剂>N0H,在复合激发剂的 作用下炉渣净浆试样的7和28d强度分别可以达到1.5和3.0MPa以上.铜炉渣尾砂充填料28d强度为1.0MPa,流动性良 好，满足充填材料要求.铜炉渣早期水化产物主要有片状的C(OH)2和C-S-H凝胶，随着养护时间的增加，C-S-H凝胶Ca/ Si比不断减小，水化产物结构更加致密.养护时间至28d时，铜炉渣中活性成分基本反应完全. 关键词铜炉渣：活性激发：复合激发剂最优配比：充填胶凝剂：水化机理 分类号TD853.3 Effect of compound activator on copper slag activity and preparation of filling materials JIANG Guan-zhao2),WU Ai-xiang),WANG Yi-ming'),WANG Hong-jiang'2),LAN Wen-tao2),LIU Chao2) 1)School of Civil and Resource Engineering,University of Science and Technology Beijing,Beijing 100083,China 2)State Key Laboratory of the Ministry of Education of China for High-efficient Mining and Safety of Metal Mines,Beijing 100083,China Corresponding author,E-mail:wuaixiang@126.com ABSTRACT The preparation of cementitious materials for filling primarily via the alkali-activated method was discussed to recycle copper slags.A mixture of lime,NaOH,and early-strength agent was selected as a composite activator to carry out copper slag activa- tion and filling material-preparation experiments,and the hydration products were analyzed by X-ray diffraction and scanning electron microscopy.The test results show that the effect of different activators on sample strength follows the order lime early-strength agent >NaOH.The strengths of slag paste samples at 7 and 28 d post-curing reach 1.5 and 3.0 MPa,respectively.The strength of filling materials mixed by copper slag and tailings is 1.0MPa as the curing ages are 28d,and the slurry has well fluidity.These values meet the requirements of a suitable filling material.The early hydration products of copper slag mainly include Ca(OH)2 and C-S-H gel. As the curing time increases,the Ca/Si ratio of the C-S-H gel decreases and the structure of the hydration products becomes more compact.After curing for 28 d,the active components in the copper slag are nearly completely reacted. KEY WORDS copper slag;activity excitation;optimal ratio of compound activator;filling gelling agent;hydration mechanism 铜金属行业是国民经济的重要组成部分，经济的 收铜后产生的尾矿再用于回收有价成分、充填井下采 发展越快，对铜金属的需求越大，同时冶炼产生的铜炉 空区；三是铜炉渣直接用于制备混凝土或者水泥等胶 渣也越多.为了实现经济的可持续发展，要对铜炉渣 凝材料[).对铜炉渣进行活性激发用于矿山充填是 进行综合利用.一是进行选矿回收铜：二是铜炉渣回 一种高效利用铜炉渣的新途径. 收稿日期：2016-09-06 基金项目：国家自然科学基金资助项目(51374034)：国家“十二五”科技支撑计划资助项目(2012BAB08B02):北京市科委资助项目 (Z161100001216002)工程科学学报,第 39 卷,第 9 期:1305鄄鄄1312,2017 年 9 月 Chinese Journal of Engineering, Vol. 39, No. 9: 1305鄄鄄1312, September 2017 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2017. 09. 002; http: / / journals. ustb. edu. cn 复合激发剂对铜炉渣活性影响及充填材料制备 姜关照1,2) , 吴爱祥1,2) 苣 , 王贻明1,2) , 王洪江1,2) , 兰文涛1,2) , 刘 超1,2) 1)北京科技大学土木与资源工程学院, 北京 100083 2) 金属矿山高效开采与安全教育部重点试验室, 北京 100083 苣通信作者, E鄄mail: wuaixiang@ 126. com 摘 要 为了实现铜炉渣的废物利用,以碱激发方式为主研究铜炉渣制备矿用胶凝材料的可能性. 选取生石灰、NaOH 和早 强剂组成的混合物作为复合激发剂,开展铜炉渣活性激发和充填材料制备试验,并采用 X 射线衍射和扫描电子显微镜对铜炉 渣水化产物进行分析. 试验结果表明,各激发剂对铜炉渣活性的影响顺序依次为生石灰 > 早强剂 > NaOH,在复合激发剂的 作用下炉渣净浆试样的 7 和 28 d 强度分别可以达到 1郾 5 和 3郾 0 MPa 以上. 铜炉渣尾砂充填料 28 d 强度为 1郾 0 MPa,流动性良 好,满足充填材料要求. 铜炉渣早期水化产物主要有片状的 Ca(OH)2和 C鄄鄄S鄄鄄H 凝胶,随着养护时间的增加,C鄄鄄S鄄鄄H 凝胶 Ca / Si 比不断减小,水化产物结构更加致密. 养护时间至 28 d 时,铜炉渣中活性成分基本反应完全. 关键词 铜炉渣; 活性激发; 复合激发剂最优配比; 充填胶凝剂; 水化机理 分类号 TD853郾 3 Effect of compound activator on copper slag activity and preparation of filling materials JIANG Guan鄄zhao 1,2) , WU Ai鄄xiang 1,2) 苣 , WANG Yi鄄ming 1,2) , WANG Hong鄄jiang 1,2) , LAN Wen鄄tao 1,2) , LIU Chao 1,2) 1) School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China 2) State Key Laboratory of the Ministry of Education of China for High鄄efficient Mining and Safety of Metal Mines, Beijing 100083, China 苣Corresponding author, E鄄mail: wuaixiang@ 126. com ABSTRACT The preparation of cementitious materials for filling primarily via the alkali鄄activated method was discussed to recycle copper slags. A mixture of lime, NaOH, and early鄄strength agent was selected as a composite activator to carry out copper slag activa鄄 tion and filling material鄄preparation experiments, and the hydration products were analyzed by X鄄ray diffraction and scanning electron microscopy. The test results show that the effect of different activators on sample strength follows the order lime > early鄄strength agent > NaOH. The strengths of slag paste samples at 7 and 28 d post鄄curing reach 1郾 5 and 3郾 0 MPa, respectively. The strength of filling materials mixed by copper slag and tailings is 1郾 0 MPa as the curing ages are 28 d, and the slurry has well fluidity. These values meet the requirements of a suitable filling material. The early hydration products of copper slag mainly include Ca(OH)2 and C鄄鄄S鄄鄄H gel. As the curing time increases, the Ca / Si ratio of the C鄄鄄 S鄄鄄 H gel decreases and the structure of the hydration products becomes more compact. After curing for 28 d, the active components in the copper slag are nearly completely reacted. KEY WORDS copper slag; activity excitation; optimal ratio of compound activator; filling gelling agent; hydration mechanism 收稿日期: 2016鄄鄄09鄄鄄06 基金项目: 国家自然科学基金资助项目( 51374034 );国家“ 十二五冶 科技支撑计划资助项目( 2012BAB08B02 );北京市科委资助项目 (Z161100001216002) 铜金属行业是国民经济的重要组成部分,经济的 发展越快,对铜金属的需求越大,同时冶炼产生的铜炉 渣也越多. 为了实现经济的可持续发展,要对铜炉渣 进行综合利用. 一是进行选矿回收铜;二是铜炉渣回 收铜后产生的尾矿再用于回收有价成分、充填井下采 空区;三是铜炉渣直接用于制备混凝土或者水泥等胶 凝材料[1鄄鄄4] . 对铜炉渣进行活性激发用于矿山充填是 一种高效利用铜炉渣的新途径