铜炉渣活性激发实验研究及水化机理分析
|
摘要
为了实现铜炉渣的回收利用,通过机械活化和碱激发的方式制备铜炉渣胶凝材料,并利用X线衍射(XRD)、扫描电镜(SEM)、能谱仪(EDS)和矿渣玻璃体分相结构模型对铜炉渣水化机理进行分析。研究结果表明:当比表面积为520 m~2/kg时,铜炉渣净浆试样的7 d和28 d强度分别达到2.4 MPa和3.3 MPa;当灰砂比为1:1时,铜炉渣全尾砂充填料的7 d和28 d强度分别达到0.7 MPa和1.0 MPa,满足当地矿山充填的要求。水化初期,炉渣玻璃体中的富钙相和高钙石灰共同水化生成了Ca(OH)2,其进一步与富硅相反应生成C-S-H凝胶等水化产物。随着水化反应的继续进行,试样内部的孔隙逐渐被水化产物填充并缩小至孔状,浆体结构更加致密。
In order to realize the recycling of copper slag, copper slag cementitious material was prepared by the way of mechanical activation and alkali activation, and the hydration mechanism of copper slag was analyzed by XRD, SEM, EDS and slag vitreous phase structure model. The results show that when the specific surface area of slag is 520 m~2/kg, 7 d strength and 28 d strength of copper slag paste specimen reach 2.4 MPa and 3.3 MPa, respectively. When cement sand ratio is 1:1, 7 d and 28 d strength of copper slag tailings filling reach 0.7 MPa and 1.0 MPa, respectively, meeting the requirements of local mine filling. In the early stage of hydration, the calcium-rich phase and high calcium lime generates calcium hydroxide, which further forms C-S-H gel and other hydration products with silicon-rich phase. As the hydration reaction continues, the internal pores of sample are filled with hydration products and gradually shrink into hole type, and the structure becomes denser.
In order to realize the recycling of copper slag, copper slag cementitious material was prepared by the way of mechanical activation and alkali activation, and the hydration mechanism of copper slag was analyzed by XRD, SEM, EDS and slag vitreous phase structure model. The results show that when the specific surface area of slag is 520 m~2/kg, 7 d strength and 28 d strength of copper slag paste specimen reach 2.4 MPa and 3.3 MPa, respectively. When cement sand ratio is 1:1, 7 d and 28 d strength of copper slag tailings filling reach 0.7 MPa and 1.0 MPa, respectively, meeting the requirements of local mine filling. In the early stage of hydration, the calcium-rich phase and high calcium lime generates calcium hydroxide, which further forms C-S-H gel and other hydration products with silicon-rich phase. As the hydration reaction continues, the internal pores of sample are filled with hydration products and gradually shrink into hole type, and the structure becomes denser.
引文
[1]李克庆,冯琳,高术杰.镍渣基矿井充填用胶凝材料的制备[J].北京科技大学学报,2015,37(1):1-6.LI Keqing,FENG Lin,GAO Shujie.Preparation of cementitious materials for backfilling by using nickel slag[J].Journal of University Science and Technology Beijing,2015,37(1):1-6.
[2]于霖.碱激发矿渣胶凝材料的制备及其性能研究[D].郑州:郑州大学材料科学与工程学院,2010:12-25.YU Lin.A study on the preparation and properties of alkali-aetivated slag cementitious material[D].Zhengzhou:Zhengzhou University.School of Materials Science and Engineering,2010:12-25.
[3]AL-JABRI K,TAHA R,AL-HARTHY A,et al.Use of cement by-pass dust in flowable fill mixtures[J].Cement Concrete&Aggregates,2002,24(2):53-57.
[4]ZHANG Yaojun,YANG Mengyang,KANG Le,et al.Research progresses of new type alkali-activated cementitious material catalyst[J].Journal of Inorganic Materials,2016,31(3):225-233.
[5]李茂辉,杨志强,王有团,等.粉煤灰复合胶凝材料充填体强度与水化机理研究[J].中国矿业大学学报,2015,44(4):650-655.LI Maohui,YANG Zhiqiang,WANG Youtuan,et al.Experiment study of compressive strength and mechanical property of filling body for fly ash composite cementitious materials[J].Journal of China University of Mining&Technology,2015,44(4):650-655.
[6]王强,黎梦圆,石梦晓.水泥—钢渣—矿渣复合胶凝材料的水化特性[J].硅酸盐学报,2014,42(5):629-634.WANG Qiang,LI Mengyuan,SHI Mengxiao.Hydration properties of cement-steel slag-ground granulated blast furnace slag complex binder[J].Journal of the Chinese Ceramic Society,2014,42(5):629-634.
[7]王有团,杨志强,李茂辉,等.全尾砂-棒磨砂新型胶凝充填材料的制备[J].材料研究学报,2015,29(4):291-298.WANG Youtuan,YANG Zhiqiang,LI Maohui,et al.Preparation of new backfill cementitious materials with unclassified tailings-rod milling sands[J].Chinese Journal of Materials Research,2015,29(4):291-298.
[8]闫国斌,许立顺,赵建文.利用脱硫灰烧结渣制备新型充填胶凝材料的试验[J].矿业研究与开发,2015,35(12):22-26.YAN Guobin,XU Lishun,ZHAO Jianwen.Test study on a new filling cementing material for iron tailings using sintering desulfurization ash[J].Mining Research and Development,2015,35(12):22-26.
[9]孙小巍,吴陶俊.碱激发矿渣胶凝材料的实验研究[J].硅酸盐通报,2014,33(11):3036-3040.SUN Xiaowei,WU Taojun.Experimental research of alkali-activated slag cementitious material[J].Bulletin of the Chinese Ceramic Society,2014,33(11):3036-3040.
[10]高术杰,倪文,祝丽萍,等.脱硫石膏对赤泥-矿渣胶结充填料强度性能的影响[J].中南大学学报(自然科学版),2013,44(6):2259-2266.GAO Shujie,NI Wen,ZHU Liping,et al.Effect of gypsum on strength performance of cemented backfilling materials of red mud-slag system[J].Journal of Central South University(Science and Technology),2013,44(6):2259-2266.
[11]诸培南.粒化高炉矿渣与活性关系的探讨[J].硅酸盐学报,1983,11(3):290-296.ZHU Peinan.Preliminary study on the relationship between structure and activity of blast furnace slag[J].Journal of the Chinese Ceramic Society,1983,11(3):290-296.
[12]孙家瑛,诸培南,吴初航.矿渣在碱性溶液激发下的水化机理探讨[J].硅酸盐通报,1988(6):16-25.SUN Jiaying,ZHU Peinan,WU Chuhang.Study on the hydration mechanism of slag in excitation alkaline solution[J].Bulletin of the Chinese Ceramic Society,1988(6):16-25.
[13]徐彬,蒲心诚.矿渣玻璃体分相结构与矿渣潜在水硬活性本质的关系探讨[J].硅酸盐学报,1997,25(6):105-109.XU Bin,PU Xincheng.Study on the relationship between the phase separation of slag glass and the latent hydraulic activity of bfs[J].Journal of the Chinese Ceramic Society,1997,25(6):105-109.
[14]李兵,杨仕教,王洪武,等.某冶炼厂炼铅炉渣制备胶凝材料的实验研究[J].硅酸盐通报,2014,33(3):583-588.LI Bing,YANG Shijiao,WANG Hongwu,et al.Experimental research on producing cementing material using Smelter’s lead refinery slag[J].Bulletin of the Chinese Ceramic Society,2014,33(3):583-588.
[15]董璐,高谦,南世卿,等.超细全尾砂新型胶结充填料水化机理与性能[J].中南大学学报(自然科学版),2013,44(4):1571-1576.DONG Lu,GAO Qian,NAN Shiqing,et al.Performance and hydration mechanism of new super fine cemented whole-tailings backfilling materials[J].Journal of Central South University(Science and Technology),2013,44(4):1571-1576.
[16]CIHANGIR F,ERCIKDI B,KESIMAL A,et al.Paste backfill of high-sulphide mill tailings using alkali-activated blast furnace slag:effect of activator nature,concentration and slag properties[J].Minerals Engineering,2015,83:117-127.
[17]王峰,张耀君,宋强,等.Na OH碱激发矿渣地质聚合物的研究[J].非金属矿,2008,31(3):9-11.WANG Feng,ZHAGN Yaojun,SONG Qiang,et al.Study on synthesis of geopolymer by naoh alkali-activated slag powder[J].Non-Metallic Mines,2008,31(3):9-11.
[18]陈益民,张洪滔,郭随华,等.磨细钢渣粉作水泥高活性混合材料的研究[J].水泥,2001(5):1-4.CHEN Yimin,ZHANG Hongtao,GUO Suihua,et al.Study on the finely ground steel slag as high reactivity blending materials of cement[J].Cement,2001(5):1-4.
[19]何娟,程从密,李烈军.细度对电炉钢渣活性指数的影响[J].混凝土,2011(7):77-78.HE Juan,CHENG Congmi,LI Liejun.Influence of fineness on electric arc furnace slag activity index[J].Concrete,2011(7):77-78.
[20]杨志强,高谦,王永前,等.利用金川水淬镍渣尾砂开发新型充填胶凝剂试验研究[J].岩土工程学报,2014,36(8):1498-1506.YANG Zhiqiang,GAO Qian,WANG Yongqian,et al.Experimental study on new filling cementing material using water-hardening nickel slag tailings of Jinchuan Mine[J].Chinese Journal of Geotechnical Engineering,2014,36(8):1498-1506.
[21]ZHAO Ruichao,HAN Yuexin,YANG Guang,et al.Mechanism of adsorption and aggregation of fine siderite,quartz and hematite[J].Journal of Northeastern University,2015,36(4):596-600.
[22]KRIVENKO P,PETROPAVLOVSKY O,PETRANEK V,et al.High strength alkali activated slag cements with controlled setting times and early strength gain[J].Advanced Materials Research,2015,1100:44-49.
[23]内维尔A M.混凝土性能[M].刘数华,冷发光,李新宇,等译.北京:中国建筑工业出版社,2011:369-372.NEVILLE A M.Properties of concrete[M].LIU Shuhua,LENG Faguang,LI Xinyu,et al trans.Beijing:China Architecture&Building Press,2011:369-372.
[24]ZACHARIASEN W H.The atomic arrangement in glass[J].Journal of the American Chemical Society,1932,44(10):3841-3851.
[2]于霖.碱激发矿渣胶凝材料的制备及其性能研究[D].郑州:郑州大学材料科学与工程学院,2010:12-25.YU Lin.A study on the preparation and properties of alkali-aetivated slag cementitious material[D].Zhengzhou:Zhengzhou University.School of Materials Science and Engineering,2010:12-25.
[3]AL-JABRI K,TAHA R,AL-HARTHY A,et al.Use of cement by-pass dust in flowable fill mixtures[J].Cement Concrete&Aggregates,2002,24(2):53-57.
[4]ZHANG Yaojun,YANG Mengyang,KANG Le,et al.Research progresses of new type alkali-activated cementitious material catalyst[J].Journal of Inorganic Materials,2016,31(3):225-233.
[5]李茂辉,杨志强,王有团,等.粉煤灰复合胶凝材料充填体强度与水化机理研究[J].中国矿业大学学报,2015,44(4):650-655.LI Maohui,YANG Zhiqiang,WANG Youtuan,et al.Experiment study of compressive strength and mechanical property of filling body for fly ash composite cementitious materials[J].Journal of China University of Mining&Technology,2015,44(4):650-655.
[6]王强,黎梦圆,石梦晓.水泥—钢渣—矿渣复合胶凝材料的水化特性[J].硅酸盐学报,2014,42(5):629-634.WANG Qiang,LI Mengyuan,SHI Mengxiao.Hydration properties of cement-steel slag-ground granulated blast furnace slag complex binder[J].Journal of the Chinese Ceramic Society,2014,42(5):629-634.
[7]王有团,杨志强,李茂辉,等.全尾砂-棒磨砂新型胶凝充填材料的制备[J].材料研究学报,2015,29(4):291-298.WANG Youtuan,YANG Zhiqiang,LI Maohui,et al.Preparation of new backfill cementitious materials with unclassified tailings-rod milling sands[J].Chinese Journal of Materials Research,2015,29(4):291-298.
[8]闫国斌,许立顺,赵建文.利用脱硫灰烧结渣制备新型充填胶凝材料的试验[J].矿业研究与开发,2015,35(12):22-26.YAN Guobin,XU Lishun,ZHAO Jianwen.Test study on a new filling cementing material for iron tailings using sintering desulfurization ash[J].Mining Research and Development,2015,35(12):22-26.
[9]孙小巍,吴陶俊.碱激发矿渣胶凝材料的实验研究[J].硅酸盐通报,2014,33(11):3036-3040.SUN Xiaowei,WU Taojun.Experimental research of alkali-activated slag cementitious material[J].Bulletin of the Chinese Ceramic Society,2014,33(11):3036-3040.
[10]高术杰,倪文,祝丽萍,等.脱硫石膏对赤泥-矿渣胶结充填料强度性能的影响[J].中南大学学报(自然科学版),2013,44(6):2259-2266.GAO Shujie,NI Wen,ZHU Liping,et al.Effect of gypsum on strength performance of cemented backfilling materials of red mud-slag system[J].Journal of Central South University(Science and Technology),2013,44(6):2259-2266.
[11]诸培南.粒化高炉矿渣与活性关系的探讨[J].硅酸盐学报,1983,11(3):290-296.ZHU Peinan.Preliminary study on the relationship between structure and activity of blast furnace slag[J].Journal of the Chinese Ceramic Society,1983,11(3):290-296.
[12]孙家瑛,诸培南,吴初航.矿渣在碱性溶液激发下的水化机理探讨[J].硅酸盐通报,1988(6):16-25.SUN Jiaying,ZHU Peinan,WU Chuhang.Study on the hydration mechanism of slag in excitation alkaline solution[J].Bulletin of the Chinese Ceramic Society,1988(6):16-25.
[13]徐彬,蒲心诚.矿渣玻璃体分相结构与矿渣潜在水硬活性本质的关系探讨[J].硅酸盐学报,1997,25(6):105-109.XU Bin,PU Xincheng.Study on the relationship between the phase separation of slag glass and the latent hydraulic activity of bfs[J].Journal of the Chinese Ceramic Society,1997,25(6):105-109.
[14]李兵,杨仕教,王洪武,等.某冶炼厂炼铅炉渣制备胶凝材料的实验研究[J].硅酸盐通报,2014,33(3):583-588.LI Bing,YANG Shijiao,WANG Hongwu,et al.Experimental research on producing cementing material using Smelter’s lead refinery slag[J].Bulletin of the Chinese Ceramic Society,2014,33(3):583-588.
[15]董璐,高谦,南世卿,等.超细全尾砂新型胶结充填料水化机理与性能[J].中南大学学报(自然科学版),2013,44(4):1571-1576.DONG Lu,GAO Qian,NAN Shiqing,et al.Performance and hydration mechanism of new super fine cemented whole-tailings backfilling materials[J].Journal of Central South University(Science and Technology),2013,44(4):1571-1576.
[16]CIHANGIR F,ERCIKDI B,KESIMAL A,et al.Paste backfill of high-sulphide mill tailings using alkali-activated blast furnace slag:effect of activator nature,concentration and slag properties[J].Minerals Engineering,2015,83:117-127.
[17]王峰,张耀君,宋强,等.Na OH碱激发矿渣地质聚合物的研究[J].非金属矿,2008,31(3):9-11.WANG Feng,ZHAGN Yaojun,SONG Qiang,et al.Study on synthesis of geopolymer by naoh alkali-activated slag powder[J].Non-Metallic Mines,2008,31(3):9-11.
[18]陈益民,张洪滔,郭随华,等.磨细钢渣粉作水泥高活性混合材料的研究[J].水泥,2001(5):1-4.CHEN Yimin,ZHANG Hongtao,GUO Suihua,et al.Study on the finely ground steel slag as high reactivity blending materials of cement[J].Cement,2001(5):1-4.
[19]何娟,程从密,李烈军.细度对电炉钢渣活性指数的影响[J].混凝土,2011(7):77-78.HE Juan,CHENG Congmi,LI Liejun.Influence of fineness on electric arc furnace slag activity index[J].Concrete,2011(7):77-78.
[20]杨志强,高谦,王永前,等.利用金川水淬镍渣尾砂开发新型充填胶凝剂试验研究[J].岩土工程学报,2014,36(8):1498-1506.YANG Zhiqiang,GAO Qian,WANG Yongqian,et al.Experimental study on new filling cementing material using water-hardening nickel slag tailings of Jinchuan Mine[J].Chinese Journal of Geotechnical Engineering,2014,36(8):1498-1506.
[21]ZHAO Ruichao,HAN Yuexin,YANG Guang,et al.Mechanism of adsorption and aggregation of fine siderite,quartz and hematite[J].Journal of Northeastern University,2015,36(4):596-600.
[22]KRIVENKO P,PETROPAVLOVSKY O,PETRANEK V,et al.High strength alkali activated slag cements with controlled setting times and early strength gain[J].Advanced Materials Research,2015,1100:44-49.
[23]内维尔A M.混凝土性能[M].刘数华,冷发光,李新宇,等译.北京:中国建筑工业出版社,2011:369-372.NEVILLE A M.Properties of concrete[M].LIU Shuhua,LENG Faguang,LI Xinyu,et al trans.Beijing:China Architecture&Building Press,2011:369-372.
[24]ZACHARIASEN W H.The atomic arrangement in glass[J].Journal of the American Chemical Society,1932,44(10):3841-3851.