硅藻基水化硅酸钙的表面改性与次甲基蓝吸附性能
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摘要
目的优化低品位硅藻土的孔结构与表面性质,改善其染料脱除性能.方法采用水热处理方法,使硅藻土与适当质量比的氢氧化钙在90℃不饱和水蒸气环境中反应24 h,所得低结晶度水化硅酸钙(CSH(B))不仅充分保留了硅藻土原有的规则多孔结构,同时引入丰富的微小孔隙;经进一步表面改性,硅藻基CSH(B)对水溶液中次甲基蓝染料表现出明显的脱色作用.结果 40℃、染料初始质量浓度25 mg/L条件下的120 min吸附量达3.033 9 mg/g,且吸附容量随染料初始质量浓度及环境温度的提高而进一步增大;动力学分析发现,水溶液中硅藻基CSH(B)对次甲基蓝的静态吸附属自发进行的吸热过程,可采用伪二次动力学方程加以描述.结论经孔结构调整并表面改性后,低品位硅藻土的染料吸附能力明显提高.
In order to adjust the pore structure of diatomaceous earth and to upgrade the corresponding capacity of dye removal,diatomaceous earth and Ca(OH)_2 in appreciable proportion were employed as the starting materials to hydrothermally synthesize calcium silicate hydrate(CSH)under the atmosphere of unsaturated H_2O vapor,i.e.,the temperature was 90 ℃ and the time 24 h.Microstructural characterizations revealed a crystal phase of CSH(B)in the obtained products,which is relative poor in crystallinity but abundant in micro-and meso-scaled pores.After a process of surface modification,the CSH(B)powders were used to remove methylene blue(MB)from its aqueous solution.MB adsorption capacity of 3.033 9 mg/g was obtained from the CSH(B)powders working at 40 ℃ for 120 min in the MB solution with an initial concentration of 25 mg/L.The adsorption capacity was found to increase evidently with the increasing temperature and initial concentration of MB.On the base of dynamic analysis,the static adsorption of MB molecules onto CSH(B)powders is demonstrated to be a spontaneous and endothermic process,which can be effectively predicted by the pseudo-second-order model.
In order to adjust the pore structure of diatomaceous earth and to upgrade the corresponding capacity of dye removal,diatomaceous earth and Ca(OH)_2 in appreciable proportion were employed as the starting materials to hydrothermally synthesize calcium silicate hydrate(CSH)under the atmosphere of unsaturated H_2O vapor,i.e.,the temperature was 90 ℃ and the time 24 h.Microstructural characterizations revealed a crystal phase of CSH(B)in the obtained products,which is relative poor in crystallinity but abundant in micro-and meso-scaled pores.After a process of surface modification,the CSH(B)powders were used to remove methylene blue(MB)from its aqueous solution.MB adsorption capacity of 3.033 9 mg/g was obtained from the CSH(B)powders working at 40 ℃ for 120 min in the MB solution with an initial concentration of 25 mg/L.The adsorption capacity was found to increase evidently with the increasing temperature and initial concentration of MB.On the base of dynamic analysis,the static adsorption of MB molecules onto CSH(B)powders is demonstrated to be a spontaneous and endothermic process,which can be effectively predicted by the pseudo-second-order model.
引文
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[2] 赵恒,何雪华,童东绅,等.硅藻土的改性及深加工利用[J].中国非金属矿工业导刊,2012(2):55-59.(ZHAO Heng,HE Xuehua,TONG Dongshen,et al.Modification and deep progressing of diatomite and its application[J].China non-metallic minerals industry,2012(2):55-59.)
[3] 佟钰,夏枫,高见,等.孔径分布特征对水热固化硅藻土使用性能的影响[J].硅酸盐通报,2014,33(6):1309-1313.(TONG Yu,XIA Feng,GAO Jian,et al.Effect of pore width distribution on the working properties of hydrothermally solidified diatomite[J].Bulletin of the Chinese ceramic society,2014,33(6):1309-1313.)
[4] 梁兴荣,张英英,向兴,等.硅藻土制备硅酸钙板的研究[J].中国非金属矿工业导刊,2014(5):15-17.(LIANG Xingrong,ZHANG Yingying,XIANG Xing,et al.Preparation of calcium silicate board by using diatomite[J].China non-metallic mineral industry,2014(5):15-17.)
[5] 孔伟,杜玉成,卜仓友,等.硅藻土基调湿材料的制备与性能研究[J].非金属矿,2011,22(1):57-59.(KONG Wei,DU Yucheng,BU Cangyou,et al.Study on preparation and performance of diatomite-based humidity controlling material[J].Non-metallic mines,2011,22(1):57-59.)
[6] 佟钰,张君男,王琳,等.硅藻土的水热固化及其湿度调节性能研究[J].新型建筑材料,2015,42(4):14-16.(TONG Yu,ZHANG Junnan,WANG Lin,et al.Hydrothermal solidification of diatomite and its humidity controlling property[J].New building materials,2015,42(4):14-16.)
[7] VU D H,WANG K S,BAC B H,et al.Humidity control materials prepared from diatomite and volcanic ash[J].Construct and build materials,2013,38(1):1066-1072.
[8] 王佼,郑水林.酸浸和焙烧对硅藻土吸附甲醛性能的影响[J].非金属矿,2011,34(6):72-74.(WANG Jiao,ZHENG Shuilin.The influence of acid-treating and calcination on adsorption properties to formaldehyde of Diatomite[J].Non-metallic mines,2011,34(6):72-74.)
[9] IM D H,CHU Y S,SONG H,et al.Formaldehyde adsorption and physical characteristics of hydrothermal reacted panel with porous materials[J].Journal of korean ceramic society,2009,46(6):627-632.
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[11] 佟钰,朱长军,刘俊秀,等.低品位硅藻土的水热固化与力学性能研究[J].硅酸盐通报,2013,32(3):379-383.(TONG Yu,ZHU Changjun,LIU Junxiu,et al.Hydrothermal solidification of low-grade diatomite and its mechanical property[J].Bulletin of the Chinese ceramic society,2013,32(3):379-383.)
[12] 赵越,郑欣,徐畅,等.改性硅酸钙(CSH)对重金属废水中Ni2+的吸附特性研究[J].安全与环境学报,2017,17(5):1904-1908.(ZHAO Yue,ZHENG Xin,XU Chang,et al.On the adsorption behaviors of calcium silicate hydrate(CSH)to Ni2+[J].Journal of safety and environment,2017,17(5):1904-1908.)
[13] 关伟,吉芳英,陈晴空,等.水化硅酸钙的制备及磷回收特性[J].功能材料,2012,43(23):3286-3290.(GUAN Wei,JI Fangying,CHEN Qingkong,et al.Preparation and phosphorus recovery performance of calcium silicate hydrate[J].Functional materials,2012,43(23):3286-3290.)
[14] 张国珍,高小波,武福平,等.十六烷基三甲基溴化铵改性沸石对腐殖酸的吸附性能研究[J].环境污染与防治,2016,38(5):12-17.(ZHANG Guozhen,GAO Xiaobo,WU Fuping,et al.Research on adsorption properties of cetyltrimethylammonium bromide modified zeolite on humic acid[J].Environmental pollution and control,2016,38(5):12-17.)
[15] 张增志,渠永平,马丹丹,等.十六烷基三甲基溴化铵改性蒙脱土的制备及其保水性能[J].功能材料,2015,46(7):67-71.(ZHANG Zengzhi,QU Yongping,MA Dandan,et al.Preparation and water retention characteristics of modified montmorillonite with hexadecyl trimethyl ammonium bromide[J].Functional materials,2015,46(7):67-71.)
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