Synthesis and structural characterization of layered double hydroxide usingsteel slag as raw material

doi:10.11949/j.issn.0438-1157.20150658

Abstract

Abstract:

Ca-Mg-Al-Fe quaternary layered double hydroxide (LDHs) was successfully synthesized using the abundant and cheap steel slag as raw material via a convenient chemical process: acetic acid-leaching and coprecipitation. The influences of pH value, crystallization temperature and time on the synthesis of Ca-Mg-Al-Fe quaternary LDHs were investigated. The samples were characterized by XRD, XRF, SEM, FT-IR, TEM, DTA/TG and BET. The results showed that pH was the dominant factor for the synthesis of LDHs, and pure LDHs could be synthesized when pH value was controlled in the range of 10.5-11.8 during coprecipitation process. Crystallization temperature and time were important factors influencing the crystal cell parameters and layer spacing. As the crystallization temperature and time increased, lattice parameters a, c and the spacing of layer first reduced and then increased. Crystal grain size of LDHs along the axis of a was larger than that along the axis of c. When LDHs was synthesized at the conditions of pH of 11.8, crystallization temperature of 150℃ and crystallization time of 16 h, it presented well-defined structure and crystal shape, clear layered structure, large aperture and well thermal stability.

Key words: steel slag, LDHs, synthesis, crystallization, purification

摘要：

以钢渣为原料,醋酸为浸出介质,在一定条件下得到浸出液,利用共沉淀法合成了Ca-Mg-Al-Fe四元层状双金属氢氧化物(LDHs),探讨了pH、晶化温度和晶化时间对Ca-Mg-Al-Fe四元LDHs层状材料合成的影响,采用XRD、XRF、SEM、FT-IR、TEM、DTA/TG和BET对样品进行了表征。研究表明,pH对层状材料合成的影响最大,pH在10.5～11.8可形成纯相水滑石;晶化温度和晶化时间是影响晶格参数和层间距的重要因素,随温度及时间的增加,其晶格参数a、c及层间距均先减小后增大;LDHs的晶粒尺寸沿a轴方向比沿c轴方向大。当pH 11.8,晶化温度150℃,晶化时间16 h时,合成的LDHs层状材料结构规整、晶型良好、层状结构明显、孔径较大且热稳定性良好。

关键词: 钢渣, LDHs, 合成, 结晶, 纯化

CLC Number:

X705

CHEN Yan, WANG Liqiu, WANG Chenye, LI Huiquan. Synthesis and structural characterization of layered double hydroxide usingsteel slag as raw material[J]. CIESC Journal, 2015, 66(12): 5149-5156.

陈艳, 王丽秋, 王晨晔, 李会泉. 以钢渣为原料合成层状双氢氧化物及其结构表征[J]. 化工学报, 2015, 66(12): 5149-5156.

References 22

[1]	Lin Y J, Fang Q L, Chen B L. Metal composition of layered double hydroxides (LDHs) regulating adsorption to calcined LDHs via the memory effect and hydrogen bonding [J]. Journal of Environmental Sciences, 2014, 26 (3): 493-501.
[2]	Badreddine M, Legrouri A, Barroug A, et al. Ion exchange of different phosphate ions into the zinc-aluminium-chloride layered double hydroxide [J]. Materials Letters, 1999, 38 (6): 391-395.
[3]	Ai Ning (艾宁), Jiang Zhe (姜哲), Xu Qian (徐茜), Qian Qifeng (钱琪枫), Wu Xi (伍希), Wang Jiawei (王家炜). The preparation of amino modified layered double hydroxide and carbon adsorption mechanism [J]. CIESC Journal (化工学报), 2013, 64 (2): 616-623.
[4]	Wang J, Fan G, Wang H, et al. Synthesis, characterization, and catalytic performance of highly dispersed supported nickel catalysts from Ni-Al layered double hydroxides [J]. Industrial & Engineering Chemistry Research, 2011, 50 (24): 13717-13726.
[5]	Wang J, Lei Z, Qin H, et al. Structure and catalytic property of Li-Al metal oxides from layered double hydroxide precursors prepared via a facile solution route [J]. Industrial & Engineering Chemistry Research, 2011, 50 (12): 7120-7128.
[6]	Shao M, Ning F, Zhao Y, et al. Core-shell layered double hydroxide microspheres with tunable interior architecture for supercapacitors [J]. Chemistry of Materials, 2012, 24 (6): 1192-1197.
[7]	Li Yanwei (李延伟), Liang Xiaoli (梁晓丽), Yao Jinhuan (姚金环), Jiang Jiqiong (姜吉琼). The preparation of Ni/Al-LDH/MCNTs in situ composite material and its electrochemical properties [J]. CIESC Journal (化工学报), 2014, 65 (8): 3298-3305.
[8]	Wang L, Xing H, Zhang S, et al. A Gd-doped Mg-Al-LDH/Au nanocomposite for CT/MR bimodal imagings and simultaneous drug delivery [J]. Biomaterials, 2013, 34 (13): 3390-3401.
[9]	Wang Z, Han E, Ke W. Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating [J]. Progress in Organic Coatings, 2005, 53 (1): 29-37.
[10]	Yang Miaomiao (杨淼淼). Preparation and properties of layered double hydroxides hollow structure [D]. Beijing: Beijing University of Chemical Technology, 2012.
[11]	Lü Zhi (吕志), Duan Xue (段雪). Controllable preparation of anionic layered materials [J]. Chinese Journal of Catalysis (催化学报), 2008, 29 (9): 199-204.
[12]	Yang R Y, Gao Y S, Wang J Y, et al. Layered double hydroxide (LDH) derived catalysts for simultaneous catalytic removal of soot and NOx [J]. Dalton Transactions, 2014, 43 (27): 10317-10327.
[13]	Feng Yongjun (冯拥军), Li Dianqing (李殿卿), Li Chunxi (李春喜), Wang Zigao (王子镐), Evans D G, Duan Xue (段雪). Synthesis and structure analysis of Cu-Ni-Mg-Al-CO3 hydrotalcite-like material [J]. Journal of Chemical Engineering (化学学报), 2003, 61 (1): 78-83.
[14]	Zhao Yuechang (赵月昌), Liu Ling (刘玲), Cheng Wenping (程文萍), Wu Haihong (吴海虹), Yang Jianguo (杨建国), He Mingyuan (何鸣元). Study on synthesis, characterization and sulfur transfer properties in FCC of MgAlZnFeCe hydrotalcite hydrothermal [J]. Journal of Inorganic Materials (无机材料学报), 2009, 24 (1): 171-174.
[15]	Gao P, Li F, Zhan H J, et al. Fluorine-modified Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol [J]. Catalysis Communications, 2014, 50: 78-82.
[16]	Kühl S, Schumann J, Kasatkin I, et al. Ternary and quaternary Cr or Ga-containing ex-LDH catalysts-influence of the additional oxides onto the microstructureand activity of Cu/ZnAl2O4 catalysts [J]. Catalysis Today, 2015, 246: 92-100.
[17]	Kuwahara Y, Ohmichi T, Kamegawa T, et al. A novel conversion process for waste slag: synthesis of a hydrotalcite-like compound and zeolite from blast furnace slag and evaluation of adsorption capacities [J]. Journal of Materials Chemistry, 2010, 20: 5052-5062.
[18]	Chen Tianhu (陈天虎), Xu Huifang (徐惠芳), Lu Anhuai (鲁安怀), Yue Shucang (岳书仓), Wang Jiaquan (汪家权), Peng Shuchuan (彭书传). The experimental study synthesis and characterization of attapulgite acid activation waste liquid prepare LDH [J]. Journal of Minerals (矿物学报), 2003, 23 (3): 199-204.
[19]	Bao W J, Li H Q, Zhang Y. Experimental investigation of enhanced carbonation by solvent extraction for indirect CO2 mineral sequestration [J]. Greenhouse Gases-Science and Technology, 2014, 4 (6): 785-799.
[20]	Yan H, Lu J, Wei M, et al. Theoretical study of the hexahydrated metal cations for the understanding of their template effects in the construction of layered double hydroxides [J]. Journal of Solid State Chemistry, 2008, 866 (1-3): 34-45.
[21]	Jitianu M, Gunness D C, Aboagye D E, et al. Nanosized Ni-Al layered double hydroxides-structural characterization [J]. Materials Research Bulletin, 2013, 48 (5): 1864-1873.
[22]	Zhao Yun (赵芸), He Jing (何静), Jiao Qinze (矫庆泽), Evans D G, Duan Xue (段雪). The selectivity growth and the grain size control of dihydroxy composite metal oxide [J]. Chinese Journal of Inorganic Chemistry (无机化学学报), 2001, 17 (4): 573-579.