Preparation of SiO2-Al2O3 composite aerogel with high specific surface area by sol-gel method from coal gangue

doi:10.11949/j.issn.0438-1157.20161577

Abstract

Abstract:

SiO₂-Al₂O₃ aerogel has been synthesized by sol-gel method followed by vacuum drying from Yanzhou coal gangue. Coal gangue was treated in the sequence of low temperature calcination, acid leaching, alkali-activation and sol-gel method. The physical and chemical characteristics of coal gangue, SiO₂-Al₂O₃ aerogel and the intermediate products during the synthesizing process were investigated by means of X-ray diffraction, scanning electron microscope, Fourier transform infrared spectroscopy and nitrogen adsorption, and the gelation mechanism of SiO₂-Al₂O₃ was studied. The results showed that both quartz and kaolinite, which were the main constituents of coal gangue, were transformed into amorphous state after alkali-activation. The SiO₂-Al₂O₃ aerogel was an aggregation of amorphous nanoparticles formed by Si-O-Si, Si-O-Al network skeleton. The SiO₂-Al₂O₃ aerogel had a bulk density of 0.37 g·cm^-3, a BET specific surface area of 483 m²·g^-1 and a mesoporous structure with a specific pore volume of 1.87 cm³·g^-1 and an average pore diameter of 10.29 nm with most probable pore size of 9.32 nm.

Key words: silica, alumina, waste treatment, coal gangue, acid leaching, alkali-activation, sol-gel, aerogel

摘要：

以兖州煤矸石为原料，经过低温焙烧、酸浸除杂、碱熔活化，采用溶胶-凝胶法和真空干燥法制备完整的块状SiO₂-Al₂O₃二元复合气凝胶。通过X射线衍射、扫描电镜、傅里叶变换红外光谱、氮气吸附等检测手段对原料、SiO₂-Al₂O₃气凝胶及其制备过程中得到的中间产物的物理、化学特性进行表征，研究SiO₂-Al₂O₃凝胶的形成机制。实验结果表明，煤矸石经过酸浸除去了大部分的铁、钾、碱土金属等杂质。在经过碱熔活化后，煤矸石主要组分石英和高岭石均转化为非晶态，反应活性提高。制备得到的SiO₂-Al₂O₃气凝胶是以Si-O-Si、Si-O-Al网络结构为骨架的非晶态纳米颗粒聚集体，其堆积密度0.37 g·cm^-3，比表面积483 m²·g^-1，比孔容1.87 cm³·g^-1，平均孔径10.29 nm，最可几孔径9.32 nm，具有较好的介孔特征。

关键词: 氧化硅, 氧化铝, 废物处理, 煤矸石, 酸浸, 碱熔活化, 溶胶-凝胶, 气凝胶

CLC Number:

TQ09

LIU Bo, LIU Moxiang, CHEN Xiaoping. Preparation of SiO₂-Al₂O₃ composite aerogel with high specific surface area by sol-gel method from coal gangue[J]. CIESC Journal, 2017, 68(5): 2096-2104.

刘博, 刘墨祥, 陈晓平. 用废弃煤矸石制备高比表面积的SiO₂-Al₂O₃二元复合气凝胶[J]. 化工学报, 2017, 68(5): 2096-2104.

References 31

[1]	李超, 赵亮, 任启欣. 煤矸石综合利用现状分析与前景探讨 [J]. 环境与发展, 2015, 27 (3): 72-74. LI C, ZHAO L, REN Q X. Status analysis and development discussion of coal gangue comprehensive utilization [J]. Environment and Development, 2015, 27 (3): 72-74.
[2]	BIAN Z F, INYANG H I, DANIELS J L, et al. Environmental issues from coal mining and their solutions [J]. Mining Science and Technology, 2010, 20: 215-223.
[3]	QUEROL X, IZQUIERDO M, MONFORT E, et al. Environmental characterization of burnt coal gangue banks at Yangquan, Shanxi Province, China [J]. International Journal of Coal Geology, 2008, 75: 93-104.
[4]	郭彦霞, 张圆圆, 程芳琴. 煤矸石综合利用的产业化及其展望 [J]. 化工学报, 2014, 63 (7): 2443-2453. GUO Y X, ZHANG Y Y, CHEN F Q. Industrial development and prospect about comprehensive utilization of coal gangue [J]. CIESC Journal, 2014, 63 (7): 2443-2453.
[5]	石斌, 刘翠玲. 中国煤矸石资源化利用专利分析 [J]. 煤炭加工与综合利用, 2013, (4): 71-76. SHI B, LIU C L. Analysis of patents in recycling utilization of coal gangue in China [J]. Coal Processing & Comprehensive Utilization, 2013, (4): 71-76.
[6]	白志民, 李桂金, 金玥, 等. 硅酸盐固体废弃物(煤矸石)应用的研究进展 [J]. 硅酸盐学报, 2010, 38 (7): 1357-1361. BAI Z M, LI G J, JIN Y, et al. Development on applications of silicate solid wastes (coal gangue) [J]. J. Chin. Ceram. Soc., 2010, 38 (7): 1357-1361.
[7]	LIU H B, LIU Z L. Recycling utilization patterns of coal mining waste in China [J]. Resources, Conservation and Recycling, 2010, 54: 1331-1340.
[8]	王真, 戴真, 赵宁, 等. 气凝胶材料研究的新进展 [J]. 高分子通报, 2013, (9): 50-55. WANG Z, DAI Z, ZHAO N, et al. Recent research progress on aerogel materials [J]. Polymer Bulletin, 2013, (9): 50-55.
[9]	蔡龙, 浦群, 曲康, 等. 酸碱催化剂浓度对柔性硅气凝胶性能和结构的影响 [J]. 化工学报, 2016, 67 (2): 648-653. CAI L, PU Q, QU K, et al. Effects of acid-base catalysts concentration on structures and properties of flexible silica aerogels [J]. CIESC Journal, 2016, 67 (2): 648-653.
[10]	ARAVIND P R, MUKUNDAN P, KRISHNA P P, et al. Mesoporous silica-alumina aerogels with high thermal pore stability through hybrid sol-gel route followed by subcritical drying [J]. Microporous and Mesoporous Materials, 2006, 96 (1/2/3): 14-20.
[11]	吴晓栋, 邵高峰, 吴君, 等. 无机铝盐法制备SiO2-Al2O3复合气凝胶隔热材料 [J]. 南京工业大学学报(自然科学版), 2016, 38 (2): 7-14. WU X D, SHAO G F, WU J, et al. Synthesis and characterization of SiO2-Al2O3 composite aerogel using inorganic aluminum salt as raw material [J]. Journal of Nanjing Tech University (Natural Science Edition), 2016, 38 (2): 7-14.
[12]	WU X D, SHAO G F, CUI S, et al. Synthesis of a novel Al2O3-SiO2 composite aerogel with high specific surface area at elevated temperatures using inexpensive inorganic salt of aluminum [J]. Ceramics International, 2016, 42 (1): 874-882.
[13]	何飞, 赫晓东, 李垚. 无机盐和有机醇盐制备Al2O3干凝胶 [J]. 硅酸盐学报, 2006, 34 (9): 1093-1097. HE F, HE X D, LI Y. Al2O3 xerogels synthesized by inorganic salt and organic alkoxide [J]. J. Chin. Ceram. Soc., 2006, 34 (9): 1093-1097.
[14]	武纬, 冯坚, 张长瑞, 等. Al2O3-SiO2气凝胶的制备及性能研究 [J]. 材料导报, 2008, 22 (S3): 349-351. WU W, FENG J, ZHANG C R, et al. Preparation and properties of Al2O3-SiO2 aerogels [J]. Materials Review, 2008, 22 (S3): 349-351.
[15]	LA PAROLA V, DEGANELLO G, SCIRÈ S, et al. Effect of the Al/Si atomic ratio on surface and structural properties of sol-gel prepared aluminosilicates [J]. Journal of Solid State Chemistry, 2003, 174: 482-488.
[16]	SZCZYGIEL I, MATRASZEK A, CHEMANOWSKI J, et al. Thermal behaviour of mixed alumina-silica gels obtained from alkoxides: Phase formation and morphology of powders [J]. Journal of Non-Crystalline Solids, 2010, 356: 2824-2830.
[17]	CHEMANOWSKI J, SZCZYGIEL B. High temperature oxidation resistance of FeCrAl alloys covered with ceramic SiO2-Al2O3 coatings deposited by sol-gel method [J]. Corrosion Science, 2008, 50: 3581-3589.
[18]	冯坚, 高庆福, 武纬, 等. 硅含量对Al2O3-SiO2气凝胶结构和性能的影响 [J]. 无机化学学报, 2009, 25 (10): 1758-1763. FENG J, GAO Q F, WU W, et al. Effect of silica content on structure and properties of Al2O3-SiO2 aerogels [J]. Chinese Journal of Inorganic Chemistry, 2009, 25 (10): 1758-1763.
[19]	DE WITTE B, AERNOUTS K, UYTTERHOEVEN J B. Aging of aluminosilicate and silica gels in aqueous solutions of various pH and Al content, a textural and structural evaluation [J]. Microporous Materials, 1996, 7: 97-108.
[20]	SINKÓ K, MEZEI R. Preparation effects on sol-gel aluminosilicate gels [J]. Journal of Non-Crystalline Solids, 1998, 231: 1-9.
[21]	陈娜, 严云, 胡志华. 用粉煤灰制备SiO2-Al2O3气凝胶的研究 [J]. 武汉理工大学学报, 2011, 33 (2): 37-41. CHEN N, YAN Y, HU Z H. Research of SiO2-Al2O3 aerogel with fly ash [J]. Journal of Wuhan University of Technology, 2011, 33 (2): 37-41.
[22]	孔德顺, 吴红, 艾德春, 等. 煤矸石酸浸除铁及废液利用的实验研究 [J]. 应用化工, 2010, 39 (10): 1482-1484. KONG D S, WU H, AI D C, et al. Research on the iron removal from gangue by acid leaching and the utilization of waste liquid [J]. Applied Chemical Industry, 2010, 39 (10): 1482-1484.
[23]	KROL M, MINKIEWICZ J, MOZGAWA W. IR spectroscopy studies of zeolites in geopolymeric materials derived from kaolinite [J]. Journal of Molecular Structure, 2016, 1126: 200-206.
[24]	FROST R L, VASSALLO A M. The dehydroxylation of the kaolinite clay minerals using infrared emission spectroscopy [J]. Clays and Clay Minerals, 1996, 44 (5): 635-651.
[25]	靳喜海, 高濂, 郭景坤. 溶胶-凝胶法制备莫来石粉体 [J]. 无机材料学报, 2001, 16 (3): 555-558. JIN X H, GAO L, GUO J K. Preparation of mullite powders by sol-gel methods [J]. Journal of Inorganic Materials, 2001, 16 (3): 555-558.
[26]	吴其胜, 黎水平, 苏沙沙. 徐州地区煤系高岭土合成4A沸石分子筛 [J]. 化工进展, 2009, 28 (1): 130-134. WU Q S, LI S P, SU S S. Preparation of 4A zeolite molecular sieve from Xuzhou coal-measure kaolin [J]. Chemical Industry and Engineering Progress, 2009, 28 (1): 130-134.
[27]	王建, 董家禄, 刘杨, 等. 偏高岭土合成4A沸石机理的研究 [J]. 无机化学学报, 2000, 16 (1): 31-36. WANG J, DONG J L, LIU Y, et al. Studies on the mechanism of synthesis of zeolite 4A from metakaolinite [J]. Chinese Journal of Inorganic Chemistry, 2000, 16 (1): 31-36.
[28]	茅宇雄. 无机先驱体溶胶凝胶法制备莫来石 [D]. 杭州: 浙江大学, 2002. MAO Y X. Preparation of mullite powder from sol-gel process with inorganic precursors [D]. Hangzhou: Zhejiang University, 2002.
[29]	何飞, 赫晓东, 李垚. SiO2-Al2O3干凝胶的制备与性能研究 [J]. 功能材料, 2007, 38 (6): 938-942. HE F, HE X D, LI Y. The synthesis and characterization of SiO2-Al2O3 xerogels [J]. Functional Materials, 2007, 38 (6): 938-942.
[30]	何飞, 赫晓东, 氮气吸附法研究 SiO2-Al2O3 干凝胶的孔结构特性 [J]. 硅酸盐学报, 2007, 35 (5): 638-642. HE F, HE X D. Porous structure characteristics of SiO2-Al2O3 xerogels by nitrogen adsorption-desorption method [J]. J. Chin. Ceram. Soc., 2007, 35 (5): 638-642.
[31]	SHI F, LIU J X, SONG K, et al. Cost-effective synthesis of silica aerogels from fly ash via ambient pressure drying [J]. Journal of Non-Crystalline Solids, 2010, 356: 2241-2246.

Preparation of SiO₂-Al₂O₃ composite aerogel with high specific surface area by sol-gel method from coal gangue

用废弃煤矸石制备高比表面积的SiO₂-Al₂O₃二元复合气凝胶

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