焙烧温度对天然沸石物化性能的影响
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摘要
以天然沸石为研究对象,研究焙烧温度对沸石总孔体积、孔径分布、表面Zeta电位、阳离子交换容量、晶体结构、硅铝配位结构和原子结合能等物化特性和颗粒结构的影响规律。结果表明:当焙烧温度≥600℃时,沸石总孔体积明显升高,其中微孔、介孔体积比例大幅减少,大孔体积比例大幅增加;随着焙烧温度升高,沸石颗粒表面Zeta电位逐渐升高,而沸石阳离子交换容量则先升高后降低,在400℃时达到最大值1.786 mmol/g。焙烧对沸石作用机理研究发现,沸石焙烧后,颗粒结晶度降低、晶胞小幅收缩;焙烧会使沸石中的Si(2Al)和Si(3Al)减少、Si(0Al)增加,且使沸石Al2p结合能小幅升高、Si2p结合能小幅下降、O1s的结合能则几乎不发生变化。
The effects of calcination temperature on the physicochemical properties were studied with the natural zolite as the study object. The results show that the total pore volumes of the modified zeolite increase significantly when the calcination temperature is higher than 600 ℃. Among them, the percentages of microporous and mesoporous volumes reduce greatly, but the percentage of macrospore volume increases greatly. Zeta potentials of the zeolite increase with increasing the calcination temperature. The cation exchange capacity of the modified zeolite increases slightly at first, and subsequently decreases. The cation exchange capacity reaches the largest value of 1.786 mmol/g at 400℃. X-ray diffraction analyses show that the modified zeolite has a lower crystallinity and contractile unit cell. The results of nuclear magnetic resonance analysis indicate that the amounts of Si(2Al) coordination structure and Si(3Al) coordination structure decrease and the amounts of Si(0Al) coordination structure increase. The results of X-ray photoelectron spectroscopy analysis show that the electron binding energies of Al2p increase slightly, the electron binding energies of Si2p decrease slightly, and the electron binding energies of O1s has little change.
The effects of calcination temperature on the physicochemical properties were studied with the natural zolite as the study object. The results show that the total pore volumes of the modified zeolite increase significantly when the calcination temperature is higher than 600 ℃. Among them, the percentages of microporous and mesoporous volumes reduce greatly, but the percentage of macrospore volume increases greatly. Zeta potentials of the zeolite increase with increasing the calcination temperature. The cation exchange capacity of the modified zeolite increases slightly at first, and subsequently decreases. The cation exchange capacity reaches the largest value of 1.786 mmol/g at 400℃. X-ray diffraction analyses show that the modified zeolite has a lower crystallinity and contractile unit cell. The results of nuclear magnetic resonance analysis indicate that the amounts of Si(2Al) coordination structure and Si(3Al) coordination structure decrease and the amounts of Si(0Al) coordination structure increase. The results of X-ray photoelectron spectroscopy analysis show that the electron binding energies of Al2p increase slightly, the electron binding energies of Si2p decrease slightly, and the electron binding energies of O1s has little change.
引文
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[16]范春辉,马宏瑞,花莉,王家宏,王海军.FTIR和XPS对沸石合成特性及Cr(Ⅲ)去除机制的谱学表征[J].光谱学与光谱分析,2012,32(2):324-328.FAN Chun-hui,MA Hong-hui,HUA Li,WANG Jia-hong,WANG Hai-jun.FTIR and XPS analysis of characteristics of synthesized zeolite and removal mechanisms for Cr(Ⅲ)[J].Spectroscopy and Spectral Analysis,2012,32(2):324-328.
[17]马广伟,谢在库.硅铝分子筛骨架脱铝模型[J].材料研究学报,2009,23(2):205-210.MA Guang-wei,XIE Zai-ku.Modelling of dealumination of silicon-aluminum molecular sieves[J].Chinese Journal of Material Research,2009,23(2):205-210.
[2]饶力,汪晓军.天然沸石处理氨氮废水的中试研究[J].水处理技术,2016,42(4):104-106.RAO Li,WANG Xiao-jun.Pilot test on treatment of ammonia nitrogen wastewater by natural zeolite[J].Technology of Water Treatment,2016,42(4):104-106.
[3]张新颖,余杨波,王美银,许冉冉,李杰.天然斜发沸石的氨氮改性吸附与化学再生[J].环境化学,2016,35(5):1058-1066.ZHANG Xin-ying,YU Yang-bo,WANG Mei-yin,XU Ran-ran,LI Jie.Modification and chemical regeneration of natural clinoptilolite for ammonium nitrogen adsorption[J].Environmental Chemistry,2016,35(5):1058-1066.
[4]ERDO?A B,SAKIZCI M,Y?RüKO?ULLARI E.Characterization and ethylene adsorption of natural and modified clinoptilolites[J].Applied Surface Science,2008,254(8):2450-2457.
[5]HUO H X,LIN H,DONG Y B,CHENG H,WANG H,CAO L X.Ammonia-nitrogenand phosphates sorption from simulated reclaimed waters by modified clinoptilolite[J].Journal of Hazardous Materials,2010,229/230:292-297.
[6]郭俊元,王彬.HDTMA改性沸石的制备及吸附废水中对硝基苯酚的性能和动力学[J].环境科学,2016,37(5):1852-1857.GUO Jun-yuan,WANG Bin.Preparation of HDTMA-modified zeolite and its performance in nitro-phenol adsorption from wastewaters[J].Environmental Science,2016,37(5):1852-1857.
[7]崔有为,李杰,杜兆富.镧、铈改性沸石对污水除磷性能和机制的比较研究[J].中国稀土学报,2016,34(4):460-466.CUI You-wei,LI Jie,DU Zhao-fu.Comparative study of performance and mechanism of lanthanum and cerium modified zeolite on phosphorus removal in wastewater[J].Journal of the Chinese Society of Rare Earths,2016,34(4):460-466.
[8]袁林,柴立元,闵小波,王云燕,舒余德,周敏,方艳,王璞,常皓.剩余污泥与人造沸石复合体系去除废水中的钙离子[J].中国有色金属学报,2007,17(5):825-829.YUAN Lin,CHAI Li-yuan,MIN Xiao-bo,WANG Yun-yan,SHU Yu-de,ZHOU Min,FANG Yan,WANG Pu,CHANG Hao.Removal of calcium ion from wastewater using waste activated sludge and artificial zeolites[J].The Chinese Journal of Nonferrous Metals,2007,17(5):825-829.
[9]ESSAIDI N,SAMET B,BAKLOUTI S,ROSSIGNOL S.Feasibility of producing geopolymers from two different Tunisian clays before and after calcination at various temperatures[J].Applied Clay Science,2014,88/89:221-227.
[10]ZHA L,MAO J B,ZHOU J X,ZHANG Z C,ZHANG S.Skeletal isomerization of unsaturated fatty acids on Beta zeolites:Effects of calcination temperature and additives[J].Applied Catalysis A,2009,356(1):52-56.
[11]LIN Hai,JIN Xin,DONG Ying-bo,HUO Han-xin,LIU Quan-li.Influence of calcination on the physical characteristics and nitrogen removal performance of clinoptilolites[J].Journal of Wuhan University of Technology(Materials Science Edition),2014,29(6):1099-1103.
[12]袁俊生,王静康.钠型斜发沸石Na+-K+离子交换特性研究(I)—离子交换过程热力学特性[J].离子交换与吸附,2004,26(6):541-547.YUNA Juan-sheng,WANG Jing-kang.Research on Na+-K+ion exchange characterization Na-clinoptilolite(I)—Thermodynamics characteristic of the process[J].Ion Exchange and Adsorption,2004,26(6):541-547.
[13]SAIG A,FINKELSTEIN Y,DANON A,KORESH J E.Study of type-A zeolites.Part 2:Effect of dehydration on the effective aperture dimension[J].Journal of Physical Chemistry B,2003,107(48):13414-13418.
[14]ZHANG Y H,LIN J W,ZHU Z L.Removal of nitrate from aqueous solution using cetylpyridinium bromide(CPB)modified zeolite as adsorbent[J].Journal of Hazardous Materials,2011,186(2/3):1972-1978.
[15]陈铁旦,苗茵,李曼尼.白庙子斜发沸石水热离子交换性能研究[J].内蒙古大学学报(自然科学版),2006,37(6):646-650.CHEN Tie-dan,MIAO Yin,LI Man-ni.Study on the hydrothermal cation exchange of baimiaozi clinoptiolite[J].Acta Scientiarum Naturalium Universitatis Nei Mongol(Natural Science Edition),2006,37(6):646-650.
[16]范春辉,马宏瑞,花莉,王家宏,王海军.FTIR和XPS对沸石合成特性及Cr(Ⅲ)去除机制的谱学表征[J].光谱学与光谱分析,2012,32(2):324-328.FAN Chun-hui,MA Hong-hui,HUA Li,WANG Jia-hong,WANG Hai-jun.FTIR and XPS analysis of characteristics of synthesized zeolite and removal mechanisms for Cr(Ⅲ)[J].Spectroscopy and Spectral Analysis,2012,32(2):324-328.
[17]马广伟,谢在库.硅铝分子筛骨架脱铝模型[J].材料研究学报,2009,23(2):205-210.MA Guang-wei,XIE Zai-ku.Modelling of dealumination of silicon-aluminum molecular sieves[J].Chinese Journal of Material Research,2009,23(2):205-210.