Y型分子筛结晶度和晶胞常数随温度变化规律
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摘要
选取1种NaY分子筛和3种Si Cl4气相超稳法制得的DY分子筛作为研究对象,通过X荧光光谱(XRF)、N2吸附-脱附、热重(TG-DSC)和场发射扫描电镜(SEM),考察4种Y型分子筛物化性质的差异,利用原位升温粉末X射线衍射(in-situ XRD)考察相对结晶度(室温升至1 000℃)和晶胞常数(室温升至600℃)随温度变化的规律。结果表明,升温过程中4种Y型分子筛相对结晶度均表现为先升后降,NaY型分子筛在900℃时晶体结构完全消失,硅铝比较高的DY分子筛在1 000℃时,相对结晶度仅15%~35%;随着温度升高,NaY分子筛晶胞常数先减后增,而DY-1和DY-2分子筛晶胞常数先增后减,DY-3分子筛晶胞常数一直减少。(555)晶面衍射峰的偏移也随温度和骨架硅铝比变化呈规律性改变。
One NaY zeolite and three DY zeolites prepared by high-temperature gas-phase Si Cl4 were characterized by X-ray fluorescence(XRF),N2 adsorption-desorption,TG-DSC and scanning electron microscopy(SEM). Relationship of relative crystallinity(from room temperature to 1000℃) and unit cell constants(from room temperature to 600℃) with temperature change was explored by in-situ XRD. The results showed that relative crystallinity of four Y zeolites firstly increased and then decreased with heating process. Crystal structure of NaY zeolite disappeared completely at 900℃,while relative crystallinity of DY zeolites with high molar Si/Al ratio was only 15% to 35% at 1000℃. Unit cell parameters of NaY zeolite firstly decreased slightly and then increased with increase of temperature,by contrast,unit cell constants of DY-1 and DY-2 zeolites firstly increased then decreased. Unit cell constants of DY-3 zeolite decreased. Diffraction peak of(555) plane shifted with change of temperature and Si/Al ratio.
One NaY zeolite and three DY zeolites prepared by high-temperature gas-phase Si Cl4 were characterized by X-ray fluorescence(XRF),N2 adsorption-desorption,TG-DSC and scanning electron microscopy(SEM). Relationship of relative crystallinity(from room temperature to 1000℃) and unit cell constants(from room temperature to 600℃) with temperature change was explored by in-situ XRD. The results showed that relative crystallinity of four Y zeolites firstly increased and then decreased with heating process. Crystal structure of NaY zeolite disappeared completely at 900℃,while relative crystallinity of DY zeolites with high molar Si/Al ratio was only 15% to 35% at 1000℃. Unit cell parameters of NaY zeolite firstly decreased slightly and then increased with increase of temperature,by contrast,unit cell constants of DY-1 and DY-2 zeolites firstly increased then decreased. Unit cell constants of DY-3 zeolite decreased. Diffraction peak of(555) plane shifted with change of temperature and Si/Al ratio.
引文
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[2]James Paterson,Mark Peacock,Ewen Ferguson,et al.In situ X-ray diffraction of Fischer-Tropsch catalysts-effect of water on the reduction of cobalt oxides[J].Applied Catalysis A General,2017,546:103-110.
[3]Wang Guanyu,Wang Hejing,Zhang Nan.In situ high temperature X-ray diffraction study of illite[J].Applied Clay Science,2017,146:254-263.
[4]黄秀敏,唐幸福,徐奕德,等.原位X射线衍射研究VOx和Mo Ox在Al2O3上的分散[J].催化学报,2016,27(4):324-328.Huang Xiumin,Tang Xingfu,Xu Yide,et al.In Situ XRay Diffraction Study of VOxand Mo OxDispersion on Al2O3[J].Chinese Journal of Catalysis,2016,27(4):324-328.
[5]方萍,何迈,谢云龙,等.γ-Al2O3高温相变的XRD和Raman光谱比较研究[J].光谱学与光谱分析,2006,26(11):2039-2042.Fang Ping,He Mai,Xie Yunlong,et al.XRD and raman spectroscopic comparative study on phase transformation ofγ-Al2O3at high temperature[J].Spectroscopy and Spectral Analysis,2006,26(11):2039-2042.
[6]Song Youngdong,Damien Thirion,Saravanan Subramanian,et al.Monitoring instability of linear amine impregnated Ui O-66 by in-situ temperature resolved powder X-ray diffraction[J].Microporous and Mesoporous Materials,2017,243:85-90.
[7]Bulavchenko O A,Smirnov A A,Khromova S A,et al.In situ powder X-ray diffraction study of the process of Ni Mo O4-Si O2reduction with hydrogen[J].Journal of Structural Chemistry,2016,57(5):955-961.
[8]Mie Mller Storm,Rune E Johnsen,Poul Norby.In situ Xray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide[J].Journal of Solid State Chemistry,2016,240:49-54.
[9]王玲,王河锦,李婷.锐钛矿金红石的高温原位X射线衍射研究[J].物理学报,2013,62(14):146402.Wang Ling,Wang Hejin,Li Ting.In situ high temperature Xray diffraction study of anatase and rutile[J].Chinese Journal of Physics,2013,62(14):146402.
[10]汤云晖,章西焕,马鸿文.人工合成Na X沸石的原位高温X射线衍射研究[J].分析测试学报,2008,27(10):1031-1034.Tang Yunhui,Zhang Xihuan,Ma Hongwen.Study on synthesized Na X zeolite by in situ high temperature X-ray diffraction[J].Journal of Analytical Tests,2008,27(10):1031-1034.
[11]Carlos A C Perez,Neuman S de Resende,Vera M M Salim,et al.Water interaction in faujasite probed by in situ X-ray powder diffraction[J].The Journal of Physical Chemistry C,2017,121:2755-2761.
[12]申宝剑,袁德林,高雄厚,等.一种Y型分子筛及其制备方法:中国,CN104843737[P].2015-08-19.
[13]徐如人,庞文琴,于吉红.分子筛与多孔材料化学[M].北京:科学出版社,2004.
[14]刘希尧.工业催化剂分析表征测试[M].北京:烃加工出版社,1990.
[15]蒋大振,吕慧娟,汤凤杰,等.SUY的晶胞参数和骨架振动频率与其硅铝比间的关系[J].高等学校化学学报[J].1988,(9):60-64.Jiang Dazhen,LüHuijuan,Tang Fengjie,et al.Relationship between the unit cell parameters and the vibration frequency of framework and the Si/Al ratio of SUY[J].Chemical Journal of Chinese Universities[M].1988,(9):60-64.
[16]Carlos A C Perez,Neuman S de Resende,Vera M M Salim,et al.Water interaction in Faujasite probed by in situ Xray powder diffraction[J].Journal of Physical Chemistry C,2017,121:2755-2761.
[17]刘百军,李敏,冯智.水热和草酸改性对Y分子筛结构和酸性的影响[J].分子催化,2007,21(4):300-303.Liu Baijun,Li Min,Feng Zhi.Effects of hydrothermal and oxalic acid modification on structure and acidity of Y molecular sieves[J].Molecular Catalysis,2007,21(4):300-303.
[18]董松涛,李宣文,李大东,等.水热处理USY二次孔形成规律研究[J].物理化学学报,2002,18(3):201-206.Dong Songtao,Li Xuanwen,Li Dadong,et al.A study on formation rule of USY secondary hydrothermal treatment[J].Acta Physico-Chimica Sinica,2002,18(3):201-206.
[19]Meier W M,Groner M.Zeolite structure type EAB:crystal structure and mechanism for the topotactic transformation of the Na,TMA form[J].Journal of Solid State Chemistry,1981,37(2):204-218.
[20]王彪,王槐平.分子筛催化剂结晶度和硅铝比的X射线分析[J].石油大学学报(自然科学版),1998,22(1):70-78.Wang Biao,Wang Huaiping.X-Ray analysis of crystallinity and Si/Al ratio of zeolite catalysts[J].Journal of University of Petroleum(Natural Science),1998,22(1):70-78.
[21]杜晓辉,高晓云,高雄厚,等.钠对Y型分子筛水热稳定性的影响[J].石化技术与应用,2013,31(4):265-279.Du Xiaohui,Gao Xiaoyun,Gao Xionghou,et al.Effect of sodium on the hydrothermal stability of Y zeolites[J].Petrochemical Technology and Application,2013,31(4):265-279.
[22]申宝剑,覃正兴,高雄厚,等.碱处理脱硅与提高Y型分子筛硅铝比——矛盾的对立与统一[J].催化学报,2002,33(1):153-163.Shen Baojian,Qin Zhengxing,Gao Xionghou,et al.Opposition and unification of desalination by alkali treatment and improvement of Si/Al ratio of Y zeolite[J].Chinese Journal of Catalysis,2002,33(1):153-163.