不同模板剂作用下CHA型沸石的制备研究

doi:10.19964/j.issn.1006-4990.2022-0244

摘要/Abstract

摘要：

CHA型沸石在化学化工行业中具有优异的催化、吸附以及膜分离性能，但是在其合成过程中极易出现MER型杂晶，因此合成纯相CHA型沸石具有一定的难度。为了制备高结晶度的纯相CHA型沸石，在FAU型沸石的配方基础上详细考察了无K⁺以及含K⁺合成体系中四甲基氢氧化铵（TMAOH）与四甲基氟化铵（TMAF）两种模板剂对产物的影响，并深入研究了FAU、MER、CHA型沸石的转晶行为，从而寻找出纯相CHA型沸石的合成途径。结果表明，相比TMAOH，TMAF模板剂更利于合成出纯相的CHA型沸石，同时在含K⁺的合成体系中产物的结晶度更高、晶型更为完整。

关键词: CHA型沸石, FAU型沸石, 有机模板剂, 高结晶度

Abstract:

CHA zeolite has the outstanding performance in the catalyzation，adsorption and membrane separation of chemical industry.However，the impurity of MER phase usually existed during the formation of CHA zeolite and it is difficult to prepare the pure CHA phase.To prepare pure phase CHA zeolite with high crystallinity，on the base of the FAU zeolite recipe，the influences of TMAOH and TMAF on the products under the synthetic condition with K⁺ and without K⁺ were thoroughly investigated.The transformation of FAU、MER and CHA zeolite was deeply researched and the appropriate way of producing the pure CHA zeolite was found.It was shown that the pure CHA zeolite could be produced with the addition of TMAF compared to TMAOH，and CHA crystals had higher crystallinity and more integrality of micromorphology under the synthetic condition with K⁺.

Key words: CHA zeolite, FAU zeolite, organic template, high crystallinity

中图分类号:

TQ649.4

尹晓燕,刘宁,宋峰,龙澍琦. 不同模板剂作用下CHA型沸石的制备研究[J]. 无机盐工业, 2023, 55(2): 55-61.

YIN Xiaoyan,LIU Ning,SONG Feng,LONG Shuqi. Research on synthesis of CHA zeolite with different templates[J]. Inorganic Chemicals Industry, 2023, 55(2): 55-61.

图/表 10

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

参考文献 17

1	GUO Ya， SUN Tianjun， LIU Xiaowei，et al.Cost-effective synthesis of CHA zeolites with controllable morphology and size[J].Chemical Engineering Journal，2019，358：331-339.
2	KIM J， KIM D H.Synthesis of faulted CHA-type zeolites with controllable faulting probability[J].Microporous and Mesoporous Materials，2018，256：266-274.
3	TSUNOJI N， OSUGA R， YASUMOTO M，et al.Controlling hydrocarbon oligomerization in phosphorus-modified CHA zeolite for a long-lived methanol-to-olefin catalyst[J].Applied Catalysis A：General，2021，620.Doi：10.1016/j.apcata.2021.118176 . doi: 10.1016/j.apcata.2021.118176
4	NASSER G A， MURAZAA O， NISHITOBA T，et al.OSDA-free chabazite（CHA） zeolite synthesized in the presence of fluoride for selective methanol-to-olefins[J].Microporous and Mesoporous Materials，2019，274：277-285.
5	KOISHYBAY A， SHANTZ D F.Water is the oxygen source for methanol produced in partial oxidation of methane in a flow reactor over Cu-SSZ-13[J].Journal of the American Chemical Society，2020，142（28）：11962-11966.
6	沈美庆，李新华，王晨，等.Cu/CHA NH₃-SCR催化剂硫中毒及再生研究进展[J].化学工业与工程，2020，37（5）：7-13.
	SHEN Meiqing， LI Xinhua， WANG Chen，et al.Progress for studying on sulfur poisoning and regeneration over Cu/CHA NH₃-SCR catalysts[J].Chemical Industry and Engineering，2020，37（5）：7-13.
7	章凌，段宏昌，谭争国，等.用于柴油车尾气消除反应（NH₃-SCR）的八元环沸石分子筛研究进展[J].高等学校化学学报，2020，41（1）：19-27.
	ZHANG Ling， DUAN Hongchang， TAN Zhengguo，et al.Recent advances in the preparation of 8MR zeolites for the selective catalytic reduction of NO _x （NH₃-SCR） in diesel engines[J].Chemical Journal of Chinese Universities，2020，41（1）：19-27.
8	孙兆颖，周志辉，吴红丹.CHA型分子筛膜的合成方法及发展前景[J].现代化工，2021，41（8）：47-51，57.
	SUN Zhaoying， ZHOU Zhihui， WU Hongdan.Synthesis methods for CHA molecular sieve membrane and development prospect[J].Modern Chemical Industry，2021，41（8）：47-51，57.
9	李璘喆，杨建华.CHA型分子筛膜的研究进展[J].膜科学与技术，2022，42（2）：138-145.
	LI Linzhe， YANG Jianhua.Research advances of CHA zeolite membrane[J].Membrane Science and Technology，2022，42（2）：138-145.
10	JIANG Ji， WANG Xuerui， PENG Li，et al.Batch-scale preparation of hollow fiber supported CHA zeolite membranes and module for solvents dehydration[J].Microporous and Mesoporous Materials，2017，250：18-26.
11	IMASAKA S， ITAKURA M， YANO K，et al.Rapid preparation of high-silica CHA-type zeolite membranes and their separation pro-perties[J].Separation and Purification Technology，2018，199：298-303.
12	JIANG Ji， WANG Xuerui， ZHANG Yuting，et al. Fabrication of pure-phase CHA zeolite membranes with ball-milled seeds at low K+ concentration[J]. Microporous and Mesoporous Materials， 2015，215：98-108.
13	贾敏，杨磊，王永旺.体型化NaA分子筛的制备研究[J].无机盐工业，2021，53（10）：98-103.
	JIA Min， YANG Lei， WANG Yongwang.Study on preparation of body-shaped NaA Zeolite[J]. Inorganic Chemicals Industry， 2021，53（10）：98-103.
14	冯春峰，马丽，马静红，等.中孔FAU型沸石的合成及孔结构表征[J].无机材料学报，2014，29（11）：1173-1178.
	FENG Chunfeng， MA Li， MA Jinghong，et al.Synthesis and pore structure of mesozeolite FAU[J].Journal of Inorganic Materials， 2014，29（11）：1173-1178.
15	EILERTSEN E A， ARSTAD B， SVELLE S，et al.Single param-eter synthesis of high silica CHA zeolites from fluoride media[J].Microporous and Mesoporous Materials，2012，153：94-99.
16	CHEONG Y W， RIGOLET S， DAOU T J，et al. Crystal growth study of nanosized K-MER zeolite from bamboo leaves ash and its catalytic behaviour in Knoevenagel condensation of benzalde-hyde with ethyl cyanoacetate[J].Materials Chemistry and Phys-ics，2020，251.Doi：10.1016/j.matchemphys.2020.123100 . doi: 10.1016/j.matchemphys.2020.123100
17	DENG Xiaojun， ZHOU Ping， YAN Xiayan，et al.Green synthesis of low-silica CHA zeolite without organic structural directing agents，fl uoride media and seeds[J]. Microporous Mesoporous Materials，2021，310.Doi：10.1016/j.micromeso.2020.110618 . doi: 10.1016/j.micromeso.2020.110618

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会