Advances in Synthesis and Application of High-Silica LTA Zeolite

doi:10.19894/j.issn.1000-0518.240080

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (9): 1248-1258.DOI: 10.19894/j.issn.1000-0518.240080

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Advances in Synthesis and Application of High-Silica LTA Zeolite

Han-Bang LIU(), Wen-Yue HAO, Jun-Hui GUO, Chang LIU, Feng-Lai WANG, Shao-Zhong PENG

Sinopec （Dalian） Petrochemical Research Institute Co. ，Ltd. ，Dalian 116045，China

Received:2024-03-20 Accepted:2024-07-22 Published:2024-09-01 Online:2024-10-09
Contact: Han-Bang LIU
About author:liuhanbang.fshy@sinopec.com
Supported by:
the Scientific Research Fund of SINOPEC(122028)

Abstract

Abstract:

The Linde type A （LTA） zeolite is one of the earliest zeolites synthesized artificially. Currently， industrial LTA zeolite typically exhibits a relatively low Si/Al ratio. While it is widely used in adsorption and separation processes， its limited acid catalytic activity and hydrothermal stability hinder its potential for further applications. High-silica LTA zeolites demonstrate enhanced thermal/hydrothermal stability compared to their low-silica counterparts， exhibiting unique application potential in adsorption， separation and catalysis. This paper presents a review of the synthesis systems of high-silica LTA zeolites since 1966， with a focus on developments in the past two decades including inorganic and organic systems. It describes the synthesis mechanisms and evaluates the advantages and disadvantages of various synthesis methods with respect to the different synthesis systems and the Si/Al ratios. Additionally， the advancement of research and applications of high-silica LTA zeolites in adsorption， separation and catalysis are discussed. The future development and application prospects of LTA zeolite are envisioned， and it is highlighted that further research will focus on understanding the crystallization mechanism， developing simple synthetic systems and cost-effective structure-directing agents for high-silica LTA zeolites.

Key words: LTA zeolite, High silica, Structure-directing agent, Adsorption separation, Catalysis

CLC Number:

O613.7

Han-Bang LIU, Wen-Yue HAO, Jun-Hui GUO, Chang LIU, Feng-Lai WANG, Shao-Zhong PENG. Advances in Synthesis and Application of High-Silica LTA Zeolite[J]. Chinese Journal of Applied Chemistry, 2024, 41(9): 1248-1258.

Figures/Tables 9

Fig.1 Frameworks and structural units of LTA zeolite

Fig.2 Ternary phase diagram of zeolites prepared at 100 ℃ for 7 d in OSDA-free conditions［22］

Fig.3 Schematic illustration of the high-silica LTA zeolite formation pathway in the TEA+/TMA+/Na+ system［27］

Fig.4 OSDA for synthesizing ITQ-29： methylated julolidine （left） and crown ether Kryptofix 222 （right）［18］

Fig.5 The position of OSDA in high silica LTA： two 12DM3（4MB）I fit in α-cage of LTA， 1 TMA+ fits in β-cage of LTA ［31］

Fig.6 CO2 （A） and N2 （B） adsorption isotherms of NaK-ZK-4 with different K+ contents at 273 K： 0% （■）， 10% （●）， 18% （▲） and 26% （▼）［33］；（C） Regenerability of LTA zeolites with different Si/Al ratios in CO2/CH4 breakthrough experiments；（D） CO2 desorption curves of LTA zeolites： Si/Al ratio of 5 （solid line）， Si/Al ratio of 1 （dash line）［34］

Table 1 N2 and O2 uptakes and selectivity of LTA and H-LTA with different Si/Al molar ratios［36］

Sample	n（Si）/n（Al）	n（Na）/n（Al）	N₂ uptake/（mmol·g^-1）（100 kPa， 25 ℃）	O₂ uptake/（mmol·g^-1）（100 kPa， 25 ℃）	O₂/N₂ selecivity（V（O₂）∶V（N₂）=21∶79， 25 ℃）
NaA	1.05	0.95	0.372	0.132	0.33
NaA-H	1.06	0.54	0.262	0.138	0.50
ZK-4	2.20	0.71	0.290	0.218	0.71
ZK-4-H	2.15	0.07	0.174	0.203	1.17
NaUZM-9	2.94	0.57	0.238	0.213	0.85
NaUZM-9-H	2.81	0.08	0.155	0.202	1.32

Fig.7 （A） Three possible acid sites of LTA zeolite： H-O1， H-O2， H-O3；（B） Comparison between experimental INS spectra and periodic DFT results for H-O1， H-O2 and H-O3［41］

Fig.8 No conversion in NH3-SCR reaction over （A） fresh，（B） 923 K，（C） 1023 K and （D） 1123 K aged zeolite catalysts： Cu-LTA （■）， Cu-SSZ-13 （●）， Cu-ZSM-5 （▲） and Cu-PST-7 （▼）［32］

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Advances in Synthesis and Application of High-Silica LTA Zeolite

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