Research Progress on Synthesis of Hierarchical Beta Zeolites

doi:10.19894/j.issn.1000-0518.210246

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (6): 912-926.DOI: 10.19894/j.issn.1000-0518.210246

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Research Progress on Synthesis of Hierarchical Beta Zeolites

Shi-Shuai LI¹, Jia-Qi LIU¹, Jia-Yi WANG¹, Jiang-Feng YANG¹^,²()

^1.Research Institute of Special Chemicals，College of Chemistry and Chemical Engineering，Taiyuan University of Technology，Taiyuan 030024，China
^2.Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization，Taiyuan 030024，China

Received:2021-05-18 Accepted:2021-08-28 Published:2022-06-01 Online:2022-06-27
Contact: Jiang-Feng YANG
About author:yangjiangfeng@tyut.edu.cn
Supported by:
the National Natural Science Foundation of China(U20B6004)

Abstract

Abstract:

Zeolite molecular sieves are indispensable catalysts in many industrial processes. Among them， Beta zeolite has become one of the most widely produced zeolite materials with industrial significance because of its three-dimensional macroporous structure. Compared with the traditional Beta zeolite， the hierarchical Beta zeolite has many advantages such as smaller steric hindrance， higher mass transfer efficiency and so on， which can reduce the formation of carbon deposition， prolong the service time of catalyst and improve the utilization efficiency of catalyst. This review introduces the synthesis of hierarchical Beta zeolite in detail from the two strategies of “bottom-up” （direct synthesis） and “top-down” （post modification）. The synthesis of hierarchical Beta zeolite by hard template method， soft template method， mesoporous template method， dealuminization method and desilication method are introduced， and the characteristics of hierarchical Beta zeolite are briefly introduced. The advantages and problems of various synthesis methods are summarized and the future development prospects are also prospected.

Key words: Hierarchical pore, Beta zeolite, Catalyst

CLC Number:

O613.7

Shi-Shuai LI, Jia-Qi LIU, Jia-Yi WANG, Jiang-Feng YANG. Research Progress on Synthesis of Hierarchical Beta Zeolites[J]. Chinese Journal of Applied Chemistry, 2022, 39(6): 912-926.

Figures/Tables 14

References 79

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硬模板剂 Hard template agent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
葡萄糖 Glucose	465，527	30	［35］
三维有序大孔碳 3Dom	665~744	2~10	［36］
问荆 Equisetum arvense	73	5~15	［38］
聚乙烯醇缩丁醛 Polyvinyl butyral	447	4	［39］

硬模板剂 Hard template agent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
葡萄糖 Glucose	465，527	30	［35］
三维有序大孔碳 3Dom	665~744	2~10	［36］
问荆 Equisetum arvense	73	5~15	［38］
聚乙烯醇缩丁醛 Polyvinyl butyral	447	4	［39］

软模板剂 Soft template agent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
聚二烯丙基二甲基氯化铵 PDADMAC	377，443	5~40	［40?41］
聚二烯丙基二甲基氯化铵 PDADMAC	473~696	20~400	［42］
聚二烯丙基二甲基氯化铵 PDADMAC	510~579	20~30	［43］
聚二烯丙基二甲基氯化铵 PDADMAC	549~721	5~55	［44］
二甲基二烯丙基氯化铵丙烯酰胺共聚物 DMDAAC	529	10~30	［45］
C_18-6-18Br₂^a	431~582	2.5~3.2	［46］
3?丙基三甲氧基硅烷 PHAPTMS	631~798	2.8~3.9	［47］
双离子液体 ^b DCILs ^b	480~685	5	［50］
哌啶类表面活性剂 ^c Piperidine based surfactants ^c	1057	2~10	［51］
Ph（C?N?C₆?N?C₁₆）₂^d	677	3.9	［52］
Ph（C?N?C₆?N?C₁₆）₂^d	803	2.5~30	［53］
聚二烯丙基二甲基氯化铵 PDADMA	693~833	4.2~9.5	［54］
聚二烯丙基二甲基氯化铵 PDADMA	661~862	5~20	［55］
N₂?p?N₂^e	646	5~15	［56］
N₂?p?N₂^e	739	3.7	［57］

软模板剂 Soft template agent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
聚二烯丙基二甲基氯化铵 PDADMAC	377，443	5~40	［40?41］
聚二烯丙基二甲基氯化铵 PDADMAC	473~696	20~400	［42］
聚二烯丙基二甲基氯化铵 PDADMAC	510~579	20~30	［43］
聚二烯丙基二甲基氯化铵 PDADMAC	549~721	5~55	［44］
二甲基二烯丙基氯化铵丙烯酰胺共聚物 DMDAAC	529	10~30	［45］
C_18-6-18Br₂^a	431~582	2.5~3.2	［46］
3?丙基三甲氧基硅烷 PHAPTMS	631~798	2.8~3.9	［47］
双离子液体 ^b DCILs ^b	480~685	5	［50］
哌啶类表面活性剂 ^c Piperidine based surfactants ^c	1057	2~10	［51］
Ph（C?N?C₆?N?C₁₆）₂^d	677	3.9	［52］
Ph（C?N?C₆?N?C₁₆）₂^d	803	2.5~30	［53］
聚二烯丙基二甲基氯化铵 PDADMA	693~833	4.2~9.5	［54］
聚二烯丙基二甲基氯化铵 PDADMA	661~862	5~20	［55］
N₂?p?N₂^e	646	5~15	［56］
N₂?p?N₂^e	739	3.7	［57］

合成方法 Synthetic method	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
蒸汽辅助晶化法 SAC	608	4~30	［60］
蒸汽辅助晶化法 SAC	692~754	2~30	［61］
层状硅酸盐前驱体 H?kanemite	643~703	≈20	［62］
柯肯特尔增长 Kirkendall growth ^a		15~48	［63］
气溶胶辅助合成法 Aerosol?assisted	447~585	2~25	［69］

Research Progress on Synthesis of Hierarchical Beta Zeolites

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References 79

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脱铝溶液 Desilication solvent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
硝酸 HNO₃	608	4~30	［71］
硝酸 HNO₃	511	3.4~3.8	［72］
有机酸 Organic acid	340~380	2~30	［73］
氟化氢/氟化铵 HF/NH₄F	559~707	5	［74］

脱硅溶液 Desilication solvent	比表面积 S_BET/（m²·g^-1）	孔径 Pore size/nm	参考文献 Ref.
氢氧化钠 NaOH	595~705	≈3	［75］
氢氧化钠 NaOH	651~653		［76］
氢氧化钠 NaOH	170~630	3.4~5.7	［77］
氢氧化钠/氢氧化铵-十六烷基三甲基溴化铵 NaOH/NH₄OH?CTAB	696~793	3~3.2	［78］
氢氧化钠-四丙基铵阳离子 NaOH?TPA⁺	656~799	3.2~5.4	［79］

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