无黏结剂ZSM-35沸石的制备与催化反应性能

doi:10.16085/j.issn.1000-6613.2019-0906

摘要/Abstract

摘要：

考察了不同硅铝比无黏结剂ZSM-35沸石分子筛的合成条件及催化反应性能。以多种有机胺（乙二胺、环己胺、正丁胺）为模板剂，在SiO₂/Al₂O₃为30～40的情况下均可以水热合成无黏结剂ZSM-35沸石。在乙二胺模板剂体系中，ZSM-35合适的晶化温度为130～160℃。提高SiO₂/Al₂O₃至58时，在乙二胺和正丁胺模板剂体系下，合成产物易出现ZSM-5和石英相，而环己胺作为模板剂可以成功制备纯相的无黏结剂ZSM-35沸石。在SiO₂/Al₂O₃为72时，以乙二胺、环己胺、正丁胺为模板剂均难合成纯相ZSM-35沸石，易产生杂晶。在二甲苯异构化反应中，制备的ZSM-35沸石表现出比ZSM-5沸石更好的对二甲苯选择性和更低的二甲苯损失。

关键词: 无黏结剂, 沸石, 水热合成, 催化剂, 二甲苯, 异构化

Abstract:

The synthesis conditions and catalytic properties of ZSM-35 zeolites with different SiO₂/Al₂O₃ratios were investigated. ZSM-35 zeolite with SiO₂/Al₂O₃ ratios in the range of 30 to 40 can be hydrothermal synthesized with various organic amines (ethylenediamine, cyclohexamine and n-butylamine) as templates. The suitable crystallization temperature in the ethylenediamine template system was 130-160℃. With ethylenediamine and n-butylamine as templates, ZSM-5 and quartz phase were easily formed when SiO₂/Al₂O₃ ratio was 58. Binderless ZSM-35 zeolite with relatively high SiO₂/Al₂O₃ ratio of 58 can be synthesized with cyclohexamine as template. When SiO₂/Al₂O₃ ratio was 72, it was difficult to synthesize pure ZSM-35 zeolite in ethylenediamine, cyclohexylamine and n-butylamine templates, and heterocrystals were also produced. In xylene isomerization reaction, ZSM-35 zeolite showed better p-xylene selectivity and lower xylene loss than ZSM-5 zeolite.

Key words: binderless, zeolite, hydrothermal synthesis, catalyst, xylene, isomerization

中图分类号:

O643.3

郭友娣,任杰,王德举. 无黏结剂ZSM-35沸石的制备与催化反应性能[J]. 化工进展, 2020, 39(2): 548-553.

Youdi GUO,Jie REN,Deju WANG. Preparation of binderless ZSM-35 zeolite and its catalytic performance[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 548-553.

图/表 10

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温度/℃	S_BET/m²·g^-1	V/cm³·g^-1	结晶度/%
130	282.1	0.158	96.5
145	281.2	0.159	98.8
160	278.0	0.157	92.3

温度/℃	S_BET/m²·g^-1	V/cm³·g^-1	结晶度/%
130	282.1	0.158	96.5
145	281.2	0.159	98.8
160	278.0	0.157	92.3

样品编号	S_BET/m²·g^-1	V/cm³·g^-1	压碎强度/N·cm^-1	结晶度/%
ZSM-35-1	291.6	0.177	67	100.0
ZSM-35-2	287.0	0.157	66	98.4
ZSM-35-3	281.9	0.168	59	96.8
ZSM-5	360.1	0.163	61	—

样品编号	S_BET/m²·g^-1	V/cm³·g^-1	压碎强度/N·cm^-1	结晶度/%
ZSM-35-1	291.6	0.177	67	100.0
ZSM-35-2	287.0	0.157	66	98.4
ZSM-35-3	281.9	0.168	59	96.8
ZSM-5	360.1	0.163	61	—

酸类型	HZSM-5		HZSM-35-1		HZSM-35-2		HZSM-35-3
酸类型	B酸	L酸	B酸	L酸	B酸	L酸	B酸	L酸
200℃酸量×10²/mmol·g^-1	16.76	10.95	29.75	4.2	33.55	3.52	8.66	3.28
300℃酸量×10²/mmol·g^-1	15.61	3.97	33.51	2.36	36.56	3.34	11.44	2.05
400℃酸量×10²/mmol·g^-1	14.89	2.46	33.57	1.86	37.65	3.00	18.14	1.65