CTAB辅助晶种法制备ZSM-5催化MTP反应

doi:10.11949/0438-1157.20240352

摘要/Abstract

摘要：

在晶种法合成过程中添加不同比例的十六烷基三甲基溴化铵（CTAB）作为晶体生长抑制剂制备了一系列纳米ZSM-5团聚体分子筛样品。采用XRD、SEM、ICP、氩气物理吸附、NH₃-TPD等分析手段表征了催化剂的孔结构和酸性等，并阐述了CTAB对ZSM-5分子筛物化性质的影响：适量CTAB的添加在促进ZSM-5分子筛晶化的同时可抑制晶体的进一步生长，使初级纳米晶粒产生团聚，增加了比表面积，促进了微孔孔道的构筑，增加了酸性位点。采用固定床反应器评价了样品在高空速下的甲醇制丙烯（MTP）催化性能。结果显示，样品Z5-2（合成初始物料中CTAB/SiO₂摩尔比为0.02）具有适宜的孔结构和酸量，表现出较好的催化性能，丙烯选择性为47.6%。

关键词: 分子筛, 晶种, 催化剂, 甲醇制丙烯

Abstract:

A series of nano-sized ZSM-5 agglomerates were prepared by adding different ratios of cetyltrimethylammonium bromide (CTAB) as a crystal growth inhibitor during the synthesis of crystal seeding method. The pore structure and acid properties of the samples are characterized by XRD, SEM, ICP, Ar adsorption-desorption, NH₃-TPD and other analytical methods, and the effects of CTAB on the physical and chemical properties of ZSM-5 molecular sieves were elaborated. The addition of appropriate amount of CTAB inhibited the further growth of crystals while promoting the crystallization of ZSM-5 molecular sieves, so that the primary nano-crystals agglomerated to increase the specific surface area, while promoting the construction of micropores and increasing the acid sites. The catalytic performance of this group of molecular sieve samples was evaluated for the methanol to propylene (MTP) reaction at high air velocity using a fixed-bed reactor. The results showed that sample Z5-2 (with a CTAB/SiO₂ molar ratio of 0.02 in the synthesized initial material) had suitable pore structure and acid volume, and exhibited good catalytic performance with propylene selectivity at 47.6%.

Key words: molecular sieve, seeds, catalyst, methanol to propylene

中图分类号:

O 643

张昊, 刘民, 郭新闻. CTAB辅助晶种法制备ZSM-5催化MTP反应[J]. 化工学报, 2024, 75(10): 3579-3587.

Hao ZHANG, Min LIU, Xinwen GUO. Preparation of ZSM-5 catalysts for MTP reaction by CTAB-assisted seeding method[J]. CIESC Journal, 2024, 75(10): 3579-3587.

图/表 9

图1 不同CTAB/SiO2摩尔比样品的XRD谱图

Fig.1 XRD patterns of samples with various CTAB/SiO2 molar ratios

图2 不同CTAB/SiO2摩尔比样品的SEM图

Fig.2 SEM images of samples with various CTAB/SiO2 molar ratios

图3 不同CTAB/SiO2摩尔比样品的氩气物理吸脱附曲线和孔径分布曲线

Fig.3 Ar adsorption-desorption isotherms and pore size distribution curves of samples with various CTAB/SiO2 molar ratios

表1 不同CTAB/SiO2摩尔比样品的Si/Al和孔结构特性

Table 1 Pore structure and solid yield of samples with various CTAB/SiO2 molar ratios

Sample	Si/Al molar ratio	S_BET/(m²/g)	S_Micro/ (m²/g)	S_Meso/(m²/g)	V_Total/ (cm³/g)	V_Micro/ (cm³/g)	V_Meso/ (cm³/g)
Z5-0	291	353	318	35	0.32	0.13	0.19
Z5-1	288	410	375	34	0.33	0.15	0.18
Z5-2	270	478	437	41	0.34	0.18	0.17
Z5-3	290	439	386	53	0.32	0.16	0.15
Z5-4	303	418	370	48	0.29	0.15	0.14
Z5-5	277	395	366	30	0.26	0.14	0.12

图4 不同CTAB/SiO2摩尔比样品的NH3-TPD曲线

Fig.4 NH3-TPD curves of samples with various CTAB/SiO2 molar ratios

表2 不同CTAB/SiO2摩尔比样品的酸量统计

Table 2 Acid amount of samples with various CTAB/SiO2 molar ratios

Sample	Total acidity/(μmol/g)	Weak acidity/(μmol/g)	Strong acidity/(μmol/g)
Z5-0	36	23	13
Z5-1	60	38	22
Z5-2	76	46	30
Z5-3	78	44	34
Z5-4	70	43	27
Z5-5	68	41	27

图5 不同CTAB/SiO2摩尔比样品在MTP反应中的催化性能

Fig.5 Catalytic performance of samples with various CTAB/SiO2 molar ratios in MTP reaction

表3 不同CTAB/SiO2摩尔比样品的平均甲醇转化率和产物选择性

Table 3 Average methanol conversion and product selectivity of samples with various CTAB/SiO2 molar ratios

Catalysts	Methanol conversion/%	Selectivity/%						P/E
Catalysts	Methanol conversion/%	CH₄	C₂H₄	C₃H₆	C₂₌~C₄₌	C₂~C₄	C₆₊	P/E
Z5-0	62.3	1.7	1.7	26.4	34.9	15.1	17.3	15.2
Z5-1	95.7	0.3	1.4	38.5	55.1	10.2	17.5	27.5
Z5-2	99.7	0.4	3.2	47.6	69.1	7.5	9.0	14.9
Z5-3	97.0	0.3	2.4	44.1	60.2	6.7	14.4	18.4
Z5-4	97.7	0.2	2.4	42.8	60.4	7.1	14.8	17.8
Z5-5	95.9	0.3	2.6	41.7	59.3	6.8	15.0	16.0

图6 丙烯选择性与不同CTAB/SiO2摩尔比样品强酸量、弱酸量及总酸量的关系

Fig.6 Correlation of propylene selectivity with strong acid amount, weak acid amount and total acid amount of samples with various CTAB/SiO2 molar ratios

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