多级孔NaX分子筛的合成及CO2吸附性能

doi:10.7503/cjcu20200083

摘要/Abstract

摘要：

采用两步晶化和氨基酸辅助的协同合成策略, 制备了具有高产率(89%)和高结晶度(微孔体积为0.30 cm ³/g)的多级孔NaX分子筛. 利用X射线粉末衍射、扫描电子显微镜、透射电子显微镜和氮气吸附等技术, 考察了两步晶化和氨基酸加入量对NaX分子筛的形貌、相对结晶度和产率的影响. 实验结果表明, 两步晶化有利于多级孔结构的产生, 氨基酸的引入有助于提高分子筛相对结晶度和产率. 与传统方法合成的NaX分子筛相比, 该合成策略制备的多级孔NaX分子筛展现出更优异的CO₂吸附性能, 在273 K和100 kPa条件下, 其CO₂吸附量达到154.2 cm ³/g, 而传统NaX分子筛的CO₂吸附量为147.6 cm ³/g. 该合成策略为绿色且高效制备高质量的多级孔分子筛提供了新思路.

关键词: NaX分子筛, 多级孔, 两步晶化, L-赖氨酸, CO₂吸附

Abstract:

High-quality hierarchical NaX zeolites with high product yield and high crystallinity were prepared by synergistically using a two-step crystallization process and L-lysine-assisted approach. XRD, SEM, TEM, XRF and N₂ adsorption-desorption tests are used to investigate the influence of L-lysine and crystallization steps on the mesoporosity, crystallinity, and the yield of NaX zeolites. In this synthetic strategy, two-step crystallization favors the generation of mesopores; and L-lysine plays an important role in improving the zeolite crystallinity as well as the product yield. Owing to the high-quality hierarchical zeolite crystals, the as-prepared NaX zeolite exhibits excellent performance in CO₂ adsorption with CO₂ uptake of 154.2 cm ³/g at 273 K and 100 kPa. This green and facile synthetic strategy opens a new way to fabricate high-quality hierarchical NaX zeolites, promising their practical applications in CO₂ adsorption.

Key words: NaX zeolite, Hierarchical structure, Two-step crystallization, L-lysine, CO₂ adsorption

中图分类号:

O613.72
O647

TrendMD:

王煜瑶, 张强, 于吉红. 多级孔NaX分子筛的合成及CO₂吸附性能. 高等学校化学学报, 2020, 41(4): 616.

WANG Yuyao, ZHANG Qiang, YU Jihong. Synthesis of Hierarchical NaX Zeolite and Its CO₂ Adsorption Performance ^†. Chem. J. Chinese Universities, 2020, 41(4): 616.

图/表 8

Table 1 Synthetic conditions, Si/Al molar ratios and yields of NaX zeolites

Sample	x	Crystallization				Si/Al molar ratio^a	Yield^b	Relative XRD crystallinity^c(%)
		Temperature/℃		Time/h
		T₁	T₂	t₁	t₂
X-L₀-60(36 h)/100(12 h)	0	60	100	36	12	1.17	82	70
X-L_1.0-60(36 h)/100(12 h)	1.0	60	100	36	12	1.16	85	82
X-L_2.0-60(36 h)/100(12 h)	2.0	60	100	36	12	1.24	89	100
X-L₀-100(24 h)	0	100		24		1.09	58	82
X-L_1.0-100(24 h)	1.0	100		24		1.14	60	85
X-L_2.0-100(24 h)	2.0	100		24		1.21	64	97

Fig.1 XRD patterns of NaX samples and simulated one(A) a. Simulated; b. X-L0-60(36 h)/100(12 h); c. X-L1.0-60(36 h)/100(12 h); d. X-L2.0-60(36 h)/100(12 h). (B) a. Simulated; b. X-L0-100(24 h); c. X-L1.0-100(24 h); d. X-L2.0-100(24 h).

Fig.2 SEM images of NaX samples with or without two-step crystallization(A) X-L0-60(36 h)100(12 h); (B) X-L1.0-60(36 h)100(12 h); (C) X-L2.0-60(36 h)100(12 h); (D) X-L0-100(24 h); (E) X-L1.0-100(24 h); (F) X-L2.0-100(24 h).

Table 2 Porosity of selected NaX samples

Sample	$S a BET$ / (m²·g^-1)	$S b micro$ / (m²·g^-1)	$S b Ext$ / (m²·g^-1)	$V b micro$ / (cm³·g^-1)	$V c meso$ / (cm³·g^-1)	$V d total$ / (cm³·g^-1)
X-L₀-60(36 h)/100(12 h)	679	579	100	0.28	0.26	0.54
X-L_1.0-60(36 h)/100(12 h)	692	593	99	0.28	0.25	0.53
X-L_2.0-60(36 h)/100(12 h)	706	624	82	0.30	0.20	0.50
X-L₀-100(24 h)	652	573	79	0.27	0.10	0.37

Table 2 Porosity of selected NaX samples

Sample	$S a BET$ / (m²·g^-1)	$S b micro$ / (m²·g^-1)	$S b Ext$ / (m²·g^-1)	$V b micro$ / (cm³·g^-1)	$V c meso$ / (cm³·g^-1)	$V d total$ / (cm³·g^-1)
X-L₀-60(36 h)/100(12 h)	679	579	100	0.28	0.26	0.54
X-L_1.0-60(36 h)/100(12 h)	692	593	99	0.28	0.25	0.53
X-L_2.0-60(36 h)/100(12 h)	706	624	82	0.30	0.20	0.50
X-L₀-100(24 h)	652	573	79	0.27	0.10	0.37

Fig.3 TEM images of NaX samples with two-step crystallization (A) X-L0-60(36 h)100(12 h); (B) X-L1.0-60(36 h)100(12 h); (C) X-L2.0-60(36 h)100(12 h).

Fig.4 XRD patterns of samples with different crystallization timea. X-L2.0-60(36 h); b. X-L2.0-60(36 h)/100(1 h); c. X-L2.0-60(36 h)/100(2 h); d. X-L2.0-60(36 h)/100(4 h); e. X-L2.0-60(36 h)/100(12 h).

Fig.5 TEM images of crystal evolution under 100 ℃ for samples X-L2.0-60(36 h)/100(1 h)(A), X-L2.0-60(36 h)/100(2 h)(B) and X-L2.0-60(36 h)/100(12 h)(C)

Table 3 CO2 adsorption quantities at 100 kPa at 273 and 298 K*

Sample	Adsorption quantitity
Sample	273 K	298 K
X-L_1.0-60(36 h)/100(12 h)	154.2	140.6
X-L_2.0-60(36 h)/100(12 h)	151.9	142.4
X-L₀-100(24 h)	147.6	129.2

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多级孔NaX分子筛的合成及CO₂吸附性能

Synthesis of Hierarchical NaX Zeolite and Its CO₂ Adsorption Performance ^†

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