分子筛基CH4-N2分离材料的研究进展

doi:10.16085/j.issn.1000-6613.2018-1060

摘要/Abstract

摘要：

实现CH₄-N₂高效分离能够极大地推动常规天然气和非常规天然气这一类绿色低碳能源的利用，分子筛基吸附剂和膜材料具有优良的气体分离特性，而且对CH₄-N₂的分离颇具应用潜力。本文从对N₂具有优先选择性吸附的N₂/CH₄分离（高浓度CH₄纯化脱氮）和对CH₄具有优先选择性吸附的CH₄/N₂分离（低浓度CH₄富集脱氮）两方面综述了国内外分子筛吸附剂及分子筛膜的研究进展。详细地分析了分子筛骨架和平衡阳离子与其CH₄-N₂吸附分离性能之间的构效关系，并结合本文作者课题组的工作，提出了电中性（近中性）骨架分子筛对CH₄-N₂分离具有较好的分离效果。最后总结和展望了CH₄-N₂分离用分子筛吸附剂及分子筛膜的未来发展趋势。

关键词: 分子筛, 吸附剂, 膜, 甲烷, 分离

Abstract:

The high efficient separation of CH₄-N₂ can greatly promote the use of the conventional and unconventional natural gas which is a kind of green and low carbon energy. Zeolite-based adsorbents and membrane materials have excellent gas separation characteristics and great potential for CH₄-N₂ separation. In this review，the state of the art of zeolite adsorbents and membranes for CH₄-N₂ separation was discussed from two aspects：N₂-selective separation（high-concentration methane purification） and CH₄-selective separation（low-concentration methane enrichment）. The structure-activity relationship between the framework and cations of zeolite and its adsorption and separation performance of CH₄-N₂ was analyzed in detail. Combining with the previous work of our group, we proposed that the electroneutral (near-neutral) framework molecular sieve has better separation of CH₄-N₂. Finally, the future trend of molecular sieve adsorbents and membrane materials for CH₄-N₂ separation is summarized and prospected.

Key words: molecular sieves, adsorbents, membranes, methane, separation

中图分类号:

TQ424.25

刘佳奇, 尚华, 唐轩, 杨江峰, 李晋平. 分子筛基CH₄-N₂分离材料的研究进展[J]. 化工进展, 2019, 38(01): 449-456.

LIUJiaqi, Hua SHANG, Xuan TANG, Jiangfeng YANG, Jinping LI. Zeolite based materials for CH₄-N₂ separation[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 449-456.

图/表 7

表1 CH4和N2的部分物化性质

气体

分子量

动力学直径/nm

临界温度

/℃

极化率

×10²⁵

/cm³

偶极矩

×10¹⁸

/esu·cm

四极矩

×10²⁶

/esu·cm²

CH₄

N₂

图1 分子筛NaSr-ETS-4（75%Sr）在543K（270℃）下脱水后对CH4和N2的等温吸附线（298K）[15]

图2 ZK-5-K和ZK-5-Cs分子筛分离N2/CH4 [22]

图3 纵横比分别大约为1、3、10、20的SAPO-34晶种[30]

表2 不同分子筛膜对N2/CH4的分离性能

分子筛膜	分离系数(α)	N₂渗透速率^①×10⁸ /mol·m^-2 ·s^-1 ·Pa^-1	参考文献
ETS-4	5.4	1	[26]
DD3R	20～45	0.01	[27]
T^②	8.7	0.26	[28]
SSZ-13	9	2	[29]
SAPO-34	5～7	10	[29]
SAPO-34	11.3	40	[30]
SAPO-34	7.4	43	[31]
SAPO-34	8.6	70	[32]
AlPO-18	4.6	100	[33]

图4 纯硅分子筛DDR、silicalite-1和beta与富铝分子筛5A和13X对CH4/N2（50%/50%）的选择性系数和混合气体穿透曲线[39]

图5 气体扩散在介孔中传质提升的示意图及CH4/N2(50%/50%)和C2H6/CH4(50%/50%)混合气体在介孔silicalite-1(实心)和微孔silicalite-1（空心）的穿透曲线 [42]

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分子筛基CH₄-N₂分离材料的研究进展

Zeolite based materials for CH₄-N₂ separation

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