沸石中碱金属阳离子对CO2/N2O吸附分离性能的影响

doi:10.11949/0438-1157.20221542

摘要/Abstract

摘要：

氧化亚氮（N₂O）是仅次于CO₂和CH₄的第三大温室气体，排放后加剧温室效应，而N₂O具有广泛的用途，因此对其进行回收具有重要意义。苯酚法和环己烷法生产己二酸时排放的尾气中CO₂与N₂O共存，二者具有相同的动力学直径和相似的物理性质，它们的分离具有很大的挑战。研究了A型沸石中一价碱金属阳离子（Li⁺、Na⁺、K⁺、Cs⁺）对CO₂/N₂O吸附分离性能的影响，通过XRD、ICP-OES、SEM和TGA进行表征，并对吸附性能、IAST选择性以及分离性能进行了研究。研究结果表明，随着碱金属阳离子半径的增大，CO₂和N₂O的吸附容量逐渐降低，CsA几乎对CO₂和N₂O均不吸附；但CO₂/N₂O选择性却呈相反的趋势，其中KA的选择性达到最高（2.6），混合气体（ $V_{C O_{2}}$ / $V_{N_{2} O}$ =50%/50%）穿透实验结果也表明KA具有一定的CO₂/N₂O吸附分离性能。

关键词: 二氧化碳, 氧化亚氮, 沸石, 碱金属阳离子, 离子交换, 吸附分离

Abstract:

Nitrous oxide (N₂O) is the third largest greenhouse gas next to CO₂ and CH₄, and its emission will aggravate the greenhouse effect. However, N₂O has a wide range of uses, so its recovery is of great significance. CO₂ and N₂O coexist in the tail gas from the production of acid via the phenol and cyclohexane processes. Since they have the same kinetic diameter and similar physical properties, it is a great challenge to separate them. In this paper, the effect of monovalent alkali metal cations (Li⁺, Na⁺, K⁺, Cs⁺) in A-type zeolites on the adsorption and separation performance of CO₂/N₂O was investigated. Then, the samples were characterized by XRD, ICP-OES, SEM and TGA and the adsorption performance, IAST selectivity and separation performance were studied. The research results show that with the increase of alkali metal cation radius, the adsorption capacity of CO₂ and N₂O decreases gradually, and CsA almost does not adsorb CO₂ and N₂O. However, the selectivity of CO₂/N₂O shows an opposite trend, with KA reaching the highest selectivity (2.6). The penetration experiment results of mixed gases ( $V_{C O_{2}}$ / $V_{N_{2} O}$ =50%/50%) also indicate that KA has some CO₂/N₂O adsorption separation performance.

Key words: carbon dioxide, nitrous oxide, zeolite, alkali metal cations, ion exchange, adsorption separation

中图分类号:

TQ 028.1

蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.

Caihong LIN, Li WANG, Yu WU, Peng LIU, Jiangfeng YANG, Jinping LI. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O[J]. CIESC Journal, 2023, 74(5): 2013-2021.

图/表 13

图1 A型分子筛的XRD谱图

Fig.1 XRD patterns of A-type zeolite

表1 A型沸石的元素含量和阳离子交换度

Table 1 Element content and cation exchange degree on A-type zeolite

样品	质量浓度/(mg/L)						$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%	分子式
样品	C_Si	C_Al	C_Li	C_Na	C_K	C_Cs	$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%	分子式
LiA	67.41	72.43	9.88	25.59	—	—	1.80	56.15	—	—	—	Na₄₄Li₅₇Al₁₀₁Si₉₁O₃₈₄
NaA	58.57	48.46	—	58.57	—	—	1.82	—	100.00	—	—	Na₁₀₁Al₁₀₁Si₉₁O₃₈₄
KA	46.61	52.98	—	29.26	23.06	—	1.78	—	—	31.70	—	Na₆₉K₃₂Al₁₀₁Si₉₁O₃₈₄
CsA	52.78	55.70	—	27.16	—	112.2	1.82	—	—	—	42.50	Na₅₉Cs₄₂Al₁₀₁Si₉₁O₃₈₄

表1 A型沸石的元素含量和阳离子交换度

Table 1 Element content and cation exchange degree on A-type zeolite

样品	质量浓度/(mg/L)						$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%	分子式
样品	C_Si	C_Al	C_Li	C_Na	C_K	C_Cs	$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%	分子式
LiA	67.41	72.43	9.88	25.59	—	—	1.80	56.15	—	—	—	Na₄₄Li₅₇Al₁₀₁Si₉₁O₃₈₄
NaA	58.57	48.46	—	58.57	—	—	1.82	—	100.00	—	—	Na₁₀₁Al₁₀₁Si₉₁O₃₈₄
KA	46.61	52.98	—	29.26	23.06	—	1.78	—	—	31.70	—	Na₆₉K₃₂Al₁₀₁Si₉₁O₃₈₄
CsA	52.78	55.70	—	27.16	—	112.2	1.82	—	—	—	42.50	Na₅₉Cs₄₂Al₁₀₁Si₉₁O₃₈₄

图2 0℃下A型分子筛的CO2吸附曲线(a)和孔径分布曲线(b)

Fig.2 CO2 adsorption curves (a) and pore size distribution curves (b) of A-type zeolite at 0℃

图3 LiA、NaA、KA、CsA的SEM图和EDS元素分布

Fig.3 SEM images and EDS elemental distribution of LiA, NaA, KA, CsA

表2 不同阳离子的A型沸石的EDS元素分布

Table 2 EDS elemental distribution of A-type zeolites with different cations

样品	$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%
LiA	1.90	—	—	—	—
NaA	1.86	—	100.0	—	—
KA	1.80	—	—	30.5	—
CsA	1.82	—	—	—	54.3

表2 不同阳离子的A型沸石的EDS元素分布

Table 2 EDS elemental distribution of A-type zeolites with different cations

样品	$n_{S i O_{2}}$ / $n_{A l_{2} O_{3}}$	E_Li/%	E_Na/%	E_K/%	E_Cs/%
LiA	1.90	—	—	—	—
NaA	1.86	—	100.0	—	—
KA	1.80	—	—	30.5	—
CsA	1.82	—	—	—	54.3

图4 A型分子筛的热重曲线

Fig.4 TGA curves of A-type zeolites

图5 LiA、NaA、KA、CsA在0℃和25℃下的CO2和N2O吸附等温线

Fig.5 CO2 and N2O adsorption isotherms of LiA, NaA, KA, CsA at 0℃ and 25℃

表3 A型沸石在25℃下对CO2和N2O的吸附等温线的Dual-Site Langmuir拟合参数

Table 3 Dual-Site Langmuir parameters for CO2 and N2O at 25℃ on A-type zeolite

吸附剂	吸附质	q₁/(cm³/g)	q₂/(cm³/g)	b₁	b₂	R²
LiA	CO₂	60.20	63.35	46.17	3.79	0.999
LiA	N₂O	66.25	40.68	34.32	1.37	0.999
NaA	CO₂	47.31	26.54	54.49	0.70	0.999
NaA	N₂O	58.03	1.92	44.29	44.40	0.999
KA	CO₂	29.55	36.53	63.67	9.06	0.999
KA	N₂O	86.72	32.71	2.94	32.71	0.999

图6 A型沸石对CO2/N2O的IAST选择性(a)；部分材料[21,43]对CO2/N2O选择性的比较(b)

Fig.6 IAST selectivity of CO2/N2O on A-type zeolite (a);Comparison of CO2/N2O selectivity on some materials[21,43] (b)

表4 A型沸石在25℃时的吸附量和IAST选择性

Table 4 Adsorption capacity and IAST selectivity of A-type zeolite at 25℃

样品	CO₂吸附量/(cm³/g)	N₂O吸附量/(cm³/g)	CO₂/N₂O选择性
LiA	81.31	81.04	0.8
NaA	92.02	87.82	2.0
KA	80.21	67.55	2.6
CsA	0.48	1.22	—

图7 LiA、NaA、KA在25℃下CO2和N2O的吸附热

Fig.7 Adsorption heats of CO2 and N2O on LiA, NaA, KA at 25℃

图8 25℃时KA上CO2和N2O混合物(50%/50%，体积分数)的穿透曲线

Fig.8 Penetration curve of CO2 and N2O mixtures (50%/50%, volume ratio) on KA at 25℃

图9 25℃、100 kPa下KA对CO2和N2O吸附循环(a)以及吸附循环前后样品的XRD谱图(b)

Fig.9 CO2 and N2O adsorption recycles of KA at 25℃ and 100 kPa (a) and XRD patterns of samples before and after adsorption recycles (b)

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沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响

Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O

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