Immobilize Cu(Ⅰ) into π-complexed MOF adsorbent for selectivity separation of ethane/ethylene

doi:10.11949/0438-1157.20240120

Abstract

Abstract:

As a common adsorbent, metal-organic frameworks (MOFs) has been widely researched in the separation of ethane and ethylene gas mixtures, and the π-complexation generated by the introduction of metal ions can significantly improve the adsorption capacity of MOFs for ethylene. Cu(Ⅰ) was loaded into the dihydroxyl-functionalized UiO-66, and a Cu(Ⅰ)@UiO-66-(OH)₂ adsorbent that preferentially adsorbed ethylene was obtained. The hydroxyl functionalized framework has a synergistic effect with Cu(Ⅰ) while enhancing the polarity, which can effectively improve the adsorption and separation performance of ethylene/ethane. The calculated C₂H₄/C₂H₆ IAST selectivity of 3% (mass) Cu(Ⅰ)@UiO-66-(OH)₂ at 298 K and 1 bar is 2.98, which is approximately 3 times of the original UiO-66-(OH)₂. Single-component adsorption experiments show that the adsorption capacity of 3%Cu(Ⅰ)@UiO-66-(OH)₂ for ethylene is higher than that of ethane in the whole pressure range, and its adsorption heat of ethylene (42.81 kJ·mol^-1) is lower than that of many reported ethylene-selective adsorbents. The breakthrough experiments of 50/50 (volume ratio) C₂H₄/C₂H₆ mixture under simulated industrial conditions further demonstrate that the 3%Cu(Ⅰ)@UiO-66-(OH)₂ adsorbent can effectively separate the ethane/ethylene mixture.

Key words: ethane, ethylene, adsorption, adsorbent, selectivity, π-complexation

摘要：

金属有机框架材料作为常见的吸附剂，已被广泛地应用于乙烷和乙烯气体混合物的分离，其中引入金属离子所产生π-络合作用可以显著提高MOFs对乙烯的吸附能力。在双羟基功能化后的UiO-66中负载Cu（Ⅰ），得到了优先吸附乙烯的Cu（Ⅰ）@UiO-66-（OH）₂吸附剂。羟基功能化的框架在增强极性的同时，可以与Cu（Ⅰ）产生协同效应，有效地提高了材料对乙烯/乙烷的吸附分离性能。得到的3%（质量分数）Cu（Ⅰ）@UiO-66-（OH）₂在298 K及1 bar（1 bar=0.1 MPa）条件下的C₂H₄/C₂H₆ IAST选择性为2.98，约为纯UiO-66-（OH）₂的3倍。单组分吸附实验证明3%Cu（Ⅰ）@UiO-66-（OH）₂在整个压力范围下对乙烯的吸附容量均高于乙烷，并且其对乙烯的吸附热（42.81 kJ·mol^-1）低于许多已报道的乙烯-选择性吸附剂。在模拟工业条件下对50/50（体积比）C₂H₄/C₂H₆混合物进行穿透实验，进一步表明了3%Cu（Ⅰ）@UiO-66-（OH）₂吸附剂可以有效分离乙烷/乙烯混合物。

关键词: 乙烷, 乙烯, 吸附, 吸附剂, 选择性, π-络合作用

CLC Number:

TQ 028.1

Taohong WANG, Chao WANG, Zheng LI, Ying LIU, Ge TIAN, Ganggang CHANG, Xiaoyu YANG, Zongbi BAO. Immobilize Cu(Ⅰ) into π-complexed MOF adsorbent for selectivity separation of ethane/ethylene[J]. CIESC Journal, 2024, 75(7): 2565-2573.

王涛虹, 王超, 李政, 刘莹, 田歌, 常刚刚, 阳晓宇, 鲍宗必. 固载Cu（Ⅰ）的π络合MOF吸附剂用于乙烷/乙烯的选择性分离[J]. 化工学报, 2024, 75(7): 2565-2573.

Figures/Tables 6

Fig.1 SEM images of UiO-66-(OH)2 (a) and 3%Cu(Ⅰ)@UiO-66-(OH)2 (b); EDS diagram of 3%Cu(Ⅰ)@UiO-66-(OH)2 (c); PXRD pattern of Cu(Ⅰ)@UiO-66-(OH)2 (d)

Fig.2 N2 adsorption isotherm of Cu(Ⅰ)@UiO-66-(OH)2 at 77 K (a); Single-component adsorption isotherms of Cu(Ⅰ)@UiO-66-(OH)2 at 298 K and 1 bar (b); Single-component adsorption-desorption isotherms of 3%Cu(Ⅰ)@UiO-66-(OH)2 at different temperatures (c); Adsorption heats of C2H6 and C2H4 in 3%Cu(Ⅰ)@UiO-66-(OH)2 (d) [in figures (a) and (c), the hollow sphere represents desorption, the solid sphere represents adsorption; in figure (b), the hollow sphere represents ethane, the solid sphere represents ethylene]

Table 1 Adsorption capacity of C2H6 and C2H4 of UiO-66-（OH）2 and different loads of Cu（Ⅰ）@UiO-66-（OH）2 and their BET specific surface area

样品名称	CuCl浸渍量/mg	C₂H₆吸附量/(mmol·g^-1)	C₂H₄吸附量/(mmol·g^-1)	BET比表面积/(m²·g^-1)
UiO-66-(OH)₂	—	2.83	3.21	788.3
0.5%Cu(Ⅰ)@UiO-66-(OH)₂	30	2.69	2.97	693.3
3%Cu(Ⅰ) @UiO-66-(OH)₂	65	2.21	2.95	352.3
11%Cu(Ⅰ)@UiO-66-(OH)₂	100	2.28	2.79	308.0

Table 2 Dual-Site Langmuir fitting parameters for adsorption isotherms of C2H4 and C2H6 of UiO-66-（OH）2 and 3%Cu（Ⅰ）@UiO-66-（OH）2 at 298 K

吸附剂	吸附质	q₁/(cm³·g^-1)	q₂/(cm³·g^-1)	b₁	b₂	R²
UiO-66-(OH)₂	C₂H₄	3.416	1.896	0.136	0.007	0.999
UiO-66-(OH)₂	C₂H₆	3.162	1.256	0.327	0.010	0.999
3%Cu(Ⅰ)@UiO-66-(OH)₂	C₂H₄	4.008	0.747	0.397	0.013	0.999
3%Cu(Ⅰ)@UiO-66-(OH)₂	C₂H₆	2.863	0.401	0.491	0.017	0.999

Fig.3 C2H4/C2H6 selectivity of UiO-66-(OH)2 and 3%Cu(Ⅰ)@UiO-66-(OH)2 (a); IAST comparison of 3%Cu(Ⅰ)@UiO-66-(OH)2 with other similar materials (b)

Fig.4 Dynamic breakthrough curve of C2H6/C2H4 (50∶50, volume ratio) gas mixture (a) and 5 cycles adsorption curve for ethylene (b)of 3%Cu(Ⅰ)@UiO-66-(OH)2 at 298 K and 1 bar; PXRD pattern (c) and N2 adsorption isotherm (d) of 3%Cu(Ⅰ)@UiO-66-(OH)2 before and after multiple cycles

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