Co-MOF-74和Mg-MOF-74的CO工作吸附容量及操作条件

doi:10.11949/0438-1157.20241210

摘要/Abstract

摘要：

Co-MOF-74和Mg-MOF-74分别代表具有强和弱CO结合位点的材料，其常温常压下的CO吸附容量不能评估其在CO/N₂变压吸附过程的适用性。通过不同操作条件下的单组分静态和双组分动态穿透实验，研究Co-MOF-74和Mg-MOF-74的CO工作吸附容量、再生性和吸附热（Q_st）及其对应的操作温度和吸-脱附压力。结果表明，当CO/N₂组成为50%/50%时，Co-MOF-74的最佳操作条件为100℃、3.0~0.2 bar（吸附-解吸总压），CO工作吸附容量和再生性分别为2.85 mmol·g^-1和83.82%；而Mg-MOF-74为25℃、2.0~0.2 bar，CO工作吸附容量和再生性分别为1.63 mmol·g^-1和79.51%。Co-MOF-74在100℃下的Q_st（34.57 kJ·mol^-1）与Mg-MOF-74在25℃下的Q_st（35.45 kJ·mol^-1）相近，表明具有不同结合位点的吸附剂对CO的Q_st在35.00 kJ·mol^-1左右所对应的温度为最佳操作温度。研究结果可以为具有不同CO结合位点的吸附剂的变压吸附工艺设计提供参考。

关键词: MOF-74, 一氧化碳, 吸附, 工作吸附容量, 再生, 吸附热, 操作条件

Abstract:

Co-MOF-74 and Mg-MOF-74 represent materials with strong and weak CO binding sites, respectively, and their CO adsorption capacities at room temperature and pressure cannot be evaluated for suitability in the CO/N₂ pressure swing adsorption process. The CO working adsorption capacity, regeneration and adsorption heat (Q_st) of Co-MOF-74 and Mg-MOF-74 and their corresponding operating temperature and adsorption-desorption pressure were studied by single-component static and two-component dynamic penetration experiments under different operating conditions. The results showed that when the CO/N₂ composition was 50%/50%, the optimal operating conditions for Co-MOF-74 were 100℃ and 3.0—0.2 bar (total adsorption-desorption pressure), with a working capacity and regenerability for CO of 2.85 mmol·g^-1 and 83.82%, respectively, for Mg-MOF-74, at 25℃, 2.0—0.2 bar, the working capacity and regeneration for CO were 1.63 mmol·g^-1 and 79.51%, respectively. The Q_st of Co-MOF-74 at 100℃ (34.57 kJ·mol^-1) is similar to that of Mg-MOF-74 at 25℃ (35.45 kJ·mol^-1), indicating that the Q_st of the adsorbents with different binding sites for CO was about 35.00 kJ·mol^-1, which is considered the optimal operating temperature. This study can provide a reference for the design of pressure swing adsorption process using adsorbents with different CO binding sites.

Key words: MOF-74, carbon monoxide, adsorption, working adsorption capacity, regeneration, adsorption heat, operating condition

中图分类号:

TQ 028.1

唐磊, 王振菲, 李聪利, 杨佳辉, 郑浩, 石琪, 董晋湘. Co-MOF-74和Mg-MOF-74的CO工作吸附容量及操作条件[J]. 化工学报, 2025, 76(5): 2279-2293.

Lei TANG, Zhenfei WANG, Congli LI, Jiahui YANG, Hao ZHENG, Qi SHI, Jinxiang DONG. CO working capacity and operating conditions of Co-MOF-74 and Mg-MOF-74[J]. CIESC Journal, 2025, 76(5): 2279-2293.

图/表 17

图1 测试CO/N2穿透曲线的装置示意图V-1,V-2,V-3,V-4,V-5,V-6,V-7—球阀;V-8—背压调节器;MFC—质量流量控制器;L-1—混合罐;L-2—吸附柱;VP—真空泵;MS—质谱分析仪;P1—吸附柱前压力表;P2—吸附柱后压力表;P3—真空泵前压力表;Vent—排空

Fig.1 Diagram of device for testing CO/N2 breakthrough curve

图2 Co-MOF-74和Mg-MOF-74样品的PXRD和FTIR图

Fig.2 Co-MOF-74 and Mg-MOF-74 samples: (a) PXRD patterns; (b) FTIR spectra

图3 两种样品的SEM图片

Fig.3 SEM images of two samples

图4 Co-MOF-74和Mg-MOF-74样品的热重曲线

Fig.4 TG curves of Co-MOF-74 and Mg-MOF-74 samples

图5 Co-MOF-74和Mg-MOF-74样品的N2吸-脱附等温线（77 K）和水蒸气吸-脱附等温线（298 K）

Fig.5 N2 adsorption-desorption isotherms (77 K) and water vapor adsorption-desorption isotherms (298 K) of Co-MOF-74 and Mg-MOF-74

图6 两种样品的CO和N2吸附等温线

Fig.6 Adsorption isotherms of CO and N2 for two samples

图7 两种样品在不同测试温度和压力范围下的CO吸附等温线

Fig.7 CO adsorption isotherms of two samples at different test temperatures and pressure ranges

图8 根据两种样品CO吸附等温线计算出的CO吸附容量、工作吸附容量和再生性

Fig.8 CO adsorption capacity, working capacity and regenerability of two samples were calculated based on CO adsorption isotherms

表1 Co-MOF-74和Mg-MOF-74的CO静态吸附容量、工作吸附容量和再生性总结

Table 1 Summary of static adsorption capacity， working capacity and regenerability of CO for Co-MOF-74 and Mg-MOF-74

样品	T/℃	吸附容量			工作吸附容量			R/%
		p/bar		n_CO/(mmol·g^-1)	p/bar		Δn_CO/(mmol·g^-1)
		解吸	吸附	n_CO/(mmol·g^-1)	解吸	吸附	Δn_CO/(mmol·g^-1)
Co-MOF-74	25	0	0.5	5.38	0.1	0.5	1.04	19.33
	60	0	0.5	4.75	0.1	0.5	1.70	35.79
	100	0	0.5	2.50	0.1	0.5	1.74	69.60
	140	0	0.5	0.93	0.1	0.5	0.77	82.80
	25	0	1.5	5.71	0.1	1.5	1.37	23.99
	60	0	1.5	5.44	0.1	1.5	2.39	43.93
	100	0	1.5	3.89	0.1	1.5	3.13	80.46
	140	0	1.5	2.10	0.1	1.5	1.94	92.38
	25	0	3.0	5.93	0.1	3.0	1.59	26.81
	60	0	3.0	5.75	0.1	3.0	2.70	46.96
	100	0	3.0	4.73	0.1	3.0	3.97	83.93
	140	0	3.0	3.12	0.1	3.0	2.96	94.87
Mg-MOF-74	25	0	0.5	2.83	0.1	0.5	1.86	65.72
	60	0	0.5	1.17	0.1	0.5	0.88	75.21
	25	0	1.0	3.73	0.1	1.0	2.76	73.99
	60	0	1.0	1.92	0.1	1.0	1.63	84.90
	25	0	2.0	4.52	0.1	2.0	3.55	78.54
	60	0	2.0	2.82	0.1	2.0	2.53	89.72

图9 两种样品在不同测试温度下的CO/N2 IAST选择性

Fig.9 CO/N2 IAST selectivity of two samples at different test temperatures

图10 Co-MOF-74的CO/N2（体积比50%/50%）穿透曲线T—操作温度;Partial—CO吸附分压;Ad.—吸附总压;De.—解吸总压

Fig.10 CO/N2 (50%/50%, vol) breakthrough curves of Co-MOF-74T—operating temperature; Partial—CO adsorption partial pressure; Ad.—total adsorption pressure; De.—total desorption pressure

图11 Mg-MOF-74的CO/N2（体积比50%/50%）穿透曲线T—操作温度;Partial—CO吸附分压;Ad.—吸附总压;De.—解吸总压

Fig.11 CO/N2 (50%/50%, vol) breakthrough curves of Mg-MOF-74T—operating temperature; Partial—CO adsorption partial pressure; Ad.—total adsorption pressure; De.—total desorption pressure

图12 根据两种样品CO/N2穿透曲线计算出的CO吸附容量、工作吸附容量和再生性

Fig.12 CO adsorption capacity, working capacity and regenerability of two samples were calculated based on CO/N2 breakthrough curves

表2 Co-MOF-74和Mg-MOF-74的CO动态吸附容量、工作吸附容量和再生性总结

Table 2 Summary of dynamic adsorption capacity， working capacity and regenerability of CO for Co-MOF-74 and Mg-MOF-74

样品	进样组成(CO/N₂)	T/℃	吸附容量			工作吸附容量			R/%
			p/bar		n_CO/(mmol·g^-1)	p/bar		Δn_CO/(mmol·g^-1)
			解吸	吸附	n_CO/(mmol·g^-1)	解吸	吸附	Δn_CO/(mmol·g^-1)
Co-MOF-74	50%/50%	25	0.07^① 0^②	1.0^① 0.5^②	3.30	0.2^① 0.1^②	1.0^① 0.5^②	1.51	45.76
		60			3.00			1.74	58.00
		100			2.70			2.10	77.78
		140			1.74			1.39	79.88
		25	0.07^① 0^②	3.0^① 1.5^②	4.25	0.2^① 0.1^②	3.0^① 1.5^②	2.13	50.12
		60			4.02			2.66	66.17
		100			3.40			2.85	83.82
		140			2.60			2.27	87.31
		25	0.07^① 0^②	5.0^① 2.5^②	4.92	0.2^① 0.1^②	5.0^① 2.5^②	2.86	58.13
		60			4.61			3.30	71.58
		100			3.82			3.44	90.05
		140			3.08			2.82	91.56
Mg-MOF-74	50%/50%	25	0.07^①	1.0^①	1.40	0.2^①	1.0^①	0.93	66.43
		60	0^②	0.5^②	0.81	0.1^②	0.5^②	0.63	77.77
		25	0.07^①	2.0^①	2.05	0.2^①	2.0^①	1.63	79.51
		60	0^②	1.0^②	1.27	0.1^②	1.0^②	1.02	80.31
		25	0.07^①	3.0^①	2.20	0.2^①	3.0^①	1.96	89.09
		60	0^②	1.5^②	1.61	0.1^②	1.5^②	1.45	90.06

图13 两种样品的工作吸附容量循环性能T—操作温度;Ad.—吸附总压;De.—解吸总压

Fig.13 Working capacity cycling performance of two samplesT—operating temperature; Ad.—total adsorption pressure; De.—total desorption pressure

图14 Co-MOF-74在不同温度下对CO和N2的吸附等温线及吸附热

Fig.14 Adsorption isotherms and heats of Co-MOF-74 for CO and N2 at different temperatures

图15 Mg-MOF-74在不同温度下对CO和N2的吸附等温线及吸附热

Fig.15 Adsorption isotherms and heats of Mg-MOF-74 for CO and N2 at different temperatures

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