CO working capacity and operating conditions of Co-MOF-74 and Mg-MOF-74

doi:10.11949/0438-1157.20241210

Abstract

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

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

CLC Number:

TQ 028.1

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.

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.

Figures/Tables 17

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

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

Fig.3 SEM images of two samples

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

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

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

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

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

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

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

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

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

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

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

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

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

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

References 42

1	Martinelli M, Gnanamani M K, LeViness S, et al. An overview of Fischer-Tropsch synthesis: XtL processes, catalysts and reactors[J]. Applied Catalysis A: General, 2020, 608: 117740.
2	Liu Y T, Deng D H, Bao X H. Catalysis for selected C1 chemistry[J]. Chem, 2020, 6(10): 2497-2514.
3	霍猛, 彭晓婉, 赵金, 等. 基于COSMO-RS的离子液体吸收CO的溶剂筛选及H₂/CO分离实验[J]. 化工学报, 2022, 73(12): 5305-5313.
	Huo M, Peng X W, Zhao J, et al. COSMO-RS based solvent screening and H₂/CO separation experiments for CO absorption by ionic liquids[J]. CIESC Journal, 2022, 73(12): 5305-5313.
4	Ramírez-Santos Á A, Castel C, Favre E. A review of gas separation technologies within emission reduction programs in the iron and steel sector: current application and development perspectives[J]. Separation and Purification Technology, 2018, 194: 425-442.
5	Mondal P, Dang G S, Garg M O. Syngas production through gasification and cleanup for downstream applications—recent developments[J]. Fuel Processing Technology, 2011, 92(8): 1395-1410.
6	Flores-Granobles M, Saeys M. Dynamic pressure-swing chemical looping process for the recovery of CO from blast furnace gas[J]. Energy Conversion and Management, 2022, 258: 115515.
7	Lee H H, Lee J C, Joo Y J, et al. Dynamic modeling of Shell entrained flow gasifier in an integrated gasification combined cycle process[J]. Applied Energy, 2014, 131: 425-440.
8	Li Y X, Li S S, Xue D M, et al. Incorporation of Cu(Ⅱ) and its selective reduction to Cu(Ⅰ) within confined spaces: efficient active sites for CO adsorption[J]. Journal of Materials Chemistry A, 2018, 6(19): 8930-8939.
9	Fakhraei Ghazvini M, Vahedi M, Najafi Nobar S, et al. Investigation of the MOF adsorbents and the gas adsorptive separation mechanisms[J]. Journal of Environmental Chemical Engineering, 2021, 9(1): 104790.
10	Oh H, Beum H T, Yoon Y S, et al. Experiment and modeling of adsorption of CO from blast furnace gas onto CuCl/boehmite[J]. Industrial & Engineering Chemistry Research, 2020, 59(26): 12176-12185.
11	蔺彩虹, 王丽, 吴瑜, 等. 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.
	Lin C H, Wang L, Wu Y, et al. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O[J]. CIESC Journal, 2023, 74(5): 2013-2021.
12	Oh H, Tae Beum H, Lee S Y, et al. Bed configurations in CO vacuum pressure swing adsorption process for basic oxygen furnace gas utilization: experiment, simulation, and techno-economic analysis[J]. Chemical Engineering Journal, 2023, 454: 140432.
13	He Y B, Xiang S C, Chen B L. A microporous hydrogen-bonded organic framework for highly selective C₂H₂/C₂H₄ separation at ambient temperature[J]. Journal of the American Chemical Society, 2011, 133(37): 14570-14573.
14	Ko K J, Kim H, Cho Y H, et al. Overview of carbon monoxide adsorption performance of pristine and modified adsorbents[J]. Journal of Chemical & Engineering Data, 2022, 67(7): 1599-1616.
15	Lopes F V S, Grande C A, Rodrigues A E. Activated carbon for hydrogen purification by pressure swing adsorption: multicomponent breakthrough curves and PSA performance[J]. Chemical Engineering Science, 2011, 66(3): 303-317.
16	Huang H Y, Padin J, Yang R T. Comparison of π-complexations of ethylene and carbon monoxide with Cu⁺ and Ag⁺ [J]. Industrial & Engineering Chemistry Research, 1999, 38(7): 2720-2725.
17	Feyzbar-Khalkhali-Nejad F, Hassani E, Rashti A, et al. Adsorption-based CO removal: principles and materials[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105317.
18	Peng J J, Xian S K, Xiao J, et al. A supported Cu(Ⅰ)@MIL-100(Fe) adsorbent with high CO adsorption capacity and CO/N₂ selectivity[J]. Chemical Engineering Journal, 2015, 270: 282-289.
19	梁晓武. Co-MOF-74的合成及CO/N₂吸附分离性能的研究[D]. 太原: 太原理工大学, 2021.
	Liang X W. Synthesis of Co-MOF-74 and study on adsorption and separation performance of CO/N₂ [D]. Taiyuan: Taiyuan University of Technology, 2021.
20	Evans A, Cummings M S, Luebke R, et al. Screening metal-organic frameworks for dynamic CO/N₂ separation using complementary adsorption measurement techniques[J]. Industrial & Engineering Chemistry Research, 2019, 58(39): 18336-18344.
21	Bloch E D, Hudson M R, Mason J A, et al. Reversible CO binding enables tunable CO/H₂ and CO/N₂ separations in metal-organic frameworks with exposed divalent metal cations[J]. Journal of the American Chemical Society, 2014, 136(30): 10752-10761.
22	Evans A, Luebke R, Petit C. The use of metal-organic frameworks for CO purification[J]. Journal of Materials Chemistry A, 2018, 6(23): 10570-10594.
23	Kim H, Sohail M, Yim K, et al. Effective CO₂ and CO separation using[M₂(DOBDC)] (M = Mg, Co, Ni) with unsaturated metal sites and excavation of their adsorption sites[J]. ACS Applied Materials & Interfaces, 2019, 11(7): 7014-7021.
24	Pandey I, Lin L C, Chen C C, et al. Understanding carbon monoxide binding and interactions in M-MOF-74 (M = Mg, Mn, Ni, Zn)[J]. Langmuir, 2023, 39(50): 18187-18197.
25	Cheng M, Wang S H, Zhang Z Y, et al. High-throughput virtual screening of metal-organic frameworks for xenon recovery from exhaled anesthetic gas mixture[J]. Chemical Engineering Journal, 2023, 451: 138218.
26	Raganati F, Chirone R, Ammendola P. CO₂ capture by temperature swing adsorption: working capacity As affected by temperature and CO₂ partial pressure[J]. Industrial & Engineering Chemistry Research, 2020, 59(8): 3593-3605.
27	Wang Z F, Li C L, Tang L, et al. The CO working capacity of Ni-MOF-74 and corresponding operating conditions for CO/N₂ adsorption separation[J]. Industrial & Engineering Chemistry Research, 2024, 63(31): 13776-13786.
28	Rowsell J L C, Yaghi O M. Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks[J]. Journal of the American Chemical Society, 2006, 128(4): 1304-1315.
29	Caskey S R, Wong-Foy A G, Matzger A J. Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores[J]. Journal of the American Chemical Society, 2008, 130(33): 10870-10871.
30	Xue C L, Hao W M, Cheng W P, et al. CO adsorption performance of CuCl/activated carbon by simultaneous Reduction-Dispersion of mixed Cu(Ⅱ) salts[J]. Materials, 2019, 12(10): 1605.
31	Oliveira M L M, Miranda A A L, Barbosa C M B M, et al. Adsorption of thiophene and toluene on NaY zeolites exchanged with Ag(Ⅰ), Ni(Ⅱ) and Zn(Ⅱ)[J]. Fuel, 2009, 88(10): 1885-1892.
32	Cessford N F, Seaton N A, Düren T. Evaluation of ideal adsorbed solution theory as a tool for the design of metal-organic framework materials[J]. Industrial & Engineering Chemistry Research, 2012, 51(13): 4911-4921.
33	Bae Y S, Lee C Y, Kim K C, et al. High propene/propane selectivity in isostructural metal-organic frameworks with high densities of open metal sites[J]. Angewandte Chemie (International Ed), 2012, 51(8): 1857-1860.
34	Choma J, Stachurska K, Marszewski M, et al. Equilibrium isotherms and isosteric heat for CO₂ adsorption on nanoporous carbons from polymers[J]. Adsorption, 2016, 22(4): 581-588.
35	Tao L R, You Y Y, Liu X J. Numerical studies of CO separation and enrichment from blast furnace gas by using a CuCl/Y fixed bed[J]. Ironmaking & Steelmaking, 2021, 48(10): 1187-1199.
36	Basdogan Y, Sezginel K B, Keskin S. Identifying highly selective metal organic frameworks for CH₄/H₂ separations using computational tools[J]. Industrial & Engineering Chemistry Research, 2015, 54(34): 8479-8491.
37	Bae Y S, Snurr R Q. Development and evaluation of porous materials for carbon dioxide separation and capture[J]. Angewandte Chemie International Edition, 2011, 50(49): 11586-11596.
38	Tong M M, Yang Q Y, Xiao Y L, et al. Revealing the structure-property relationship of covalent organic frameworks for CO₂ capture from postcombustion gas: a multi-scale computational study[J]. Physical Chemistry Chemical Physics, 2014, 16(29): 15189-15198.
39	Jiang H X, Wang Q Y, Wang H Q, et al. MOF-74 as an efficient catalyst for the low-temperature selective catalytic reduction of NO _x with NH₃ [J]. ACS Applied Materials & Interfaces, 2016, 8(40): 26817-26826.
40	Sun H, Ren D N, Kong R Q, et al. Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks[J]. Microporous and Mesoporous Materials, 2019, 284: 151-160.
41	Wu Y Q, Chen Z A, Li B, et al. Highly selective adsorption of CO over N₂ on CuCl-loaded SAPO-34 adsorbent[J]. Journal of Energy Chemistry, 2019, 36: 122-128.
42	Álvarez-Gutiérrez N, Gil M V, Rubiera F, et al. Adsorption performance indicators for the CO₂/CH₄ separation: application to biomass-based activated carbons[J]. Fuel Processing Technology, 2016, 142: 361-369.

[1]	Ruijie MA, Zixuan HUANG, Xueqian GUAN, Guangjin CHEN, Bei LIU. Efficient ethane and methane separation using ZIF-8/DMPU slurry [J]. CIESC Journal, 2025, 76(5): 2262-2269.
[2]	Zhichao XU, Zhendong YU, Haofeng WU, Peiwen WU, Hongxiang WU, Yanhong CHAO, Wenshuai ZHU, Zhichang LIU, Chunming XU. Preparation of acid-rich 13X molecular sieve and its ultra-deep adsorption removal of mercaptan in biodiesel [J]. CIESC Journal, 2025, 76(5): 2198-2208.
[3]	Pengtao GUO, Ting WANG, Bo XUE, Yunpan YING, Dahuan LIU. Ultramicroporous MOF with multiple adsorption sites for CH₄/N₂ separation [J]. CIESC Journal, 2025, 76(5): 2304-2312.
[4]	Yan LI, Meili LEI, Xingang LI. Regulation strategy of sequential simulated moving bed structure based on separation performance [J]. CIESC Journal, 2025, 76(5): 2219-2229.
[5]	Yaqi BA, Tao WU, Andi DI, Anhui LU. Progress in porous carbons for efficient separation of gaseous light hydrocarbon [J]. CIESC Journal, 2025, 76(5): 2136-2157.
[6]	Peng TAN, Xuemei LI, Xiaoqin LIU, Linbing SUN. Study on magnetically responsive composite materials based on flexible MOFs and their propylene adsorption performance [J]. CIESC Journal, 2025, 76(5): 2230-2240.
[7]	Hao QI, Yujie WANG, Shenhui LI, Qi ZOU, Yiqun LIU, Zhiping ZHAO. Molecular simulation study on adsorption and diffusion of C₃H₆ and C₃H₈ on Co/Zn-ZIFs [J]. CIESC Journal, 2025, 76(5): 2313-2326.
[8]	Chunhui TAO, Yinhui LI, Yu FU, Ran DUAN, Zeyi ZHAO, Yufeng TANG, Gang ZHANG, Heping MA. Selective adsorption and purification of low-concentration Kr gas using various adsorbents [J]. CIESC Journal, 2025, 76(5): 2358-2366.
[9]	Yue ZHANG, Jiaxin LIU, Jing MA, Yi LIU. Recent progress on metal-organic framework membranes towards uranium separation from seawater [J]. CIESC Journal, 2025, 76(5): 2087-2100.
[10]	Jialang HU, Mingyuan JIANG, Lyuming JIN, Yonggang ZHANG, Peng HU, Hongbing JI. Machine learning-assisted high-throughput computational screening of MOFs and advances in gas separation research [J]. CIESC Journal, 2025, 76(5): 1973-1996.
[11]	Junde ZHAO, Aiguo ZHOU, Yanlin CHEN, Jiale ZHENG, Tianshu GE. Current status of energy consumption of adsorption CO₂ direct air capture [J]. CIESC Journal, 2025, 76(4): 1375-1390.
[12]	Yihao JIN, Junxin LUO, Zhangmao HU, Wei WANG, Qian YIN. Experimental investigation on hydrophilic functionalized MgSO₄/expanded vermiculite composites for water adsorption and heat storage [J]. CIESC Journal, 2025, 76(4): 1852-1862.
[13]	Tianzi CAI, Haifeng ZHANG, Haidan LIN, Zilong ZHANG, Pengyu ZHOU, Bolin WANG, Xiaonian LI. A density functional theory study on the sensing of dissolved gases CO and CO₂ in transformer oil using boron-doped nitrogen-based graphene [J]. CIESC Journal, 2025, 76(4): 1841-1851.
[14]	Yao FU, Yingjuan SHAO, Wenqi ZHONG. Experimental study on cyclic heat storage performance of TiO₂-doped calcium based materials under pressurized carbonation [J]. CIESC Journal, 2025, 76(3): 1180-1190.
[15]	Liwen ZHAO, Guilian LIU. Performance enhancement and parameter optimization of complex catalytic reaction system based on system integration [J]. CIESC Journal, 2025, 76(3): 1111-1119.