Study on the carbon capture performance of highly selective PEI@MOF-808 adsorbent in humid flue gas

doi:10.11949/0438-1157.20230584

Abstract

Abstract:

Zr-based metal organic framework MOF-808 is used as the carrier and is functionalized with polyethylenimine (PEI) to obtain PEI@M-808 composite material, which is used to selectively capture humid flue gas (10% CO₂ + 90 % N₂ + 10 kPa H₂O). The physicochemical properties of the sorbents are characterized by XRD, FT-IR, SEM, and BET techniques, and the effectiveness of the modification scheme is assessed. The sorption performance of PEI300-30@M-808 at trace CO₂ with moisture is dramatically enhanced due to the abundant amine groups on the surface of PEI@M-808 corresponding to the loading of PEI molecules. The adsorption performance of the composite adsorbent at trace CO₂ concentration is greatly enhanced by the introduction of abundant amine functional groups on the surface of MOF-808 due to the loading of PEI. The PEI300-30@M-808 could trap 0.89 mmol/g at 343 K and 0.1 bar while the MOF-808 manifests sorption capacity of approximately 0.052 mmol/g under the same condition. Furthermore, the sorption selectivity of PEI300-30@M-808 is 5524.65 at 10/90 CO₂/N₂ at 0.1 bar and 343 K, which is about 56 times larger compared to that of MOF-808. Additionally, per gram of PEI300-30@M-808 could react with 1.47 mmol/g at the sorption condition with 5% RH, indicating that the moisture has a positive effect for CO₂ capture with PEI-based materials. After 5 cycles, the CO₂ saturated adsorption capacity of PEI300-30@M-808 can still be maintained at 90.7%. Therefore, the PEI300-30@M-808 feature great potential for trace carbon capture in moist flue gas.

Key words: carbon dioxide capture, adsorbents, polyethyleneimine, selectivity, flue gas

摘要：

以Zr基金属有机框架MOF-808为载体，采用聚乙烯亚胺（polyethylenimine， PEI）进行官能化，得到PEI@M-808复合材料，用于选择性捕集潮湿烟气（10% CO₂+90% N₂+10 kPa H₂O）中的低浓度CO₂。采用XRD、FT-IR、SEM以及BET等表征了吸附剂的物理化学性质，并评估改性方案的可行性。由于MOF-808表面PEI的负载引入了丰富胺基官能团，使复合吸附剂在低浓度CO₂下的吸附性能大幅提升。PEI300-30@M-808在典型烟气温度（343 K）的低压CO₂吸附量相比原材料由0.052 mmol/g上升到0.89 mmol/g，增加了约16倍。此外，CO₂/N₂吸附选择性在0.1 bar（1 bar=10⁵ Pa）时能达到5524.65，相比原材料提升了约56倍。更重要的是，当吸附剂放置到5% RH工况中时吸附量由0.89 mmol/g提高到1.47 mmol/g，证明了水分对其CO₂吸附起着良好的促进作用。经过5次循环后，PEI300-30@M-808的CO₂饱和吸附量仍可维持在90.7%。

关键词: 二氧化碳捕集, 吸附剂, 聚乙烯亚胺, 选择性, 烟道气

CLC Number:

O 647.32

Xinqi ZHANG, Chen ZHANG, Duoyong ZHANG, Tao XUAN, Zhuozhen GAN, Xuancan ZHU, Liwei WANG. Study on the carbon capture performance of highly selective PEI@MOF-808 adsorbent in humid flue gas[J]. CIESC Journal, 2023, 74(10): 4330-4342.

张鑫琦, 张宸, 张舵咏, 宣涛, 干桌臻, 朱炫灿, 王丽伟. 高选择性PEI@MOF-808吸附剂在潮湿烟气中的碳捕集性能研究[J]. 化工学报, 2023, 74(10): 4330-4342.

Figures/Tables 14

Fig.1 M-808 synthesis scheme and PEI modification mechanism explanation

Fig.2 CO2 fixed bed sorption testing unit

Fig.3 XRD patterns and FT-IR spectra of PEIx-y@M-808

Fig.4 SEM images and energy distribution of C, N and Zr elements of PEI300-30@M-808

Fig.5 N2 sorption isotherms and pore size distribution of PEI300-y@M-808 at 77 K

Fig.6 CO2 sorption isotherm of PEIx-10@M-808 at 343 K

Fig.7 CO2 and N2 sorption isotherms of PEI300-y@M-808 at 343 K

Table 1 Textural properties of PEI300-y@M-808

样品名称	比表面积/ (m²/g)	全孔体积/ (cm³/g)	微孔体积/ (cm³/g)
M-808	1742.09	1.04	0.60
PEI300-10@M-808	105.58	0.28	0.01
PEI300-20@M-808	74.83	0.29	0
PEI300-30@M-808	48.30	0.18	0

Table 2 CO2 sorption capacity， CO2/N2 selectivity and amine efficiency of PEI300-y@M-808 at 343 K

样品名称	PEI实际负载量/ %(质量)	0.1 bar CO₂吸附量/(mmol/g)	1 bar CO₂吸附量/(mmol/g)	0.1 bar CO₂/N₂选择性	1 bar CO₂/N₂选择性	0.1 bar胺效率/(mol/mol)
M-808	—	0.052	0.51	96.69	110.29	—
PEI300-10@M-808	6.81	0.63	1.06	2574.39	609.79	0.34
PEI300-20@M-808	16.19	0.78	1.21	4480.93	851.27	0.22
PEI300-30@M-808	24.25	0.89	1.29	5524.65	1043.86	0.16

Table 3 Parameters obtained by fitting the PEI300-y@M-808 isotherm with the Langmuir/Freundlich model

样品名称	CO₂拟合参数				N₂拟合参数
样品名称	q_max/(mmol/g)	K_L-F	n	R²	q_max/(mmol/g)	K_L-F	n	R²
M-808	1.040	0.81	0.8009	0.9926	0.184	0.280	1.0001	0.9998
PEI300-10@M-808	1.076	15.46	0.8938	0.9710	0.055	0.374	1.0038	0.9999
PEI300-20@M-808	1.266	11.01	1.1954	0.9690	0.044	0.373	1.0043	0.9999
PEI300-30@M-808	1.297	24.62	0.9557	0.9845	0.040	0.372	1.0043	0.9999

Fig.8 IAST CO2/N2 selectivity of PEI300-y@M-808 at 343 K (CO2∶N2=0.1∶0.9)

Fig.9 Sorption capacity and structural stability of PEI300-y@M-808 for CO2 under dry and water vapor partial pressure of 10 kPa at 343 K

Fig.10 PEI-CO2 interaction configurations and DFT calculation of adsorption energy under dry and humid conditions

Fig.11 Cycling performance and thermal stability of PEI300-y@M-808

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