高选择性PEI@MOF-808吸附剂在潮湿烟气中的碳捕集性能研究

doi:10.11949/0438-1157.20230584

摘要/Abstract

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

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

中图分类号:

O 647.32

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.

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.

图/表 14

图1 M-808合成方案和PEI修饰机理解释（1 Å =0.1 nm）

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

图2 CO2固定床吸附装置1—氮气;2—混合气;3—截止阀;4—压力调节器;5—质量流量控制器;6—针阀;7—单向阀;8—水浴锅;9—鼓泡发生器;10—三通阀;11—温度和湿度传感器;12—干燥管;13—热追踪;14—吸附柱;15—压力表;16—在线质谱仪

Fig.2 CO2 fixed bed sorption testing unit

图3 PEIx-y@M-808的XRD谱图和FT-IR红外光谱

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

图4 扫面电镜图和PEI300-30@M-808的C、N、Zr元素的能量分布

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

图5 PEI300-y@M-808在77 K下的N2吸附等温线及孔径分布

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

图6 PEIx-10@M-808在343 K的CO2吸附等温线

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

图7 PEI300-y@M-808在343 K的CO2和N2吸附等温线

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

表1 PEI300-y@M-808孔结构参数

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

表2 PEI300-y@M-808在343 K的CO2吸附量、CO2/N2选择性和胺效率

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

表3 Langmuir/Freundlich模型拟合PEI300-y@M-808等温线参数

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

图8 PEI300-y@M-808在343 K的IAST CO2/N2吸附选择性(CO2∶N2=0.1∶0.9)

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

图9 343 K下PEI300-y@M-808在干燥和水汽分压10 kPa条件下对CO2的吸附能力及结构稳定性

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

图10 干燥、潮湿条件下PEI与CO2相互作用构型和吸附能量DFT计算

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

图11 PEI300-y@M-808的循环性能及热稳定性

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

参考文献 33

34	Kang J H, Yoon T U, Kim S Y, et al. Extraordinarily selective adsorption of CO₂ over N₂ in a polyethyleneimine-impregnated NU-1000 material[J]. Microporous and Mesoporous Materials, 2019, 281: 84-91.
35	Zhu H J, Xue W J, Huang H L, et al. Water boosted CO₂/C₂H₂ separation in L-arginine functionalized metal-organic framework[J]. Nano Research, 2023, 16(5): 6113-6119.
36	Lee J J, Chen C H, Shimon D, et al. Effect of humidity on the CO₂ adsorption of tertiary amine grafted SBA-15[J]. The Journal of Physical Chemistry C, 2017, 121(42): 23480-23487.
37	Didas S A, Sakwa-Novak M A, Foo G S, et al. Effect of amine surface coverage on the co-adsorption of CO₂ and water: spectral deconvolution of adsorbed species[J]. The Journal of Physical Chemistry Letters, 2014, 5(23): 4194-4200.
38	Zhang G J, Zhao P Y, Hao L X, et al. A novel amine double functionalized adsorbent for carbon dioxide capture using original mesoporous silica molecular sieves as support[J]. Separation and Purification Technology, 2019, 209: 516-527.
1	Quan C, Chu H, Zhou Y Y, et al. Amine-modified silica zeolite from coal gangue for CO₂ capture[J]. Fuel, 2022, 322: 124184.
2	Ochedi F O, Yu J L, Yu H, et al. Carbon dioxide capture using liquid absorption methods: a review[J]. Environmental Chemistry Letters, 2021, 19(1): 77-109.
3	Dutcher B, Fan M H, Russell A G. Amine-based CO₂ capture technology development from the beginning of 2013—a review[J]. ACS Applied Materials & Interfaces, 2015, 7(4): 2137-2148.
4	Wang M H, Joel A S, Ramshaw C, et al. Process intensification for post-combustion CO₂ capture with chemical absorption: a critical review[J]. Applied Energy, 2015, 158: 275-291.
5	Samanta A, Zhao A, Shimizu G K H, et al. Post-combustion CO₂ capture using solid sorbents: a review[J]. Industrial & Engineering Chemistry Research, 2012, 51(4): 1438-1463.
6	Zhang C, Zhang Y H, Su T Y, et al. Molecular simulation on carbon dioxide capture performance for carbons doped with various elements[J]. Energy Storage and Saving, 2023, 2(2): 435-441.
7	Wurzbacher J A, Gebald C, Steinfeld A. Separation of CO₂ from air by temperature-vacuum swing adsorption using diamine-functionalized silica gel[J]. Energy & Environmental Science, 2011, 4(9): 3584-3592.
8	Hudson M R, Queen W L, Mason J A, et al. Unconventional, highly selective CO₂ adsorption in zeolite SSZ-13[J]. Journal of the American Chemical Society, 2012, 134(4): 1970-1973.
9	Boyd P G, Chidambaram A, García-Díez E, et al. Data-driven design of metal-organic frameworks for wet flue gas CO₂ capture[J]. Nature, 2019, 576(7786): 253-256.
10	González-Zamora E, Ibarra I A. CO₂ capture under humid conditions in metal-organic frameworks[J]. Materials Chemistry Frontiers, 2017, 1(8): 1471-1484.
11	Trickett C A, Helal A, Al-Maythalony B A, et al. The chemistry of metal-organic frameworks for CO₂ capture, regeneration and conversion[J]. Nature Reviews Materials, 2017, 2: 17045.
12	Lei L, Cheng Y, Chen C W, et al. Taming structure and modulating carbon dioxide (CO₂) adsorption isosteric heat of nickel-based metal organic framework (MOF-74(Ni)) for remarkable CO₂ capture[J]. Journal of Colloid and Interface Science, 2022, 612: 132-145.
13	Zheng W J, Ding R, Dai Y, et al. Regulating the pore engineering of MOFs by the confined dissolving of PSA template to improve CO₂ capture[J]. Journal of Membrane Science, 2023, 670: 121373.
14	Jun H J, Yoo D K, Jhung S H. Metal-organic framework (MOF-808) functionalized with ethyleneamines: selective adsorbent to capture CO₂ under low pressure[J]. Journal of CO₂ Utilization, 2022, 58: 101932.
15	Xian S K, Wu Y, Wu J L, et al. Enhanced dynamic CO₂ adsorption capacity and CO₂/CH₄ selectivity on polyethylenimine-impregnated UiO-66[J]. Industrial & Engineering Chemistry Research, 2015, 54(44): 11151-11158.
16	Su X A, Bromberg L, Martis V, et al. Postsynthetic functionalization of Mg-MOF-74 with tetraethylenepentamine: structural characterization and enhanced CO₂ adsorption[J]. ACS Applied Materials & Interfaces, 2017, 9(12): 11299-11306.
17	Sanjit G, Yeonhee K, Ranjit G, et al. Enhanced CO₂ capture capacity of amine-functionalized MOF-177 metal organic framework[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105523.
18	Miao Y H, Wang Y Z, Ge B Y, et al. Mixed diethanolamine and polyethyleneimine with enhanced CO₂ capture capacity from air[J]. Advanced Science, 2023, 10(16): 2207253.
19	Zhu J J, Wu L B, Bu Z Y, et al. Polyethyleneimine-modified UiO-66-NH₂(Zr) metal-organic frameworks: preparation and enhanced CO₂ selective adsorption[J]. ACS Omega, 2019, 4(2): 3188-3197.
20	Xian S K, Xu F, Ma C, et al. Vapor-enhanced CO₂ adsorption mechanism of composite PEI@ZIF-8 modified by polyethyleneimine for CO₂/N₂ separation[J]. Chemical Engineering Journal, 2015, 280: 363-369.
21	Pander M, Gil-San-Millan R, Delgado P, et al. MOF/polymer hybrids through in situ free radical polymerization in metal-organic frameworks[J]. Materials Horizons, 2023, 10(4): 1301-1308.
22	Lam I T Y, Choi S, Lu D, et al. Functionalized metal-organic frameworks for heavy metal ion removal from water[J]. Nanoscale, 2023, 15(24): 10189-10205.
23	Park J M, Yoo D K, Jhung S H. Selective CO₂ adsorption over functionalized Zr-based metal organic framework under atmospheric or lower pressure: contribution of functional groups to adsorption[J]. Chemical Engineering Journal, 2020, 402: 126254.
24	Lyu H, Chen O I F, Hanikel N, et al. Carbon dioxide capture chemistry of amino acid functionalized metal-organic frameworks in humid flue gas[J]. Journal of the American Chemical Society, 2022, 144(5): 2387-2396.
25	Ahmed S, Ramli A, Yusup S, et al. Adsorption behavior of tetraethylenepentamine-functionalized Si-MCM-41 for CO₂ adsorption[J]. Chemical Engineering Research and Design, 2017, 122: 33-42.
26	Hiroyasu F, Felipe G, Zhang Y B, et al. Water adsorption in porous metal-organic frameworks and related materials[J]. Journal of the American Chemical Society, 2014, 136(11): 4369-4381.
27	Rojas-Buzo S, García-García P, Corma A. Zr-MOF-808@MCM-41 catalyzed phosgene-free synthesis of polyurethane precursors[J]. Catalysis Science & Technology, 2019, 9(1): 146-156.
28	Hao Y X, Li J S, Yang X J, et al. Preparation of ZrO₂-Al₂O₃ composite membranes by sol-gel process and their characterization[J]. Materials Science and Engineering: A, 2004, 367(1/2): 243-247.
29	Elvira M R, Mazo M A, Tamayo A, et al. Study and characterization of organically modified silica-zirconia anti-graffiti coatings obtained by sol-gel[J]. Journal of Chemistry and Chemical Engineering, 2013, 7(2): 120.
30	DeCoste J B, Peterson G W, Jasuja H, et al. Stability and degradation mechanisms of metal-organic frameworks containing the Zr₆O₄(OH)₄ secondary building unit[J]. Journal of Materials Chemistry A, 2013, 1(18): 5642-5650.
31	Lin Y C, Lin H, Wang H M, et al. Enhanced selective CO₂ adsorption on polyamine/MIL-101(Cr) composites[J]. Journal of Materials Chemistry A, 2014, 2(35): 14658-14665.
32	Li Z, Chen H F, Chen C, et al. High dispersion of polyethyleneimine within mesoporous UiO-66s through pore size engineering for selective CO₂ capture[J]. Chemical Engineering Journal, 2019, 375: 121962.
33	Russel W W. The adsorption of gases and vapors(Ⅰ): Physical adsorption (Brunauer, Stephen)[J]. Journal of Chemical Education, 1944, 21(1): 52.

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