ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

CO2 Sorption Performance of Composite Polymer/Aminosilica Hollow Fiber Sorbents: An Experimental and Modeling Study

View Author Information
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, Georgia 30332, United States
Department of Chemical & Biochemical Engineering, Missouri University of Science & Technology, 1101 East State Street, Rolla, Missouri 65409, United States
Cite this: Ind. Eng. Chem. Res. 2015, 54, 6, 1783–1795
Publication Date (Web):January 23, 2015
Copyright © 2015 American Chemical Society

    Article Views





    Read OnlinePDF (2 MB)
    Supporting Info (1)»


    Abstract Image

    The dynamic CO2 sorption performance of polymer/silica supported polyethylenimine hollow fiber sorbents (CA-S-PEI), focusing on heat and mass transport effects, is investigated experimentally and computationally during sorption of CO2 from simulated, dry flue gases. The effect of the nonisothermality on the sorption performance is investigated by varying the module materials of construction. The heat effects are minimized by using a heat conductive module case with a diameter of 0.25 in., and, accordingly, the breakthrough capacities are increased by 30% over a similar module constructed from less conductive components, thereby improving fiber sorbents utilization efficiency. The sorption kinetics in CA-S-PEI hollow fiber sorbents are investigated in terms of flow rates, module packing fraction, module length, and silica particle size. A mathematical model developed previously is successfully utilized to predict various contributions to the overall mass transfer resistance. In fiber sorbents where the amine loading is high, such as those employed here, the sorption process is found to be controlled by intraparticle mass transfer resistances. Unlike fiber sorbents based on physisorbents, the external gas diffusion resistance has minimal effects on the breakthrough capacities, as evidenced with the negligible effects of the module packing fraction on the sorption capacities. Sorption capacities are found to increase with the fiber module length as a result of self-sharpening effects. The increase of particle size increases the mass transfer resistance of the fiber sorbents as illustrated by the more diffuse CO2 breakthrough fronts in fiber modules containing bigger silica particles. The capacities in fiber sorbents with the largest silica particles exhibit the lowest sorption capacity, as expected.

    Supporting Information

    Jump To

    Figure S1 shows model prediction of CO2 isotherm profiles based on Toth adsorption isothermal model. Model equations including mass balance equations and energy balance equations are included in pp S2–S5. Figure S2 shows CO2 breakthrough profiles (left) and fiber temperature profiles (right) at different flue gas flow rates; solid line without marker is the model prediction. Figure S3 presents CO2 breakthrough profiles at different packing fractions for Qfluegas = 80 sccm, and temperature profile at ϕ = 0.69; solid line without marker is the model prediction. Figure S4 shows CO2 breakthrough profiles (left) at different particle sizes and temperature profiles (right) at a particle size = 25 μm; solid line without marker is the model prediction. Figure S5 model analysis: Profiles of concentration and temperature along the length of the fiber module at time t1 and t2 at 80 sccm. Figure S6 displays model prediction of the front velocity as a function of the flue gas velocity. Figure S7 shows model analysis showing the effect of flue gas flow rate on 1/Kg at τ = 70. Figure S8 is model analysis: mass transfer resistance components of bulk PEI sites (1/Kov,bulk) for the fiber modules with packing fraction of ϕ = 0.46 and ϕ = 0.69 at τ = 40. The inset shows a zoomed view of the y-axis from 0 to 1.0. Figure S9 shows model analysis of (top) propagation of the concentration front along the 34 in. fiber length and (bottom) concentration front plotted against the normalized length scale, z′ = z/zbreak. Figure S10 compares overall mass transfer resistances in the different silica sorbents at t = 28 s. Overall resistance comparison for bulk PEI 1/Kov,bulk is plotted in the main figure and for the exposed PEI 1/Kov,exposed is plotted in the inset figure. Table S1 shows the physical properties of silica supports after impregnating PEI. Table S2 shows all parameters for estimation of ψ. All of this information is cited from ref 55. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 30 publications.

    1. Michael T. Broud, Mohsen Samandari, Lu Yu, David P. Harper, David J. Keffer. Selective Carbon Dioxide Binding on Carbon Quantum Dots. The Journal of Physical Chemistry C 2023, 127 (28) , 13639-13650.
    2. Wenying Quan, Hannah E. Holmes, Fengyi Zhang, Breanne L. Hamlett, M. G. Finn, Carter W. Abney, Matthew T. Kapelewski, Simon C. Weston, Ryan P. Lively, William J. Koros. Scalable Formation of Diamine-Appended Metal–Organic Framework Hollow Fiber Sorbents for Postcombustion CO2 Capture. JACS Au 2022, 2 (6) , 1350-1358.
    3. Young Hun Lee, Jinhong Jeong, Kyunam Kim, Taehoon Hyun, Aqil Jamal, Dong-Yeun Koh. Microporous Materials in Scalable Shapes: Fiber Sorbents. Chemistry of Materials 2020, 32 (17) , 7081-7104.
    4. Jongwoo Park, Héctor Octavio Rubiera Landa, Yoshiaki Kawajiri, Matthew J. Realff, Ryan P. Lively, David S. Sholl. How Well Do Approximate Models of Adsorption-Based CO2 Capture Processes Predict Results of Detailed Process Models?. Industrial & Engineering Chemistry Research 2020, 59 (15) , 7097-7108.
    5. Achintya R. Sujan, Simon H. Pang, Guanghui Zhu, Christopher W. Jones, Ryan P. Lively. Direct CO2 Capture from Air using Poly(ethylenimine)-Loaded Polymer/Silica Fiber Sorbents. ACS Sustainable Chemistry & Engineering 2019, 7 (5) , 5264-5273.
    6. Sunghyun Park, Jongsik Kim, Young-June Won, Chaehoon Kim, Minkee Choi, Wonho Jung, Kwang Soon Lee, Jeong-Geol Na, So-Hye Cho, Seung Yong Lee, Jong Suk Lee. Epoxide-Functionalized, Poly(ethylenimine)-Confined Silica/Polymer Module Affording Sustainable CO2 Capture in Rapid Thermal Swing Adsorption. Industrial & Engineering Chemistry Research 2018, 57 (42) , 13923-13931.
    7. Brian R. Pimentel, Ryan P. Lively. Propylene Enrichment via Kinetic Vacuum Pressure Swing Adsorption Using ZIF-8 Fiber Sorbents. ACS Applied Materials & Interfaces 2018, 10 (42) , 36323-36331.
    8. Manda Yang, Linxi Wang, Seyed Mehdi Kamali Shahri, Robert M. Rioux, Antonios Armaou. Investigation of CO2 Sorption Mechanisms in Isothermal Columns via Transient Material and Energy Balance PDE Models. Industrial & Engineering Chemistry Research 2018, 57 (31) , 10303-10314.
    9. Linxi Wang, Seyed Mehdi Kamali Shahri, Robert M. Rioux. CO2 Capacity and Heat of Sorption on a Polyethylenimine-Impregnated Silica under Equilibrium and Transient Sorption Conditions. The Journal of Physical Chemistry C 2018, 122 (21) , 11442-11449.
    10. Zhuonan Song, Fen Qiu, Edmond W. Zaia, Zhongying Wang, Martin Kunz, Jinghua Guo, Michael Brady, Baoxia Mi, and Jeffrey J. Urban . Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation. Nano Letters 2017, 17 (11) , 6752-6758.
    11. Jan-Michael Y. Carrillo, Matthew E. Potter, Miles A. Sakwa-Novak, Simon H. Pang, Christopher W. Jones, and Bobby G. Sumpter . Linking Silica Support Morphology to the Dynamics of Aminopolymers in Composites. Langmuir 2017, 33 (22) , 5412-5422.
    12. Brian R. Pimentel, Adam W. Fultz, Kristin V. Presnell, and Ryan P. Lively . Synthesis of Water-Sensitive Metal–Organic Frameworks within Fiber Sorbent Modules. Industrial & Engineering Chemistry Research 2017, 56 (17) , 5070-5077.
    13. Zhihong Yuan and Mario R. Eden , Rafiqul Gani . Toward the Development and Deployment of Large-Scale Carbon Dioxide Capture and Conversion Processes. Industrial & Engineering Chemistry Research 2016, 55 (12) , 3383-3419.
    14. Jan-Michael Y. Carrillo, Miles A. Sakwa-Novak, Adam Holewinski, Matthew E. Potter, Gernot Rother, Christopher W. Jones, and Bobby G. Sumpter . Unraveling the Dynamics of Aminopolymer/Silica Composites. Langmuir 2016, 32 (11) , 2617-2625.
    15. Adam Holewinski, Miles A. Sakwa-Novak, and Christopher W. Jones . Linking CO2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering. Journal of the American Chemical Society 2015, 137 (36) , 11749-11759.
    16. Junye Wu, Xuancan Zhu, Fan Yang, Ruzhu Wang, Tianshu Ge. Shaping techniques of adsorbents and their applications in gas separation: a review. Journal of Materials Chemistry A 2022, 10 (43) , 22853-22895.
    17. Yongyue Zhang, Meiyue Sun, Lin Li, Ruisong Xu, Yanqiu Pan, Tonghua Wang. Carbon molecular sieve/ZSM-5 mixed matrix membranes with enhanced gas separation performance and the performance recovery of the aging membranes. Journal of Membrane Science 2022, 660 , 120869.
    18. Walter C. Wilfong, Qiuming Wang, Tuo Ji, James S. Baker, Fan Shi, Shouliang Yi, McMahan L. Gray. Directly Spun Epoxy‐Crosslinked Polyethylenimine Fiber Sorbents for Direct Air Capture and Postcombustion Capture of CO 2. Energy Technology 2022, 10 (9)
    19. Xuancan Zhu, Wenwen Xie, Junye Wu, Yihe Miao, Chengjie Xiang, Chunping Chen, Bingyao Ge, Zhuozhen Gan, Fan Yang, Man Zhang, Dermot O'Hare, Jia Li, Tianshu Ge, Ruzhu Wang. Recent advances in direct air capture by adsorption. Chemical Society Reviews 2022, 51 (15) , 6574-6651.
    20. Roberto Mennitto, Ishan Sharma, Stefano Brandani. Extruded monoliths for gas separation processes: Height equivalent to a theoretical plate and pressure drop correlations. AIChE Journal 2022, 68 (6)
    21. Dong Hwi Jeong, Matthew J. Realff. Modular monolith adsorbent systems for CO2 capture and its parameterized optimization. Chemical Engineering Research and Design 2021, 176 , 1-13.
    22. Stephen J. A. DeWitt, Rohan Awati, Héctor Octavio Rubiera Landa, Jongwoo Park, Yoshiaki Kawajiri, David S. Sholl, Matthew J. Realff, Ryan P. Lively. Analysis of energetics and economics of sub‐ambient hybrid post‐combustion carbon dioxide capture. AIChE Journal 2021, 67 (11)
    23. Ahmad Sattari, Ali Ramazani, Hamideh Aghahosseini, Mohamed Kheireddine Aroua. The application of polymer containing materials in CO2 capturing via absorption and adsorption methods. Journal of CO2 Utilization 2021, 48 , 101526.
    24. Seongbin Ga, Sangwon Lee, Jihan Kim, Jay H. Lee. Isotherm parameter library and evaluation software for CO2 capture adsorbents. Computers & Chemical Engineering 2020, 143 , 107105.
    25. A.A. Azmi, M.A.A. Aziz. Mesoporous adsorbent for CO2 capture application under mild condition: A review. Journal of Environmental Chemical Engineering 2019, 7 (2) , 103022.
    26. Laura Keller, Burkhard Ohs, Lorenz Abduly, Matthias Wessling. Carbon nanotube silica composite hollow fibers impregnated with polyethylenimine for CO2 capture. Chemical Engineering Journal 2019, 359 , 476-484.
    27. Harshul Thakkar, Shane Lawson, Ali A. Rownaghi, Fateme Rezaei. Development of 3D-printed polymer-zeolite composite monoliths for gas separation. Chemical Engineering Journal 2018, 348 , 109-116.
    28. Stephen J.A. DeWitt, Anshuman Sinha, Jayashree Kalyanaraman, Fengyi Zhang, Matthew J. Realff, Ryan P. Lively. Critical Comparison of Structured Contactors for Adsorption-Based Gas Separations. Annual Review of Chemical and Biomolecular Engineering 2018, 9 (1) , 129-152.
    29. Christopher W. Jones. Advice for emerging researchers on research program development: A personal case study. AIChE Journal 2017, 63 (9) , 3627-3635.
    30. Yanping Ren, Ruiyu Ding, Hairong Yue, Siyang Tang, Changjun Liu, Jinbo Zhao, Wen Lin, Bin Liang. Amine-grafted mesoporous copper silicates as recyclable solid amine sorbents for post-combustion CO 2 capture. Applied Energy 2017, 198 , 250-260.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect