AJAC  Vol.6 No.4 , March 2015
Adsorption of CO2 on Polyethyleneimine 10k—Mesoporous silica Sorbent: XPS and TGA Studies
Abstract: A CO2 solid sorbent based on polyethyleneimine 10k (PEI-10k) impregnated into mesoporous silica (MPS) foam was synthesized and utilized to capture CO2 at temperatures ranged from 65°C to 95°C. The calculated nitrogen and carbon contents in the bulk of the PEI-10k/MPS sorbent were similar to the XPS results measured on the surface of the foam, suggesting that the PEI was homo-geneously distributed throughout the MPS support. After CO2 adsorptionthe N 1s peak was broadened and could be resolved into two components: a high binding energy component (~401 eV) and a lower binding energy one (396 eV), respectively. The former nitrogen states are consistent with a protonated amine, presumably, due to carbamate formation. The lower binding energy component (~396 eV) could possibly be due to strongly chemisorbed CO2. The maximum sorption capacity was about 4 mmole CO2/g sorbent at 85°C and 1 bar. This capacity was doubled by raising the CO2 pressure to 24.95 bars. The adsorption results can be described by a Langmuir adsorption isotherm.
Cite this paper: Khader, M. , Al-Marri, M. , Ali, S. , Qi, G. and Giannelis, E. (2015) Adsorption of CO2 on Polyethyleneimine 10k—Mesoporous silica Sorbent: XPS and TGA Studies. American Journal of Analytical Chemistry, 6, 274-284. doi: 10.4236/ajac.2015.64026.

[1]   Rao, A.B. and Rubin, E.S. (2002) A Technical, Economic, and Environmental Assessment of Amine-Based CO2 Capture Technology for Power Plant Greenhouse Gas Control. Environmental Science Technology, 36, 4467-4475.

[2]   Wolsky, A.M., Daniels, E.J. and Jody, B.J. (1994) CO2 Capture from the Flue Gas of Conventional Fossil-Fuel-Fired Power Plants. Environmental Progress, 13, 214-219.

[3]   Mandal, B.P., Biswas, A.K. and Bandyopadhyay, S.S. (2003) Absorption of Carbon Dioxide into Aqueous Blends of 2-Amino-2-Methyl-1-Propanol and Diethanolamine. Chemical Engineering Science, 58, 4137-4144.

[4]   Mandal, B.P. and Bandyopadhyay, S.S. (2006) Absorption of Carbon Dioxide into Aqueous Blends of 2-Amino-2-Methyl-1-Propanol and Monoethanolamine. Chemical Engineering Science, 61, 5440-5457.

[5]   Liu, Z.-L., Teng, Y., Zhang, K., Cao, Y. and Pan, W.-P. (2013) CO2 Adsorption Properties and Thermal Stability of Different Amine-Impregnated MCM-41 Materials. Journal of Fuel Chemistry and Technology, 41, 469-476.

[6]   Yang, S.T., Kim, J.Y., Kim, J. and Ahn, W.S. (2012) CO2 Capture over Amine-Functionalized MCM-22, MCM-36 and ITQ-2. Fuel, 97, 435-442.

[7]   Bhagiyalakshmi, M., Yun, L.J., Anuradha, R. and Jang, H.T. (2010) Synthesis of Chloropropylamine Grafted Mesoporous MCM-41, MCM-48 and SBA-15 from Rice Husk Ash: Their Application to CO2 Chemisorption. Journal of Porous Materials, 17, 475-484.

[8]   Fan, Y.F., Lively, R.P., Labreche, Y., Rezaei, F., Koros, W.J. and Jones, C.W. (2014) Evaluation of CO2 Adsorption Dynamics of Polymer/Silica Supported Poly(ethylenimine) Hollow Fiber Sorbents in Rapid Temperature Swing Adsorption. International Journal of Greenhouse Gas Control, 21, 61-71.

[9]   Mustafa, A.A., Ratayakorn, K. and Christopher, W.J. (2014) Guanidinylated Poly(allylamine) Supported on Mesoporous silica for CO2 Capture from Flue Gas. Fuel, 121, 79-85.

[10]   Dong, H.J., Hyunchul, J., Dong, K.S., Chang, H.L. and Sung, H.K. (2014) Effect of Amine Structure on CO2 Adsorption over Tetraethylenepentamine Impregnated Poly Methyl Methacrylate Supports. Separation and Purification Technology, 125, 187-193.

[11]   Ko, Y.G., Leea, H.J., Oh, H.C. and Choi, U.S. (2013) Amines Immobilized Double-Walled Silica Nanotubes for CO2 Capture. Journal of Hazardous Materials, 250-251, 53-60.

[12]   Al-Marri, M.J., Khader, M.M., Giannelis, E.P. and Shibl, S.F. (2014) Optimization of Selection of Chain Amine Scrubbers for CO2 Capture. Journal of Molecular Modeling, 20, 1-10.

[13]   Wang, K., Shang, H., Li, L., Yan, X., Yan, Z., Liu, C. and Zha, Q. (2012) Efficient CO2 Capture on Low-Cost Silica Gel Modified by Polyethyleneimine. Journal of Natural Gas Chemistry, 21, 319-323.

[14]   Brilman, D.W.F. and Veneman, R. (2013) Capturing Atmospheric CO2 Using Supported Amine Sorbents. Energy Procedia, 37, 6070-6078.

[15]   Qi, G., Wang, Y., Estevez, L., Duan, X., Anako, N., Park, A.A., Li, W., Jones, C.W. and Giannelis, E.P. (2011) High Efficiency Nanocomposite Sorbents for CO2 Capture Based on Amine-Functionalized Mesoporous Capsules. Energy & Environmental Science, 4, 444-452.

[16]   Qi, G., Fu, L., Choi, B.H. and Giannelis, E.P. (2012) Efficient CO2 Sorbents Based on Silica Foam with Ultra-Large Mesopores. Energy & Environmental Science, 5, 7368-7375.

[17]   Chen, C., Son, W.J., Youb, K.S., Ahn, J.W. and Ahn, W.S. (2010) Carbon Dioxide Capture Using Amine-Impregnated HMS Having Textural Mesoporosity. Chemical Engineering Journal, 161, 46-52.

[18]   Labreche, Y., Lively, R.P., Rezaei, F., Chen, G., Jones, C.W. and Koros, W.J. (2013) Post-Spinning Infusion of Poly(ethyleneimine) into Polymer/Silica Hollow Fibre Sorbents for Carbon Dioxide Capture. Chemical Engineering Journal, 221, 166-175.

[19]   Cheung, O., Bacsik, Z., Liu, Q., Mace, A. and Hedin, N. (2013) Adsorption Kinetics for CO2 on Highly Selective Zeolites NaKA and Nano-NaKA. Applied Energy, 112, 1326-1336.

[20]   Xu, X., Zhao, X., Sun, L. and Liu, X. (2009) Adsorption Separation of Carbon Dioxide, Methane and Nitrogen on Monoethanol Amine Modified β-Zeolite. Journal of Natural Gas Chemistry, 18, 167-172.

[21]   Rashidi, N.A., Yusup, S. and Loong, L.H. (2013) Kinetic Studies on Carbon Dioxide Capture Using Activated Carbon. Chemical Engineering Transactions, 35, 361-366.

[22]   Guo, B., Chang, L. and Xie, K. (2006) Adsorption of Carbon Dioxide on Activated Carbon. Journal of Natural Gas Chemistry, 15, 223-229.

[23]   Dantas, T.L.P., Luna, F.M.T., Silva Jr., I.J., de Azevedo, D.C.S., Grande, C.A., Rodrigues, A.E. and Moreira, R.F.P.M. (2011) Carbon Dioxide-Nitrogen Separation through Adsorption on Activated Carbon in a Fixed Bed. Chemical Engineering Journal, 169, 11-19.

[24]   Shafeeyan, M.S., Daud, W.M.A.W., Houshmand, A. and Shamiri, A. (2010) A Review on Surface Modification of Activated Carbon for Carbon Dioxide Adsorption. Journal of Analytical and Applied Pyrolysis, 89, 143-151.

[25]   Auta, M., AmatDarbis, N.D., Mohd Din, A.T. and Hameed, B.H. (2013) Fixed-Bed Column Adsorption of Carbon Dioxide by Sodium Hydroxide Modified Activated Alumina. Chemical Engineering Journal, 233, 80-87.

[26]   Chen, C. and Ahn, W.S. (2011) CO2 Capture Using Mesoporous Alumina Prepared by a Sol-Gel Process. Chemical Engineering Journal, 166, 646-651.

[27]   Thote, J.A., Chatti, R.V., Iyer, K.S., Kumar, V., Valechha, A.N., Labhsetwar, N.K., Biniwale, R.B., Yenkie, M.K.N. and Rayalu, S.S. (2012) N-Doped Mesoporous Alumina for Adsorption of Carbon Dioxide. Journal of Environmental Sciences, 24, 1979-1984.

[28]   Nafisi, V. and H?gg, M.B. (2014) Development of Dual Layer of ZIF-8/PEBAX-2533 Mixed Matrix Membrane for CO2 Capture. Journal of Membrane Science, 459, 244-255.

[29]   Kim, J.Y., Kim, J., Yang, S.T. and Ahn, W.S. (2013) Mesoporous SAPO-34 with Amine-Grafting for CO2 Capture. Fuel, 108, 515-520.

[30]   Dutcher, B., Fan, M., Cui, S., Shen, X.D., Kong, Y., Russell, A.G., McCurdy, P. and Giotto, M. (2013) Characterization and Stability of a New, High-Capacity Amine-Functionalized CO2 Sorbent. International Journal of Greenhouse Gas Control, 18, 51-56.

[31]   McCann, N., Phan, D., Fernandes, D. and Maeder, M. (2011) A Systematic Investigation of Carbamate Stability Constants by 1H NMR. International Journal of Greenhouse Gas Control, 5, 396-400.

[32]   Sanz, R., Calleja, G., Arencibia, A. and Sanz-Pèrez, E.S. (2010) CO2 Adsorption on Branched Polyethyleneimine-Impregnated Mesoporous silica SBA-15. Applied Surface Science, 256, 5323-5328.

[33]   Hiyoshi, N., Yogo, K. and Yashima, T. (2005) Adsorption Characteristics of Carbon Dioxide on Organically Functionalized SBA-15. Microporous and Mesoporous Materials, 84, 357-365.

[34]   Aresta, M. and Quaranta, E. (1992) Role of the Macro-cyclic Polyether in the Synthesis of N-Alkylcarbamate Esters from Primary Amines, CO2 and Alkyl Halides in the Presence of Crown-Ethers. Tetrahedron, 48, 1515-1530.

[35]   Wang, X.X., Schwartz, V., Clark, J.C., Ma, M.L., Overbury, S.H., Xu, X.C. and Song, C.S. (2009) Infrared Study of CO2 Sorption over “Molecular Basket” Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve. Journal of Physical Chemistry, 113, 7260-7268.

[36]   El Nahhal, I.M., Chehimi, M.M., Cordier, C. and Dodin, G. (2000) XPS, NMR and FTIR Structural Characterization of Polysiloxane-Immobilized Amine Ligand Systems. Journal of Non-Crystalline Solids, 275, 142-146.

[37]   Wang, J., Chen, H., Zhou, H., Liu, X., Qiao, W., Long, D. and Ling, L. (2013) Carbon Dioxide Capture Using Polyethylenimine-Loaded Mesoporous Carbons. Journal of Environmental Sciences, 25, 124-132.

[38]   Chang, A.C.C., Chuang, S., Gray, M. and Soong, Y. (2003) In-Situ Infrared Study of CO2 Adsorption on SBA-15 Grafted with γ-(Aminopropyl)triethoxysilane. Energy & Fuels, 17, 468-473.

[39]   Son, W.J., Choi, J.S. and Ahn, W.S. (2008) Adsorptive Removal of Carbon Dioxide Using Polyethylene-imine-Loaded Mesoporous silica Materials. Microporous and Mesoporous Materials, 113, 31-40.