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CO 2 ADSORPTION ON Li + MODIFIED 4A ZEOLITE: EFFECT OF ACTIVATION TEMPERATURE

CO 2 ADSORPTION ON Li + MODIFIED 4A ZEOLITE: EFFECT OF ACTIVATION TEMPERATURE Joziane G. Meneguin Leonardo H. de Oliveira Maria Angélica S. D. de Barros Pedro A. Arroyo Wilson M. Grava Jailton F. do Nascimento 10/04/2013. INTRODUCTION. CO 2 separation techniques:

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CO 2 ADSORPTION ON Li + MODIFIED 4A ZEOLITE: EFFECT OF ACTIVATION TEMPERATURE

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  1. CO2 ADSORPTION ON Li+ MODIFIED 4A ZEOLITE: EFFECT OF ACTIVATION TEMPERATURE Joziane G. Meneguin Leonardo H. de Oliveira Maria Angélica S. D. de Barros Pedro A. Arroyo Wilson M. Grava Jailton F. do Nascimento 10/04/2013

  2. INTRODUCTION • CO2 separation techniques: • Amines, Membranes, Distillation and Adsorption • Two mainly purposes (Saha et al., 2010;Zukal et al., 2011): • - Exhaust gas • - Natural gas mixtures

  3. INTRODUCTION • Adsorption recently researches: • Yi et al. (2012): equilibriumandkinetics in FAU and LTA • Montanari et al. (2011): comparison of 4A and 13X with IR spectroscopy • Yang et al. (2010): ion-exchanged zeolite beta with alkali and alkaline earth metal ions

  4. OBJECTIVE • What is the effect of activation temperature on: • 1. volatiles removal from zeolite? • 2. zeolite’s crystallinity? • 3. CO2 adsorption/desorption isotherms at 30°C ? • Material: Li+ modified 4A zeolite.

  5. METHODOLOGY Preparation Ion exchange process: LiNO3, 75ºC Li+ content: 19 mg/g Varian SpectrAA 50B atomic absorption spectrometer Activation P = 0.1 bar at T = 150, 200, 300 or 400ºC for 25h Adsorption/desorption P = 0.1 to 40 bar at T = 30ºC and teq = 30min Rubotherm MSB, precise to ± 1×10-6 g X-ray Diffraction Shimadzu XRD-6000 X-ray diffractometer Thermogravimetric Analysis Netzsch STA 409 PG Luxx thermobalance

  6. METHODOLOGY Activation, Adsorption and Desorption: raw data.

  7. METHODOLOGY Raw data treatment used Experiment equation: Tóth equation (Tóth, 2001): Objetive function (Keller and Staudt, 2005):

  8. METHODOLOGY Fitting procedure • Density parameters: • ρs: estimatedbased on He experiments • (Dreisbach et al., 2002) • ρa= 1.117853 g/cm³ • CO2 at its triple point • (Span and Wagner, 1996) • ρ: calculated by PR EoS • (Peng and Robinson, 1976) Guess new parameters values

  9. RESULTS AND DISCUSSION • Volatiles removal from zeolite • Loss of mass during activation time

  10. RESULTS AND DISCUSSION • Volatiles removal from zeolite • Loss of mass: MSB and TGA

  11. RESULTS AND DISCUSSION 2. Zeolites’ crystallinity

  12. RESULTS AND DISCUSSION 3. CO2 adsorption isotherms at 30°C

  13. RESULTS AND DISCUSSION 3. CO2 adsorption isotherms at 30°C Adsorption capacity (40 bar) and crystallinity

  14. RESULTS AND DISCUSSION 3. CO2 adsorption/desorption isotherms at 30°C

  15. CONCLUSIONS • Increase activation temperature causes: • increase in loss of mass of material; • decrease in zeolite’s crystallinity; • increase in CO2 adsorption capacity.

  16. A FUTURE WORK Adsorption of CH4: Effects on material’s selectivity.

  17. REFERENCES DREISBACH, F., LÖSCH, H. W., HARTING, P. Highest Pressure Adsorption Equilibria Data: Measurement with Magnetic Suspension Balance and Analysis with a New Adsorbent/Adsorbate-Volume. Adsorption, v. 8, p. 95-109, 2002. KELLER, J., STAUDT, R. Gas Adsorption Equilibria, Springer Science, 2005. Montanari, T., Finocchio, E., Salvatore, E., Garuti, G., Giordano, A., Pistarino, C., Busca, G. CO2 separation and landfill biogas upgrading: A comparison of 4A and 13X zeolite adsorbents. Energy, v, 36, p. 314-319, 2011. PENG, D. Y., and ROBINSON, D. B. A New Two-Constant Equation of State. Ind. Eng. Chem. Fund., v. 15, p. 59-64, 1976. SAHA, D., BAO, Z., JIA, F., DENG, S. Adsorption of CO2, CH4, N2O, and N2 on MOF-5, MOF-177, and Zeolite 5A. Environ. Sci. Technol., v. 44, p. 1820-1826, 2010. SPAN, R., WAGNER, W. A new equation of state for carbon dioxide covering the full region from the triple-point temperature to 1100 K at pressure up to 800 Mpa. J. Phys. Chem. Ref. Data, v. 25, n. 6, p. 1509-1596, 1996. TÓTH, J. Adsorption. Theory, modeling, and analysis, Marcel Dekker Inc., 2001. Zukal, A., Arean, C. O., Delgado, M. R., Nachtigall, P., Pulido, A., J. Mayerová, J., Čejka, J. Combined volumetric, infrared spectroscopic and theoretical investigation of CO2 adsorption on Na-A zeolite. Micropor. Mesopor. Mat., v. 146, p. 97-105, 2011. Yang, S. T., Kim, J., Ahn, W. S. CO2 Adsorption over ion-exchanged zeolite beta with alkali and alkaline earth metal ions Micropor. Mesopor. Mater., v. 135, p. 90-94, 2010. Yi, H., Deng, H., Tang, X., Yu, Q., Zhou, X, Liu, H. Adsorption equilibrium and kinetics for SO2, NO, CO2 on zeolites FAU and LTA. J. Hazard. Mater., v. 111-117, p. 203-204, 2012.

  18. ACKNOWLEDGEMENTS Contact: leonardoh.deoliveira@gmail.com

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