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Study of Natural Clay Adsorbent Sepiolite for the Removal of Caffeine from Aqueous Solutions: Batch and Fixed-Bed Column Operation

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Sepiolite reveals as a low-cost and efficient adsorbent for the adsorption of caffeine from aqueous solutions. The characterization of this material was carried out by N2 adsorption–desorption at 77 K, Fourier transform infrared spectroscopy, thermogravimetric analysis, and electronic microscopy. Initially, batch adsorption experiments were developed in order to determine the equilibrium time and the adsorption isotherm of the system. Pseudo–first-order, Elovich equation, pseudo–second-order, and intra-particle diffusion models were applied to the experimental data to determine the adsorption kinetics. In continuous adsorption, the influence of several operation conditions (initial caffeine concentration, volumetric flow rate, and mass of adsorbent) on the shape of breakthrough curves and the mass transfer resistance was evaluated. Experimental data were fitted to the bed-depth service-time model bed-depth service-time (BDST). Through the calculation of the adsorption, parameters as breakthrough time or caffeine removal percentage can be concluded that the removal of this compound from aqueous solutions by adsorption in sepiolite beds is an alternative technique to the current methods, in order to eliminate this micropollutant.

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α :

Elovich model initial adsorption rate, milligrams per gram per hour

b :

Langmuir adsorption equilibrium constant, liters per milligram

β :

Elovich model desorption constant, grams per milligram

C 0 :

Adsorbate inlet concentration, milligrams per liter

C :

Adsorbate concentration at any time, milligrams per liter

C b :

Adsorbate concentration at breakthrough time, milligrams per liter

C e :

Equilibrium adsorbate concentration, milligrams per liter

D :

Diffusion coefficient, square centimeters per hour

E :

Mean free energy of adsorption, kilojoules per mole

ε :

Polanyi potential


Fractional bed utilization

K :

Dubinin–Radushkevich constant, moles squared per kilojoules squared

k AB :

BDST model adsorption rate constant, liters per milligram per hour

K F :

Freundlich constant, milligrams per gram

k 1 :

Pseudo–first-order model rate adsorption constant, per hour

k 2 :

Pseudo–second-order model rate adsorption constant, grams per milligram per hour

k i :

Intra-particle diffusion model rate parameter, milligram per gram per half hour


Mass transfer zone, centimeter

n F :

Freundlich constant

N 0 :

BDST model adsorption capacity, milligrams per liter

Q :

Volumetric flow rate, millimeters per minute

Q m :

Dubinin–Radushkevich maximum adsorption capacity, moles per gram

q :

Adsorption capacity at any time, milligrams per gram

q b :

Breakthrough adsorption capacity, milligrams per gram

q e :

Adsorption capacity at equilibrium, milligrams per gram

q s :

Saturation adsorption capacity, milligrams per gram

q sat :

Langmuir maximum adsorption capacity, milligrams per gram

r 0 :

Radius of the adsorbent particle, centimeters

R :

Gas constant, Joules per mole Kelvin

R L :

Separation factor

t :

Operation time, hours

t b :

Column breakthrough time, hours

t s :

Column saturation time, hours

t 1/2 :

Half adsorption time, hours

T :

Absolute temperature, Kelvin

U :

Linear flow velocity, centimeters per hour

W :

Mass of adsorbent, grams

Z :

Column length, centimeters


  1. Aguayo-Villarreal, I. A., Bonilla-Petriciolet, A., Hernández-Montoya, V., Montes-Morán, M. A., & Reynel-Avila, H. E. (2011). Batch and column studies of Zn+2 removal from aqueous solution using chicken feathers as sorbents. Chemical Engineering Journal, 167, 67–76.

  2. Ahmad, A. A., & Hameed, B. H. (2010). Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste. Journal of Hazardous Materials, 175, 298–303.

  3. Aksu, Z., & Gönen, F. (2004). Biosorption of phenol by immobilized activated sludge in a continuous packed bed: Prediction of breakthrough curves. Process Biochemistry, 39, 599–613.

  4. Aksu, Z., Çağatay, S. S., & Gönen, F. (2007). Continuous fixed bed biosorption of reactive dyes by dried Rhizopus arrhizus: Determination of column capacity. Journal of Hazardous Materials, 143, 362–371.

  5. Balci, S. (2004). Nature of ammonium ion adsorption by sepiolite: Analysis of equilibrium data with several isotherms. Water Research, 38, 1129–1138.

  6. Baral, S. S., Das, N., Ramulu, T. S., Sahoo, S. K., Das, S. N., & Chaudhury, G. R. (2009). Removal of Cr (VI) by thermally activated weed Salvinia cucullata in a fixed-bed column. Journal of Hazardous Materials, 161, 1427–1435.

  7. Bautista, F., Campelo, J. M., Luna, D., Luque, J., & Marinas, J. M. (2007). Vanadium oxides supported on TiO2-sepiolite and sepiolite: Preparation, structural and acid characterization and catalytic behavior in selective oxidation of toluene. Applied Catalysis A: General, 325, 336–344.

  8. Bekçi, Z., Seki, Y., & Yurdakoç, M. K. (2006). Equilibrium studies for trimethoprim adsorption on montmorillonite KSF. Journal of Hazardous Materials, B133, 233–242.

  9. Buerge, I. J., Poiger, T., Müller, M. D., & Buser, H.-R. (2003). Caffeine, an anthropogenic marker for wastewater contamination of surface waters. Environmental Science and Technology, 37, 691–700.

  10. Chang, P.-H., Jean, J.-S., Jiang, W. T., & Li, Z. (2009). Mechanism of tetracycline sorption on rectorite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 339, 94–99.

  11. Chen, S., Yue, Q., Gao, B., Li, Q., & Fu, X. K. (2012). Adsorption of hexavalent chromium from aqueous solution by modified corn stalk: A fixed-bed column study. Bioresource Technology, 113, 114–120.

  12. Dogan, M., & Alkan, M. (2003). Adsorption kinetics of methyl violet onto perlite. Chemosphere, 50, 517–528.

  13. Dogan, M., Özdemir, Y., & Alkan, M. (2007). Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite. Dyes and Pigments, 75, 701–713.

  14. Han, R., Zou, L., Zhao, X., et al. (2009). Characterization and properties of iron oxide-coated zeolite as adsorbent for removal of copper (II) from solution in fixed bed column. Chemical Engineering Journal, 149, 123–131.

  15. Ho, Y. S., & McKay, G. (2003). Sorption of dyes and copper ions onto biosorbents. Process Biochemistry, 38, 1047–1061.

  16. Jiang, J.-Q., & Ashekuzzaman, S. M. (2012). Development of novel inorganic adsorbent for water treatment. Current Opinion in Chemical Engineering, 1, 1–9.

  17. Jones, O. A. H., Voulvoulis, N., & Lester, J. N. (2004). Potential ecological and human health risks associated with the presence of pharmaceutically active compounds in the aquatic environment. Critical Reviews in Toxicology, 34, 335–350.

  18. Joss, A., Keller, E., Alder, A. C., et al. (2005). Removal of pharmaceuticals and fragrances in biological wastewater treatment. Water Research, 39, 3139–3152.

  19. Kannan, N., & Sundaram, M. (2001). Kinetics and mechanism of removal of methylene blue by adsorption on various carbons—A comparative study. Dyes and Pigments, 51, 25–40.

  20. Khan, M. R., Mozumder, S. I., Islam, A., Prasad, D. M. R., & Alam, M. M. (2012). Methylene Blue adsorption onto water hyacinth: Batch and column study. Water, Air, and Soil Pollution, 223, 2943–2953.

  21. Kümmerer, K. (2009). Antibiotics in the aquatic environment—A review—Part I. Chemosphere, 75, 417–434.

  22. Kundu, S., & Gupta, A. K. (2005). Analysis and modeling of fixed bed column operations on As (V) removal by adsorption onto iron oxide-coated cement (IOCC). Journal of Colloid and Interface Science, 290, 52–60.

  23. Lezehari, M., Baudu, M., Bouras, O., & Basly, J. P. (2012). Fixed-bed column studies of pentachlorophenol removal by use of alginate-encapsulated pillared clay microbeads. Journal of Colloid and Interface Science, 379, 101–106.

  24. Liu, P., & Zhang, L. (2007). Adsorption of dyes from aqueous solutions or suspensions with clay nano-adsorbents. Separation and Purification Technology, 58, 32–39.

  25. Maji, S. K., Pal, A., Pal, T., & Adak, A. (2007). Modeling and fixed bed column adsorption of As (III) on laterite soil. Separation and Purification Technology, 56, 284–290.

  26. Mersal, G. A. M. (2012). Experimental and computational studies on the electrochemical oxidation of caffeine at pseudo carbon paste electrode and its voltammetric determination in different real samples. Food Analytical Methods, 5, 520–529.

  27. Nagata, H., Shimoda, S., & Sudo, T. (1974). Dehydration of bound water of sepiolite. Clays and Clay Minerals, 22, 285–293.

  28. Özdemir, Y., Dogan, M., & Alkan, M. (2006). Adsorption of cationic dyes from aqueous solutions by sepiolite. Microporous and Mesoporous Materials, 96, 419–427.

  29. Özcan, A., Özcan, A. S., Tunali, S., Akar, T., & Kiran, I. (2005). Determination of the equilibrium, kinetic and thermodynamic parameters of adsorption of copper(II) ions onto seeds of Capsicum annuum. Journal of Hazardous Materials, 124, 200–208.

  30. Padilla-Ortega, E., Leyva-Ramos, R., Mendoza-Barron, J., Guerrero-Coronado, R. M., Jacobo-Azuara, A., & Aragón, A. (2011). Adsorption of heavy metal ions from aqueous solution onto sepiolite. Adsorption Science and Technology, 29, 569–584.

  31. Putra, E. K., Pranowo, R., Sunarso, J., Indraswati, N., & Ismadji, S. (2009). Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater: Mechanisms, isotherms and kinetics. Water Research, 43, 2419–2430.

  32. Rodríguez, A., Garcia, J., Ovejero, G., & Mestanza, M. (2009). Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions: Equilibrium and kinetics. Journal of Hazardous Materials, 172, 1311–1320.

  33. Rosal, R., Rodríguez, A., Perdigón-Melón, J. A., et al. (2010). Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Research, 44, 578–588.

  34. Sljivic, M., Smičiklas, I., Plećaš, L., & Pejanović, S. (2011). The role of external and internal mass transfer in the process of Cu2+ removal by natural mineral sorbents. Environmental Technology, 32, 933–943.

  35. Sotelo, J. L., Rodriguez, A., Alvarez, S., & Garcia, J. (2012). Removal of caffeine and diclofenac on activated carbon in fixed bed column. Chemical Engineering Research and Design, 90, 967–974.

  36. Sotelo, J. L., Rodriguez, A., Mestanza, M., Diez, S., Alvarez, S., & Garcia, J. (2012). Adsorption of pharmaceutical compounds and an endocrine disruptor from aqueous solutions by carbon materials. Journal of Environmental Science and Health. Part. B, 47, 640–652.

  37. Ternes, T. (1998). Occurrence of drugs in German sewage treatment plants and rivers. Water Research, 32, 3245–3260.

  38. Treybal, R. E. (1955). Mass-transfer operations. New York: McGraw-Hill.

  39. Uddin, T. M., Rukanuzzaman, M., Khan, M. R. M., & Islam, A. M. (2009). Adsorption of methylene blue from aqueous solution by jackfruit (Artocarpus heteropyllus) leaf powder: A fixed-bed column study. Journal of Environmental Management, 90, 3443–3450.

  40. Ünlü, N., & Ersoz, M. (2006). Adsorption characteristics of heavy metal ions onto a low cost biopolymer sorbent from aqueous solutions. Journal of Hazardous Materials, Part B, 136, 272–280.

  41. Valladares-Linares, R., Yangali-Quintanilla, V., Li, Z., & Amy, G. (2011). Rejection of micropollutants by clean and fouled forward osmosis membrane. Water Research, 45, 6737–6744.

  42. Vicente-Rodríguez, M. A., Suarez, M., Bañares-Muñoz, M. A., & Lopez-Gonzalez, J. D. (1996). Comparative FT-IR study of the removal of octahedral cations and structural modifications during acid treatment of several silicates. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 52, 1685–1694.

  43. Vieira, M. G. A., Gimenes, M. L., & da Silva, M. G. C. (2009). Modeling of the process of adsorption of nickel in bentonite clay. Chemical Engineering Transactions, 17, 421–426.

  44. Vijayaraghavan, K., & Yun, Y. S. (2008). Polysulfone-immobilized Corynebacterium glutamicum: A biosorbent for Reactive Black 5 from aqueous solution in an up-flow packed column. Chemical Engineering Journal, 145, 44–49.

  45. Vinodhini, V., & Das, N. (2010). Packed bed column studies on Cr (VI) removal from tannery wastewater by neem sawdust. Desalination, 264, 9–14.

  46. Volesky, B., Weber, J., & Park, J. M. (2003). Continuous-flow metal biosorption in a regenerable Sargassum column. Water Research, 37, 297–306.

  47. Wang, C. J., Li, Z., & Jiang, W.-T. (2011). Adsorption of ciprofloxacin on 2:1 dioctahedral clay minerals. Applied Clay Science, 53, 723–728.

  48. Wankat, P. C. (1990). Rate-controlled separations. Amsterdam: Kluwer.

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The authors gratefully acknowledge the financial support from Ministerio de Economía y Competitividad CTQ2011-27169, by CONSOLIDER Program through TRAGUA Network CSD2006-44, and Comunidad de Madrid through REMTAVARES Network S2009/AMB-1588. Also, the authors would like to thank TOLSA, S.A., for providing the sepiolite.

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Correspondence to Juan García.

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Sotelo, J.L., Ovejero, G., Rodríguez, A. et al. Study of Natural Clay Adsorbent Sepiolite for the Removal of Caffeine from Aqueous Solutions: Batch and Fixed-Bed Column Operation. Water Air Soil Pollut 224, 1466 (2013). https://doi.org/10.1007/s11270-013-1466-8

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  • Adsorption
  • Caffeine
  • Emerging contaminant
  • Fixed-bed
  • Sepiolite