Journal of Thermal Analysis and Calorimetry

, Volume 138, Issue 4, pp 2577–2595 | Cite as

Adsorption calorimetry

Isotherms models, kinetics study and thermodynamic parameters of asphaltenes adsorption onto activated carbons prepared from corncobs waste from toluene solutions
  • Paola Rodríguez-Estupiñán
  • Liliana GiraldoEmail author
  • Juan Carlos Moreno-Piraján


The efficiency of activated carbons prepared from corncob, to remove asphaltenes from toluene modeled solutions, has been studied in this work. The activating agent effect over carbonaceous solid preparation , and also temperature effect on the asphaltenes adsorption on the prepared activated carbons, was studied. The asphaltene adsorption isotherms were determined, and the experimental data were analyzed applying the Langmuir, Freundlich, Redlich–Peterson, Toth and Radke–Prausnitz and Sips models. Redlich–Peterson model described the asphaltenes isotherm on the activated carbons better. The asphaltenes adsorption capacities at 25° for activated carbons were: 1305 mg g−1, 1654 mg g−1 and 559.1 mg g−1 for GACKOH, GACKP and GACH3PO4, respectively. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated from the adsorption isotherms in asphaltene solutions from toluene solutions, and it was found that the adsorption process was spontaneous and exothermic in nature. Kinetic parameters, reaction rate constant and equilibrium adsorption capacities were evaluated and correlated for each kinetic model. The results show that asphaltene adsorption is described by pseudo-second-order kinetics, suggesting that the adsorption process is chemisorption. The adsorption calorimetry was used to analyze the type of interaction between the asphaltenes and the activated carbons prepared in this work, and their values were compared with the enthalpic values obtained from the Clausius–Clapeyron equation.


Asphaltenes Isotherms Thermodynamics Immersion calorimetry Gibbs energy Entropy Immersion enthalpy Isotherms Langmuir Freundlich Sips 



The authors thank the Framework Agreement between the Universidad de Los Andes and the Universidad Nacional de Colombia and the act of agreement established between the Chemistry Departments of the two universities. The authors also appreciate the grant for the funding of research programs for Associate Professors, Full Professors, and Emeritus Professors announced by the Faculty of Sciences of the University of the Andes, 20-12-2019–2020, 2019, according to the project “Enthalpy, free energy and adsorption energy of the activated carbon interaction and solutions of emerging organic compounds”.


  1. 1.
    Franco CA, Lozano MM, Acevedo S, Nassar NN, Cortes FB. Effects of resin I on asphaltene adsorption onto nanoparticles: a novel method for obtaining asphaltenes/resin isotherms. Energy Fuels. 2016;30:264–72. Scholar
  2. 2.
    Franco CA, Nassar NN, Ruiz MA, Pereira-Almao P, Cortés FB. Nanoparticles for inhibition of asphaltenes damage: adsorption study and displacement test on porous media. Energy Fuels. 2013;27:2899–907. Scholar
  3. 3.
    Kokal SL, Sayegh SG. Asphaltenes: the cholesterol of petroleum. In: Middle East oil show, Bahrain, 1995.
  4. 4.
    Akbarzadeh K, Hammami A, Kharrat A, Zhang D, Allenson S, Creek J, Kabir S, Jamaluddin A, Marshall AG, Rodgers RP. Asphaltenes problematic but rich in potential. Oilfield Rev. 2007;19:22–43.Google Scholar
  5. 5.
    Adams JJ. Asphaltene adsorption, a literature review. Energy Fuels. 2014;28:2831–56. Scholar
  6. 6.
    de la Cruz JLM, Castellanos-Ramírez IV, Ortiz-Tapia A, Buenrostro-Gonzaĺez E, Durań-Valencia C, Loṕez-Ramírez S. Study of monolayer to multilayer adsorption of asphaltenes on reservoir rock minerals. Colloids Surf A. 2009;340:149–54. Scholar
  7. 7.
    Piro G, Canonico LB, Galbariggi G, Bertero L, Carniani C. Asphaltene adsorption onto formation rock: an approach to asphaltene formation damage prevention. SPE Prod Facil. 1996;11:156–60. Scholar
  8. 8.
    Jienian Y, Plancher H, Morrow N. Wettability changes induced by adsorption of asphaltenes. Oceanogr Lit Rev. 1998;3:587–8. Scholar
  9. 9.
    Leontaritis K, Mansoori G. Asphaltene flocculation during oil production and processing: a thermodynamic collodial model. In: SPE international symposium on oilfield chemistry, 1987.
  10. 10.
    Alboudwarej H, Pole D, Svrcek WY, Yarranton HW. Adsorption of asphaltenes on metals. Ind Eng Chem Res. 2005;44:5585–92. Scholar
  11. 11.
    Gawel I, Bociarska D, Biskupski P. Effect of asphaltenes on hydroprocessing of heavy oils and residua. Appl Catal A. 2005;295:89–94. Scholar
  12. 12.
    Speight J. Petroleum asphaltenes-part 1: asphaltenes, resins and the structure of petroleum. Oil Gas Sci Technol. 2004;59:467–77. Scholar
  13. 13.
    Andersen SI, Speight JG. Petroleum resins: separation, character, and role in petroleum. Pet Sci Technol. 2001;19:1–34. Scholar
  14. 14.
    Murgich J, Rodríguez J, Aray Y. Molecular recognition and molecular mechanics of micelles of some model asphaltenes and resins. Energy Fuels. 1996;10:68–76. Scholar
  15. 15.
    Leoń O, Contreras E, Rogel E, Dambakli G, Acevedo S, Carbognani L, Espidel J. Adsorption of native resins on asphaltene particles: a correlation between adsorption and activity. Langmuir. 2002;18(13):5106–12. Scholar
  16. 16.
    Nassar NN. Asphaltene adsorption onto alumina nanoparticles: kinetics and thermodynamic studies. Energy Fuels. 2010;24:4116–22. Scholar
  17. 17.
    Mochida I, Xing Zhe Z, Sakanishi K. Catalyst deactivation during the hydrotreatment of asphaltene in an Australian brown coal liquid. Fuel. 1988;67:1101–5. Scholar
  18. 18.
    Melo F, Grange P, Delmon B. Influence of asphaltene deposition on catalytic activity of cobalt molybdenum on alumina catalysts. Appl Catal. 1984;11:281–93. Scholar
  19. 19.
    McLean JD, Kilpatrick PKJ. Effects of asphaltene aggregation in model heptane-toluene mixtures on stability of water-in-oil emulsions. Colloid Interface Sci. 1997;196:23–34. Scholar
  20. 20.
    McLean JD, Kilpatrick PKJ. Effects of asphaltene solvency on stability of water-in-crude-oil emulsions. Colloid Interface Sci. 1997;189:242–53. Scholar
  21. 21.
    Ekholm P, Blomberg E, Claesson P, Auflem IH, Sjöblom J, Kornfeldt AJ. A quartz crystal microbalance study of the adsorption of asphaltenes and resins onto a hydrophilic surface. Colloid Interface Sci. 2002;247:342–50. Scholar
  22. 22.
    Abdallah WA, Taylor SD. Surface characterization of adsorbed asphaltene on a stainless steel surface. Nucl Instrum Methods Phys Res, Sect B. 2007;258:213–7. Scholar
  23. 23.
    Marczewski AW, Szymula M. Adsorption of asphaltenes from toluene on mineral surface. Colloids Surf A. 2002;208:259–66. Scholar
  24. 24.
    Marlow BJ, Sresty GC, Hughes RD, Mahajan OP. Colloidal stabilization of clays by asphaltenes in hydrocarbon media. Colloids Surf. 1987;24:283–97. Scholar
  25. 25.
    Menon VB, Wasan DT. Particle—fluid interactions with applications to solid-stabilized emulsions part III. Asphaltene adsorption in the presence of quinaldine and 1,2-dimethylindole. Colloids Surf. 1987;23:353–62. Scholar
  26. 26.
    Pernyeszi T, Patzkó A, Berkesi O, Dékany I. Asphaltene adsorption on clays and crude oil reservoir rocks. Colloids Surf A. 1998;137:373–84. Scholar
  27. 27.
    Saada A, Siffert B, Papirer E. Comparison of the hydrophilicity/hydrophobicity of illites and kaolinites. J Colloid Interface Sci. 1995;174:185–90. Scholar
  28. 28.
    González G, Moreira MBC. The wettability of mineral surfaces containing adsorbed asphaltene. Colloids Surf. 1991;58:293–302. Scholar
  29. 29.
    Pernyeszi T, Dékany I. Sorption and elution of asphaltenes from porous silica surfaces. Colloids Surf A. 2001;194:25–39. Scholar
  30. 30.
    Bantignies J-L, dit Moulin CC, Dexpert H. Asphaltene adsorption on kaolinite characterized by infrared and X-ray absorption spectroscopies. J Pet Sci Eng. 1998;20:233–7. Scholar
  31. 31.
    Gaboriau H, Saada A. Influence of heavy organic pollutants of anthropic origin on PAH retention by kaolinite. Chemosphere. 2001;44:1633–9. Scholar
  32. 32.
    Drummond C, Israelachvili J. Fundamental studies of crude oil–surface water interactions and its relationship to reservoir wettability. J Pet Sci Eng. 2004;45:61–81. Scholar
  33. 33.
    Tong ZX, Morrow NR, Xie X. Spontaneous imbibition for mixed-wettability states in sandstonesinduced by adsorption from crude oil. J Pet Sci Eng. 2003;39:351–61. Scholar
  34. 34.
    Kumar K, Dao E, Mohanty KKJ. AFM study of mineral wettability with reservoir oils. Colloid Interface Sci. 2005;289:206–17. Scholar
  35. 35.
    Acevedo S, Ranaudo MA, García C, Castillo J, Fernández A, Caetano M, Goncalvez S. Importance of asphaltene aggregation in solution in determining the adsorption of this sample on mineral surfaces. Colloids Surf A. 2000;166:145–52. Scholar
  36. 36.
    Alkafeef SF, Algharaib MK, Alajmi AFJ. Hydrodynamic thickness of petroleum oil adsorbed layers in the pores of reservoir rocks. Colloid Interface Sci. 2006;298:13–9. Scholar
  37. 37.
    Cosultchi A, Garcia E, Mar B, García-Bórquez A, Lara VH, Bosch P. Formation of petroleum organic deposits on steel surfaces. Fuel. 2002;81:413–21. Scholar
  38. 38.
    Sakanishi K, Saito I, Watanabe I, Mochida I. Dissolution and demetallation treatment of asphaltene in residusing adsorbent and oil-soluble Mo complex. Fuel. 2004;83:1889–93. Scholar
  39. 39.
    Akhlaq MS, Göetze P, Kessel D, Dornow W. Adsorption of crude oil colloids on glass plates: measurements of contact angles and the factors influencing glass surface properties. Colloids Surf A. 1997;126:25–32. Scholar
  40. 40.
    Castillo J, Goncalves S, Fernández A, Mujica V. Applications of photothermal displacement spectroscopy to the study of asphaltenes adsorption. Opt Commun. 1998;145:69–75. Scholar
  41. 41.
    Jeribi M, Almir-Assad B, Langevin D, Hénaut I, Argillier JFJ. Adsorption kinetics of asphaltenes at liquid interfaces. Colloid Interface Sci. 2002;256:268–72. Scholar
  42. 42.
    Cagna A, Esposito G, Quinquis AS, Langevin D. On the reversibility of asphaltene adsorption at oil-water interfaces. Colloids Surf A. 2018;548:46–53. Scholar
  43. 43.
    Langevin D, Argillier JF. Interfacial behavior of asphaltenes. Adv Colloid Interface Sci. 2016;233:83–93. Scholar
  44. 44.
    Nassar NN, Husein MM. Effect of microemulsion variables on copper oxide nanoparticle uptake by AOT microemulsions. Colloid Interface Sci. 2007;316:442–50. Scholar
  45. 45.
    Nassar NN, Husein MM. Study and modeling of iron hydroxide nanoparticle uptake by AOT(w/o) microemulsions. Langmuir. 2007;23:13093–103. Scholar
  46. 46.
    Nassar NN, Husein MM. Ultradispersed particles in heavy oil: part I, preparation and stabilization of iron oxide/hydroxide. Fuel Process Technol. 2010;91:164–8. Scholar
  47. 47.
    Husein MM, Patruyo L, Pereira-Almao P, Nassar NN. Scavenging H2S(g) from oil phases by means of ultradispersed sorbents. J Colloid Interface Sci. 2010;342:253–60. Scholar
  48. 48.
    El-Sayed GO, Yehia MM, Asaad AA. Assessment of activated carbon prepared from corncob by chemical activation with phosphoric acid. Water Resour Ind. 2014;7:66–75. Scholar
  49. 49.
    Brunauer S, Emmet PH, Teller E. Absorption of gases in multimolecular layers. J Am Chem Soc. 1938;60:309–19. Scholar
  50. 50.
    Gregg SJ, Sing KSW. Adsorption, surface area and porosity. 2nd ed. London: Academic Press; 1982.Google Scholar
  51. 51.
    McClellan AL, Harnsberger HF. Cross-sectional areas of molecules adsorbed on solid surfaces. J Colloid Interface Sci. 1967;23:577–99. Scholar
  52. 52.
    Cerofolini G. A unified theory for Freundlich, Dubinin-Radushkevich, and Temkin behaviors. J Colloid Interface Sci. 1982;86:204–12. Scholar
  53. 53.
    Ravikovitch PI, Neimark AV. Density functional theory model of adsorption on amorphous and microporous silica materials. Langmuir. 2006;22:11171–9. Scholar
  54. 54.
    Dubinin MM. Progress in surface and membrane science. In: Danielli JF, Rosenberg MD, Cadenhead DA, editors; Academic Press: New York, 1975; 9. p. 10–15.Google Scholar
  55. 55.
    Neimark AV, Lin Y, Ravikovitch PI, Thommes M. Quenched solid density functional theory and pore size analysis of micro-mesoporous carbons. Carbon. 2009;47:1617–28. Scholar
  56. 56.
    Fonseca-Correa RA, Giraldo L, Moreno-Piraján JC. Trivalent chromium removal from aqueous solution with physically and chemically modified corncob waste. J Anal Appl Pyrol. 2013;101:132–41. Scholar
  57. 57.
    Franco CA, Montoya T, Nassar NN, Pereira-Almao P, Cortés FB. Adsorption and subsequent oxidation of colombian asphaltenes onto nickel and/or palladium oxide supported on fumed silica nanoparticles. Energy Fuels. 2013;27:7336–47. Scholar
  58. 58.
    Cortés FB, Mejía JM, Ruiz MA, Benjumea P, Riffel DB. Sorption of asphaltenes onto nanoparticles of nickel oxide supported on nanoparticulated silica gel. Energy Fuels. 2012;26:1725–30. Scholar
  59. 59.
    Weber WJ, Morris JC. Kinetics of adsorption on carbon from solution. J Sanit Eng Div. 1963;89:31–59.Google Scholar
  60. 60.
    Moreno-Pirajan JC, Bastidas-Barranco MJ, Giraldo L. Preparation of activated carbons for storage of methane and its study by adsorption calorimetry. J Therm Anal Calorim. 2018;131:259–71. Scholar
  61. 61.
    Rouquerol J, Rouquerol F, Sing KS. Adsorption by powders and porous solids: principles, methodology and applications. London: Academic Press; 1999.Google Scholar
  62. 62.
    Moreno-Piraján JC, Gómez-Cruz R, García-Cuello V, Giraldo L. Binary system Cu(II)/Pb(II) adsorption on activated carbon obtained by pyrolysis of cow bone study. J Anal Appl Pyrol. 2010;89:122–8. Scholar
  63. 63.
    Marsh H, Rodríguez-Reinoso F. Activated carbon. Amsterdam: Elsevier; 2006.CrossRefGoogle Scholar
  64. 64.
    Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem. 2015;87:1052–69. Scholar
  65. 65.
    Dubinin MM, Astakhov VA. Description of adsorption equilibria of vapors on zeolites over wide ranges of temperature and pressure. Adv Chem Ser. 1971;102:69–85. Scholar
  66. 66.
    Martínez A, Izquierdo MT, Valenciano R, Rubio B. Toluene and n-hexane adsorption and recovery behavior on activated carbons derived from almond shell wastes. Fuel Process Technol. 2013;110:1–7. Scholar
  67. 67.
    Girgis BS, Ishak MF. Activated carbon from cotton stalks by impregnation with phosphoric acid. Mater Lett. 1999;39:107–14. Scholar
  68. 68.
    Olivier JP. Improving the models used for calculating the size distribution of micropore volume of activated carbons from adsorption data. Carbon. 1998;36:1469–72. Scholar
  69. 69.
    Marsh H, Rodríguez-Reinoso F. Activated carbon. Oxford: Elsevier Ltd; 2006.CrossRefGoogle Scholar
  70. 70.
    Zuo S, Yang J, Liu J. Effects of the heating history of impregnated lignocellulosic material on pore development during phosphoric acid activation. Carbon. 2010;48:3293–311. Scholar
  71. 71.
    Cao Q, Xie K-C, Lv Y-K, Bao W-R. Process effects on activated carbon with large specific surface area from corncob. Bioresour Technol. 2006;97:110–5. Scholar
  72. 72.
    Sych NV, Trofymenko SI, Poddubnaya OI, Tsyba MM, Sapsay VI, Klymchuk DO, Puziy AM. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob. Appl Surf Sci. 2012;261:75–82. Scholar
  73. 73.
    Langmuir I. The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc. 1918;40:1361–403. Scholar
  74. 74.
    Langmuir I. the evaporation, condensation and reflection of molecules and the mechanism of adsorption. Phys Rev. 1916;8:149–76. Scholar
  75. 75.
    Freundlich H. Adsorption in solution. Phys Chem. 1906;57:384–410.Google Scholar
  76. 76.
    Langmuir I. Adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc. 1918;40:1361–403.CrossRefGoogle Scholar
  77. 77.
    Redlich O, Petersen DL. A useful adsorption isotherm. J Phys Chem. 1959;63:1024. Scholar
  78. 78.
    Toth J. State equations of the solid-gas interphase layers. Acta Chim Acad Sci Hung. 1971;69:311–7.Google Scholar
  79. 79.
    Sips R. On the structure of a catalyst surface. J Chem Phys. 1948;16:490–5. Scholar
  80. 80.
    Carvajal-Bernal AM, Gomez-Granados F, Giraldo L, Moreno-Pirajan JC. Application of the Sips model to the calculation of maximum adsorption capacity and immersion enthalpy of phenol aqueous solutions on activated carbons. Eur J Chem. 2017;8:112–8. Scholar
  81. 81.
    Radke CJ, Prausnitz JM. Adsorption of organic solutes from dilute aqueous solution on activated carbon. Ind Eng Chem Fundam. 1972;11:445–51. Scholar
  82. 82.
    Foo KY, Hameed BH. Insights into the modeling of adsorption isotherm systems. Chem Eng J. 2010;156:2–10. Scholar
  83. 83.
    Mirzayi B, Shayan NN. Adsorption kinetics and catalytic oxidation of asphaltene on synthesized maghemite nanoparticles. J Petrol Sci Eng. 2014;121:134–41.CrossRefGoogle Scholar
  84. 84.
    Myers AL, Valenzuela DP. Adsorption equilibrium data handbook. Englewood Cliffs: Prentice Hall; 1989.Google Scholar
  85. 85.
    Ho YS. Citation review of Lagergren kinetic rate equation on adsorption reactions. Scientometrics. 2004;59:171–7. Scholar
  86. 86.
    Weber TW, Chakkravorti RK. Pore and solid diffusion models for fixed-bed adsorbers. AlChE J. 1974;20:228–38. Scholar

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© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Departamento de Química, Grupo de Investigación en Sólidos Porosos y Calorimetría, Facultad de CienciasUniversidad de los AndesBogotáColombia
  2. 2.Departamento de Química, Facultad de CienciasUniversidad Nacional de ColombiaBogotáColombia

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