SCTA and Catalysis

  • E. A. Fesenko
  • P. A. Barnes
  • G. M. B. Parkes
Part of the Hot Topics in Thermal Analysis and Calorimetry book series (HTTC, volume 3)

Abstract

Usually catalysts and their precursors are prepared by temperature programmed thermolyses carried out isothermally for a given time at a predetermined temperature, which is reached using a linear heating rate. Under such conditions, uncontrolled temperature and pressure gradients are created in the system and the reaction rates vary significantly during the preparation procedure [1]. Hence, catalysts obtained at the beginning and the end of conventional thermolysis, when the reaction rate is low, are made under very different conditions from those prevailing when the reaction rates are at their highest level. Furthermore, it is well known that rates of many thermal reactions are influenced by the partial pressure of product gases that vary from one instrument to another and lead to irreproducible reaction environments. SCTA techniques can be applied with advantages to avoid these problems and produce catalysts in a reproducible and uniform manner, with pre-determined properties [2].

Keywords

Apparent Activation Energy Nickel Oxide Calcium Hydroxide Linear Heating Nickel Nitrate 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Weisz, P.B. and Hicks, J.S. The behaviour of porous catalyst particles in view of internal mass and heat diffusion effects (Reprinted from Chem. Engng. Sci., Vol. 17, p. 265–275, 1962). Chemical Engineering Science 50, 3951–3958 (1995).CrossRefGoogle Scholar
  2. 2.
    Tiernan, M.J., Barnes, P.A. and Parkes, G.M.B. Use of solid insertion probe mass spectrometry and constant rate thermal analysis in the study of materials: Determination of apparent activation energies and mechanisms of solid-state decomposition reactions. Journal of Physical Chemistry B 103, 6944–6949 (1999).CrossRefGoogle Scholar
  3. 3.
    Thomas, J.M. and Thomas, W.J. Principles and practice of heterogeneous catalysis (VCH, Weinheim, New York, Basel, Cambridge, Tokyo, 1996).Google Scholar
  4. 4.
    Barnes, P.A., Parkes, G.M.B. and Charsley, E.L. High-performance evolved gas-analysis system for catalyst characterisation. Analytical Chemistry 66, 2226–2231 (1994).CrossRefGoogle Scholar
  5. 5.
    Rouquerol, J. Controlled rate evolved gas analysis: 35 years of rewarding services. Thermochimica Acta 300, 247–253 (1997).CrossRefGoogle Scholar
  6. 6.
    Alcala, M.D. et al. Constant Rate Thermal Analysis (CRTA) as a tool for the synthesis of materials with controlled texture and structure. Journal of Thermal Analysis and Calorimetry 56, 1447–1452 (1999).CrossRefGoogle Scholar
  7. 7.
    Sorensen, O.T. Quasi-Isothermal Methods in Thermal-analysis. Thermochimica Acta 50, 163–175 (1981).CrossRefGoogle Scholar
  8. 8.
    Sorensen, O.T. RCTA techniques used in studies of solid state reactions in inorganic compounds. Journal of Thermal Analysis and Calorimetry 56, 17–26 (1999).CrossRefGoogle Scholar
  9. 9.
    Parkes, G.M.B., Barnes, P.A., Charsley, E.L., Reading, M. and Abrahams, I. Real-time analysis of peak shape: a theoretical approach to sample controlled thermal analysis. Thermochimica Acta 354, 39–43 (2000).CrossRefGoogle Scholar
  10. 10.
    Parkes, G.M.B., Barnes, P.A. and Charsley, E.L. New concepts in sample controlled thermal analysis: Resolution in the time and temperature domains. Analytical Chemistry 71, 2482–2487 (1999).CrossRefGoogle Scholar
  11. 11.
    Ozawa, T. Temperature control modes in thermal analysis. Journal of Thermal Analysis and Calorimetry 64, 109–126 (2001).CrossRefGoogle Scholar
  12. 12.
    Paulik, F., Paulik, J. and Arnold, M. Investigation of the Phase-Diagram For the System Ni(NO3)2-H2O and Examination of the Decomposition of Ni(NO3)2.6H2O. Thermochimica Acta 121, 137–149 (1987).CrossRefGoogle Scholar
  13. 13.
    Llewellyn, P.L. et al. Preparation of reactive nickel oxide by the controlled thermolysis of hexahydrated nickel nitrate. Solid State Ionics 101, 1293–1298 (1997).CrossRefGoogle Scholar
  14. 14.
    Criado, J.M., Ortega, A. and Real, C. Mechanism of the Thermal Decomposition of Anhydrous Nickel Nitrate. Reactivity of Solids 4, 93–103 (1987).CrossRefGoogle Scholar
  15. 15.
    Gotor, F.J., Perez-Maqueda, L.A., Ortega, A. and Criado, J.M. Kinetic analysis of solid state reactions by means of stepwise isothermal analysis (SIA) and constant rate thermal analysis (CRTA) — A comparative study. Journal of Thermal Analysis and Calorimetry 53, 389–396 (1998).CrossRefGoogle Scholar
  16. 16.
    Naono, H., Nakai, K., Sueyoshi, T. and Yagi, H. Porous Texture in Hematite Derived From Goethite-Mechanism of Thermal-Decomposition of Goethite. Journal of Colloid and Interface Science 120, 439–450 (1987).CrossRefGoogle Scholar
  17. 17.
    Perez-Maqueda, L.A., Criado, J.M., Subrt, J. and Real, C. Synthesis of acicular hematite catalysts with tailored porosity. Catalysis Letters 60, 151–156 (1999).CrossRefGoogle Scholar
  18. 18.
    Perez-Maqueda, L.A., Criado, J.M., Real, C., Subrt, J. and Bohacek, J. The use of constant rate thermal analysis (CRTA) for controlling the texture of hematite obtained from the thermal decomposition of goethite. Journal of Materials Chemistry 9, 1839–1845 (1999).CrossRefGoogle Scholar
  19. 19.
    Chopra, G.S. et al. Factors influencing the texture and stability of maghemite obtained from the thermal decomposition of lepidocrocite. Chemistry of Materials 11, 1128–1137 (1999).CrossRefGoogle Scholar
  20. 20.
    Henmi, H., Hirayama, T., Mizutani, N. and Kato, M. Thermal-decomposition of basic copper carbonate, CuCO3.Cu(OH)2.H2O, in carbon-dioxide atmosphere (0–50 Atm). Thermochimica Acta 96, 145–153 (1985).CrossRefGoogle Scholar
  21. 21.
    Koga, N., Criado, J.M. and Tanaka, H. Apparent kinetic behavior of the thermal decomposition of synthetic malachite. Thermochimica Acta 341, 387— 394 (1999).CrossRefGoogle Scholar
  22. 22.
    Brown, I.W.M., Mackenzie, K.J.D. and Gainsford, G.J. Thermal-decomposition of the basic copper carbonates malachite and azurite. Thermochimica Acta 75, 23–32 (1984).CrossRefGoogle Scholar
  23. 23.
    Reading, M. and Dollimore, D. The application of constant rate thermal-analysis to the study of the thermal-decomposition of copper hydroxy carbonate. Thermochimica Acta 240, 117–127 (1994).CrossRefGoogle Scholar
  24. 24.
    Stacey, M.H. and Shannon, M.D. The decomposition of Cu-Zn hydroxy-carbonate solid solutions. Material Science Monographs 28, 713–718 (1985).Google Scholar
  25. 25.
    Koga, N., Criado, J.M. and Tanaka, H. Kinetic analysis of the thermal decomposition of synthetic malachite by CRTA. Journal of Thermal Analysis and Calorimetry 60, 943–954 (2000).CrossRefGoogle Scholar
  26. 26.
    Ortega, A. CRTA or TG? Thermochimica Acta 298, 205–214 (1997).CrossRefGoogle Scholar
  27. 27.
    Reading, M. The kinetics of heterogeneous solid state decomposition reactions; a new way forward? Thermochimica Acta 135, 37–57 (1988).CrossRefGoogle Scholar
  28. 28.
    Tiernan, M.J., Fesenko, E.A., Barnes, P.A., Parkes, G.M.B. and Ronane, M. The application of CRTA and linear heating thermoanalytical techniques to the study of supported cobalt oxide methane combustion catalysts. Thermochimica Acta 379, 163–175 (2001).CrossRefGoogle Scholar
  29. 29.
    Parkes, G.M.B., Barnes, P.A. and Charsley, E.L. Gas concentration programming — a new approach to sample controlled thermal analysis. Thermochimica Acta 320, 297–301 (1998).CrossRefGoogle Scholar
  30. 30.
    Barnes, P.A., Tiernan, M.J. and Parkes, G.M.B. Sample controlled thermal analysis — Temperature programmed reduction of bulk and supported copper oxide. Journal of Thermal Analysis and Calorimetry 56, 733–737 (1999).CrossRefGoogle Scholar
  31. 31.
    Barnes, P.A., Parkes, G.M.B., Brown, D.R. and Charsley, E.L. Applications of new high resolution evolved gas analysis systems for the characterisation of catalysts using rate-controlled thermal analysis. Thermochimica Acta 269, 665–676 (1995).CrossRefGoogle Scholar
  32. 32.
    Stacey, M.H. Constant rate thermal analysis for catalyst activation. Analytical Proceedings 22, 242–243 (1985).Google Scholar
  33. 33.
    Criado, J.M., Ortega, A. and Gotor, F. Correlation between the shape of controlled-rate thermal-analysis curves and the kinetics of solid-state reactions. Thermochimica Acta 157, 171–179 (1990).CrossRefGoogle Scholar
  34. 34.
    Ortega, A., Akhouayri, S., Rouquerol, F. and Rouquerol, J. On the suitability of Controlled Transformation Rate Thermal-Analysis (CRTA) for kinetic-studies. 2. Comparison with conventional TG for the thermolysis of dolomite with different particle sizes. Thermochimica Acta 235, 197–204 (1994).CrossRefGoogle Scholar
  35. 35.
    Vyazovkin, S. Two types of uncertainty in the values of activation energy. Journal of Thermal Analysis and Calorimetry 64, 829–835 (2001).CrossRefGoogle Scholar
  36. 36.
    Reading, M., Dollimore, D., Rouquerol, J. and Rouquerol, F. The measurement of meaningful activation-energies — using thermoanalytical methods — a tentative proposal. Journal of Thermal Analysis 29, 775–785 (1984).CrossRefGoogle Scholar
  37. 37.
    Tiernan, M.J., Barnes, P.A. and Parkes, G.M.B. New approach to the investigation of mechanisms and apparent activation energies for the reduction of metal oxides using constant reaction rate temperature-programmed reduction. Journal of Physical Chemistry B 103, 338–345 (1999).CrossRefGoogle Scholar
  38. 38.
    Criado, J.M., Gotor, F.J., Ortega, A. and Real, C. The new method of Constant Rate Thermal-Analysis (CRTA) — application to discrimination of the kinetic-model of solid — state reactions and the synthesis of materials. Thermochimica Acta 199, 235–238 (1992).CrossRefGoogle Scholar
  39. 39.
    Tiernan, M.J., Barnes, P.A. and Parkes, G.M.B. Reduction of iron oxide catalysts: The investigation of kinetic parameters using rate perturbation and linear heating thermoanalytical techniques. Journal of Physical Chemistry B 105, 220–228 (2001).CrossRefGoogle Scholar
  40. 40.
    Dawson, E.A., Parkes, G.M.B., Barnes, P.A., Chinn, M.J. and Norman, P.R. A study of the activation of carbon using sample controlled thermal analysis. Journal of Thermal Analysis and Calorimetry 56, 267–273 (1999).CrossRefGoogle Scholar
  41. 41.
    Real, C., Alcala, M.D. and Criado, J.M. Development of a new equipment for applying the Constant Rate Thermal-Analysis (CRTA) to Temperature Programmed Oxidation (TPO) of catalysis. Journal of Thermal Analysis 38, 797–802 (1992).CrossRefGoogle Scholar
  42. 42.
    Dawson, E.A., Parkes, G.M.B., Barnes, P.A., Chinn, M.J. and Norman, P.R. Comparison of new thermal and reactant gas blending methods for the controlled oxidation of carbon. Thermochimica Acta 335, 141–146 (1999).CrossRefGoogle Scholar
  43. 43.
    Fesenko, E.A., Barnes, P.A., Parkes, G.M.B., Dawson, E.A. and Tiernan, M.J. Catalysts characterisation and preparation using sample controlled thermal techniques — high resolution studies and the determination of the energetics of surface and bulk processes. Topics in catalysis 19, 291–309 (2002).CrossRefGoogle Scholar
  44. 44.
    Farneth, W.E. and Gorte, R.J. Methods for characterizing zeolite acidity. Chemical Reviews 95, 615–635 (1995).CrossRefGoogle Scholar
  45. 45.
    Salvador, F. and Merchan, M.D. Controlled-rate thermal desorption. Journal of Thermal Analysis and Calorimetry 51, 383–396 (1998).Google Scholar
  46. 46.
    Torralvo, M.J., Grillet, Y., Rouquerol, F. and Rouquerol, J. Application of CRTA to the study of microporosity by thermodesorption of preadsorbed water. Journal of Thermal Analysis 41, 1529–1534 (1994).CrossRefGoogle Scholar
  47. 47.
    Chevrot, V., Llewellyn, P.L., Rouquerol, F., Godlewski, J. and Rouquerol, J. Low temperature constant rate thermodesorption as a tool to characterise porous solids. Thermochimica Acta 360, 77–83 (2000).CrossRefGoogle Scholar
  48. 48.
    Fesenko, E.A., Barnes, P.A., Parkes, G.M.B., Brown, D.R. and Naderi, M. A new approach to the study of the reactivity of solid-acid catalysts: The application of constant rate thermal analysis to the desorption and surface reaction of isopropylamine from NaY and HY zeolites. Journal of Physical Chemistry B 105, 6178–6185 (2001).CrossRefGoogle Scholar
  49. 49.
    Aramendia, M.A. et al. Comparison of different organic test reactions over acid-base catalysts. Applied Catalysis A-General 184, 115–125 (1999).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2003

Authors and Affiliations

  • E. A. Fesenko
    • 1
  • P. A. Barnes
    • 1
  • G. M. B. Parkes
    • 1
  1. 1.Centre for Applied CatalysisUniversity of HuddersfieldUK

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