Catalysis Surveys from Asia

, Volume 1, Issue 2, pp 215–226 | Cite as

Measurements of acidic property of zeolites by temperature programmed desorption of ammonia

  • Miki Niwa
  • Naonobu Katada
Article

Abstract

The overall view of the TPD of ammonia to measure the acidic property of zeolites is described. The desorption peaks were identified and the significance of readsorption of ammonia was pointed out for the first time. This part of the work was done using reference catalysts of the Catalysis Society of Japan. The theoretical equation for the TPD with free readsorption of ammonia was then derived. Two methods for determining the strength of zeolite acidity based on the derived equation were proposed. A curve fitting method was then proposed to determine the zeolite acidity; based on this method, not only the strength of acidity but also its distribution could be determined. This method was applied to mordenite and ZSM-5 zeolites with different contents of Al and Na cations, and a simple conclusion was reached; namely, the strength of the acidity was not influenced by the number of acid sites but by the structure of the zeolite. Finally, water vapor treatment to rub out the l-peak (lower temperature peak) was briefly mentioned. This method was applied to precisely determine the acidity of Y-zeolite. A case study about the beta zeolite as the catalyst for the amination of phenol was exemplified; the catalytic activity was discussed in terms of the measured acidity.

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References

  1. [1]
    A. Corma, Chem. Rev. 95(1995)559.Google Scholar
  2. [2]
    W.E. Farneth and R.J. Gorte, Chem. Rev. 95(1995)615.Google Scholar
  3. [3]
    H.G. Karge and V. Dondur, J. Phys. Chem. 94(1990)765.Google Scholar
  4. [4]
    H.G. Karge, V. Dondur and J. Weitkamp, J. Phys. Chem. 95(1991) 283.Google Scholar
  5. [5]
    J.T. Miller, P.D. Hopkins, B.L. Meyers, G.J. Ray, R.T. Roginski, G.W. Zajac and N.H. Rosenbaum, J. Catal. 138(1992)115.Google Scholar
  6. [6]
    H. Stach, J. Janchen, H.-G. Jerschkewitz, U. Lohse, B. Parlitz, B. Zibrowius and M. Hunger, J. Phys. Chem. 96(1992)8473.Google Scholar
  7. [7]
    H. Stach, J. Janchen, H.-G. Jerschkewitz, U. Lohse, B. Parlitz, B. Zibrowius and M. Hunger, J. Phys. Chem. 96(1992)8480.Google Scholar
  8. [8]
    M. Crocker, R.H.M. Herold, M.H.W. Sonnemans, C.A. Emeis, A.E. Wilson and J.N. van der Moolen, J. Phys. Chem. 97(1993) 432.Google Scholar
  9. [9]
    J.-H. Kim, S. Namba and T. Yashima, Appl. Catal., A: General 100 (1993)27.Google Scholar
  10. [10]
    W.O. Haag, Stud. Surf. Sci. Catal. 94(1994)1375.Google Scholar
  11. [11]
    A.K. Neyestanaki, N. Kumar and L.-E. Lindfors, Appl. Catal., B: Environmental 7(1995)95.Google Scholar
  12. [12]
    A.W. O'Donovan, C.T. O'Connor and K.R. Koch, Microporous Mater. 5(1995)185.Google Scholar
  13. [13]
    F.M. Bautista and B. Delmon, Appl. Catal., A: General 130(1995)47.Google Scholar
  14. [14]
    T. Xiao, L. An and H. Wang, Appl. Catal., A: General 130(1995) 187.Google Scholar
  15. [15]
    J. Janchen, G. Vorbeck, H. Stach, B. Parlitz and J.H. van Hooff, Stud. Surf. Sci. Catal. 94(1995)108.Google Scholar
  16. [16]
    M. Laniecki and H.G. Karge, Stud. Surf. Sci. Catal. 94(1995)211.Google Scholar
  17. [17]
    B. Hunger, M. von Szombathely, J. Hoffmann and P. Braeuer, J. Therm. Anal. 44(1995)293.Google Scholar
  18. [18]
    W.-O. Xu, Y.-G. Yin, S.L. Suib and C.-L. O'Young, J. Phys. Chem. 99(1995)758.Google Scholar
  19. [19]
    W.-O. Xu, Y.-G. Tin, S.L. Suib, J.C. Edwards and C.-L. O'Young, J. Phys. Chem. 99(1995)9443.Google Scholar
  20. [20]
    A.M. Prakash, S. Ashtekar, D.K. Chakrabarty and S.V.V. Chilukuri, J. Chem. Soc., Faraday Trans. 91(1995)1045.Google Scholar
  21. [21]
    U. Lohse, A. Brueckner, K. Kintscher, B. Parlitz and E. Schreier, J. Chem. Soc., Faraday Trans. 91(1995)1173.Google Scholar
  22. [22]
    R. Vomscheid, M. Briend, M.-J. Peltre, D. Barthomeuf and P.P. Man, J. Chem. Soc., Faraday Trans. 91(1995)3281.Google Scholar
  23. [23]
    B. Hunger, M. Hans, M. Szombathely and E. Geidel, J. Chem. Soc., Faraday Trans. 92(1996)499.Google Scholar
  24. [24]
    Y. Xu, W. Liu, S.-T. Wong, L. Wang and X. Guo, Catal. Lett. 40(1996)207Google Scholar
  25. [25]
    E.-Y. Choi, I.-S. Nam and Y.G. Kim, J. Catal. 161(1996)597.Google Scholar
  26. [26]
    W.-O. Xu, Y.-G. Yin, S.L. Suib, J.C. Edwards and C.-L. O'Young, J. Catal. 163(1996)232.Google Scholar
  27. [27]
    N. Kumar, L.E. Lindfors and R. Byggningsbacka, Appl. Catal., A: General 139(1996)189.Google Scholar
  28. [28]
    Y. Murakami, in: Preparation of Catalysis III, G. Poncelet, P. Grange and P.A. Jacobs, eds., Elsevier, Amsterdam, 1983, p. 775.Google Scholar
  29. [29]
    M. Niwa, M. Iwamoto and K. Segawa, Bull. Chem. Soc. Jpn. 59 (1986)3735.Google Scholar
  30. [30]
    M. Sawa, M. Niwa and Y. Murakami, Zeolites 10(1990)307.Google Scholar
  31. [31]
    M. Niwa, M. Sawa, N. Katada and Y. Murakami, J. Phys. Chem. 99(1995)8812.Google Scholar
  32. [32]
    R.J. Cvetanovic and Y. Amenomiya, Advan. Catal. 17(1967)103.Google Scholar
  33. [33]
    T. Hashiguchi and S. Sakai, in: Preprint of the 11th Meeting on the Reference Catalyst of Japan, The Catalysis Society of Japan, Tokyo, 1987, p. 6.Google Scholar
  34. [34]
    A.W. Chester, J.B. Higgins, G.H. Kuehl, J.L. Schlenker and G.L. Woolery, in: Preprint of the 11th Meeting on the Reference Catalyst of Japan, The Catalysis Society of Japan, Tokyo, 1987, p. 22.Google Scholar
  35. [35]
    M. Sawa, M. Niwa and Y. Murakami, Zeolites 10(1990)532.Google Scholar
  36. [36]
    D. Barthomeuf, J. Phys. Chem. 97(1993)10092.Google Scholar
  37. [37]
    D. Ding, P. Sum, Q. Jin, B. Li and J. Wang, Zeolites 14(1994)65.Google Scholar
  38. [38]
    M. Sawa, M. Niwa and Y. Murakami, in: Proceedings of the 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1988, p. 380.Google Scholar
  39. [39]
    K. Tsutsumi and K. Nishiyama, Thermochim. Acta 143(1989)299.Google Scholar
  40. [40]
    N. Katada, H. Igi, J.-H. Kim and M. Niwa, J. Phys. Chem. B 101 (1997)5969.Google Scholar
  41. [41]
    G.M. Barrow, Physical Chemistry, 5th ed., McGraw-Hill, 1988.Google Scholar
  42. [42]
    The increase of translation entropy by vaporization can be calculated as follows: where Vm,VyVm, fis the ratio of the free volume of gas to liquid. The ratio is 40,000 to 80,000 for most materials at 1 bar, corresponding to 88 to 94 J K-1 mol-1 of the entropy change. This has experimentally been found as Trouton's rule, which states that the entropy increase by vaporization is 80 to 110 J K-1 mol-1 for various materials, and later confirmed by modern molecular dynamics [41].Google Scholar
  43. [43]
    The translation entropy of gaseous ammonia is more than 200 J K-1 mol-1, based on the following calculation [41]: where mis the molecular weight [2.829 ??10-25 kg molecule-1 for ammonia, kis the Boltzmann constant [1.381 ??10-23 J K-1], his the Planck constant [6.626 ??10-34 J sec], Vmis the volume [m3] and N A is Avogadro's number [6.023 ??1023]. This can be simplified for ammonia under 1 bar pressure as 111.92 + 20.79 ln T(J K-1 mol-1), corresponding to 235 and 250 J K-1 mol-1 for 373 and 773 K, respectively. On the contrary, the rotation and vibration terms are usually less than a few ten joules per Kelvin per mole. For example, the entropy of deformation vibration of the adsorbed ammonium cation, which shows an IR absorption at 1460 cm-1, can be calculated as follows [41]: where x= h?vib/(kT), and ?vib is the frequency (= 4.377 ??1013 sec-1 in this case). The calculated value was only 0.2-2.1 J K-1 mol-1 at 373-773 K. For the physisorbed ammonia, the calculation gives 0.1-1.7 J K-1 mol-1 based on the 1620 cm-1 IR absorption. Although the chemical species is changed, the difference in the vibration entropies of the physisorbed ammonia and ammonium cation is less than 1 J K-1 mol-1.Google Scholar
  44. [44]
    L.C. Jozefowics, H.G. Karge and E.N. Coker, J. Phys. Chem. 98 (1994)8053.Google Scholar
  45. [45]
    D.J. Parrillo, C. Lee and R.J. Gorte, Appl. Catal., A: General. 110 (1994)6Google Scholar
  46. [46]
    J. Shen, R.D. Cortright, Y. Chen and J.A. Dumesic, J. Phys. Chem. 98(1994)8067.Google Scholar
  47. [47]
    N. Katada, S. Iijima, H. Igi and M. Niwa, Stud. Surf. Sci. Catal. 105(1996)1227.Google Scholar
  48. [48]
    H. Igi, N. Katada and M., Niwa, International Symposium on Zeolites and Microporous Crystals '97, Tokyo, 1997.Google Scholar
  49. [49]
    G. Bagnasco, J. Catal. 159(1996)249.Google Scholar
  50. [50]
    G.L. Woolery, G.H. Kuehl, H.C. Timken and A.W. Chester, in: Preprint of the 11th International Zeolite Conference, Seoul, 1996, RP61.Google Scholar
  51. [51]
    M. Sawa, E. Yamada, M. Niwa and Y. Murakami, Nippon Kagaku Kaishi (1989)504.Google Scholar
  52. [52]
    K. Tanabe, M. Ito and M. Sato, J. Chem. Soc., Chem. Commun. (1973)676.Google Scholar

Copyright information

© Kluwer Academic Publishers 1997

Authors and Affiliations

  • Miki Niwa
  • Naonobu Katada

There are no affiliations available

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