Kinetic model of the temperature-programmed desorption of ammonia to study the acidity of heterogeneous catalysts

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Abstract

A new method for processing the results of the temperature-programmed desorption (TPD) of ammonia from heterogeneous catalyst surfaces and an approach for automatic deconvolution of TPD kinetic curves are proposed. This method uses the Polanyi-Wigner kinetic model with formal kinetics approaches for simple reactions, which imposes restrictions on the observed orders of 1, 2, or 3. The parameters of TPD curves are selected based on the inverse simulation using the Runge-Kutta method and fitting them to experimental points using dynamic model parameters changes. As an example, several heterogeneous catalysts are presented in this work. TPD-NH3 of titanium silicalite-1 and silicalite-1 is obtained using one third-order desorption kinetic equation. TPD-NH3 of the three samples of γ-alumina is obtained using two desorption peaks with similar kinetic parameters.

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About the authors

A. I. Lysikov

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Author for correspondence.
Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

V. A. Vdovichenko

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

E. E. Vorob’eva

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

I. A. Shamanaeva

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

E. V. Luzina

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

L. V. Piryutko

Boreskov Institute of Catalysis SB RAS (IC SB RAS)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090

Zh. V. Veselovskaya

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

E. V. Parkhomchuk

Boreskov Institute of Catalysis SB RAS (IC SB RAS); Novosibirsk State University (NSU)

Email: lyanig@catalysis.ru
Russian Federation, Novosibirsk, 630090; Novosibirsk, 630090

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Supplementary files

Supplementary Files
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2. Fig. 1. Evaluation of the Gibbs potential change for the process of reversible desorption of ammonia from low-temperature aluminum oxide centers in comparison with the threshold of the reaction reversibility [18].

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3. Fig. 2. Diffractograms of the studied samples: silicalite-1 (Sil-1) (a) and aluminum oxide (Yar-800) (b). Comparison data (blue) are taken from COD for structural type MFI zeolite and ICDD PDF-2 for γ-Al2O3.

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4. Fig. 3. Ammonia TPD curves of the studied samples.

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5. Fig. 4. Effect of different parameters of the kinetic equation on the general appearance of the kinetic curve: observed order (a); pre-exponential multiplier (reduced frequency along the desorption coordinate) (b); desorption activation energy (c); integral acidity (d).

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6. Fig. 5. Initialization of parameters from the database, where the section of kinetic curves that best fits the maximum desorption rate is selected (a), and afterwards the curve with the highest coefficient of determination (blue line) is chosen (b).

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7. Fig. 6. Initialization of kinetic parameters for the Yar-800 aluminum γ-oxide TPD curve, fitting of the parameters of the first curve from the database with verification of model convergence (a) and addition of an additional kinetic curve due to low R2 value after fitting the first curve (b).

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8. Fig. 7. Block diagram of the algorithm for parameter selection of the kinetic model of NH3 TPD.

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9. Fig. 8. Ammonia TPD curves for samples ZD-07031 (a) and Sil-1 (b) with deconvolution via the proposed kinetic model.

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10. Fig. 9. Ammonia TPD curves of samples A1 (a), Yar-700 (b) and Yar-800 (c) with deconvolution via the proposed kinetic model.

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11. Fig. 10. Peculiarities of surface diffusion of ammonia molecules and their desorption from Lewis (a, b) and Brensted (c, d) acid centers.

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12. Supplementary
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