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Water adsorption in fresh and thermally aged zeolites: equilibrium and kinetics

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Abstract

Zeolites are widely employed in the industrial drying of gases by Temperature Swing Adsorption (TSA). In a typical TSA process, the adsorbent is packed in a fixed bed, which is sequentially subjected to a “cold” feed (adsorption) and a hot flush (desorption). Due to the hydrothermal stress, adsorbents may suffer from reduced drying capacity in long-term service. The aim of this work is to assess the impact of thermal aging of two zeolite materials (LTA and CHA) having similar pore openings but different Si/Al ratios. We examined how simulated thermal aging affected porous texture, coke deposition and water vapor adsorption equilibrium and kinetics. Both zeolites showed reduced uptake of probe molecules (N2 at 77 K and CO2 at 273 K) and water vapor (303 K) when subjected to simulated thermal aging. In Fourier-Transform Infrared Spectroscopy (FTIR) analyses, only the aged LTA zeolite showed bands related to the presence of aromatic compounds. Water vapor adsorption uptake decreased 28.6% and 18.4% for LTA and CHA at 30 mbar, respectively. Kinetic studies indicate a reduction in water diffusion coefficient after the aging cycles. Although LTA has a significantly higher affinity for water as compared to CHA, the latter is much more resistant to hydrothermal aging with comparatively faster water diffusion.

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Abbreviations

a :

Conglomerate external surface area per unit volume (m−1)

\(C_{ps}\) :

Solid specific heat capacity (J kg−1 K−1)

\(C_{pw}\) :

Water specific heat capacity (J kg−1 K−1)

\(\overline{{C_{p} }}\) :

Specific heat capacity average (J kg−1 K−1)

\(D_{\mu }\) :

Diffusion coefficient (m2 s−1)

\(D_{\mu }^{0}\) :

Corrected diffusion coefficient (m2 s−1)

\(D_{\mu , b}^{0}\) :

Diffusion coefficient in a reference temperature (m2 s−1)

\(\Delta H_{ads}\) :

Adsorption enthalpy (J mol−1)

\(\Delta t\) :

Time interval to achieve the final pressure (s)

\(E_{a}\) :

Adsorption activation energy (J mol−1 K−1)

\(h_{f}\) :

Heat transfer coefficient (W m−2 K−1)

P:

Pressure (Pa)

\(P_{b}\) :

Phase bulk pressure (Pa)

\(P_{bi}\) :

Phase bulk initial pressure (Pa)

\(P_{f}\) :

Final pressure (Pa)

\(P_{i}\) :

Initial pressure (Pa)

q:

Adsorbed amount (mol kg−1)

\(q_{s}\) :

Maximum adsorbed amount (mol kg−1)

\(\overline{q}\) :

Volumetric average adsorbed amount (mol kg−1)

r:

Radial coordinate (m)

R:

Particle radius (m)

\(R_{IG}\) :

Universal gas constant (J mol−1 K−1)

\(\rho_{s}\) :

Solid specific volume (kg m−3)

t:

Time (s)

T:

Temperature (K)

\(T_{b}\) :

Phase bulk temperature (K)

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Acknowledgements

The authors acknowledged the financial support from PETROBRAS and the ANP (Agência Nacional de Petróleo, Gás Natural e Biocombustíveis – ANP, Brasil) through the Clause of Investments in Research, Development and Innovation in contracts for Exploration, Development and Production of Petroleum and Natural Gas. They also thank CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) process 402561/2007-4, Notice MCY/CNPq nº10/2007 for XRD analyses and LEVM (Laboratório de Microscopia Vibracional) for the FTIR analyses.

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Authors and Affiliations

  1. GPSA, Chemical Engineering Department, Universidade Federal do Ceará, Campus do Pici, bl. 731, Fortaleza, Ceará, 60760-400, Brazil

    Beatriz O. Nascimento, Bianca F. dos Santos, Débora A. S. Maia, Enrique Vilarrasa-Garcia, Antônio Eurico B. Torres, Moisés Bastos-Neto & Diana C. S. Azevedo

  2. PETROBRAS/CENPES, Rio de Janeiro, RJ, 21941-915, Brazil

    Darley C. de Melo

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  1. Beatriz O. Nascimento
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Correspondence to Diana C. S. Azevedo.

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Nascimento, B.O., dos Santos, B.F., Maia, D.A.S. et al. Water adsorption in fresh and thermally aged zeolites: equilibrium and kinetics. Adsorption 27, 1043–1053 (2021). https://doi.org/10.1007/s10450-021-00331-x

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