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Adsorption and diffusion of nitrogen, methane and carbon dioxide in aluminophosphate molecular sieve AlPO4-11

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Abstract

The knowledge about the adsorption and diffusion properties (specially about diffusion) of aluminophosphate molecular sieves is very scarce in the literature. These materials offer interesting properties as adsorbents as they have a polar framework and do not contain charge-balancing cations. In this work, the adsorption isotherms of nitrogen, methane and carbon dioxide over an AlPO4-11 sample synthesized in our laboratories have been measured with a volumetric method at 25, 35, 50 and 65 °C over a pressure range up to 110 kPa. The adsorption capacities of each gas are determined by the strength of interaction with the pore surface (carbon dioxide > methane > nitrogen). The equilibrium selectivity to carbon dioxide is quite high with respect to other adsorbents without cations due to the polarity of the aluminophosphate framework. The adsorption Henry’s law constants and diffusion time constants of nitrogen, methane and carbon dioxide in the synthesized AlPO4-11 material have been measured from pulse experiments. A pressure swing adsorption (PSA) process for recovering methane from a carbon dioxide/methane mixture (resembling biogas) has been designed using a dynamic model where the measured adsorption equilibrium and kinetic information has been incorporated. The simulation results show that the proposed process could be simpler than other PSA processes for biogas upgrading based on cation-containing molecular sieves such as 13X zeolite, as it can treat the biogas at atmospheric pressure, and it requires a lower pressure ratio, to produce high purity methane with high recovery.

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Abbreviations

b :

Adsorption affinity (Pa−1)

b 0 :

Pre exponential constant (Eq. 1) (Pa−1)

c :

Adsorptive concentration in the gas phase (mol m−3)

C :

Total gas concentration (mol m−3)

c p,g :

Gas heat capacity at constant pressure (J mol−1 K−1)

c p,s :

Adsorbent heat capacity (J kg−1 K−1)

c v,g :

Gas heat capacity at constant volume (J mol−1 K−1)

D c :

Intracrystalline diffusivity (m2 s−1)

D L :

Axial dispersion coefficient (m2 s−1)

D m :

Molecular diffusivity (m2 s−1)

f pulse :

Function defined in Eq. (13)

h ext :

Wall to air heat transfer coefficient (W m−2 K−1)

h w :

Gas to wall heat transfer coefficient (W m−2 K−1)

K c :

Dimensionless Henry’s law constant

k f :

External mass transfer coefficient (m s−1)

k macro :

Combined mass transfer coefficient in the external film and the macropores (m s−1)

k s :

LDF mass transfer coefficient (s−1)

L :

Bed length (m)

l :

Wall thickness (m)

n :

Adsorbed concentration (mol kg−1)

n max :

Maximal adsorbed concentration (mol kg−1)

p :

Adsorptive pressure (Pa)

P :

Pressure (Pa)

q :

Adsorbed concentration (mol m−3)

Q :

Volumetric flow rate (m3 s−1)

R :

Gas constant (J mol−1 K−1)

r c :

Half diffusion length in the spherulites (m)

r 2 :

Coefficient of determination

Re :

Particle Reynolds number

R l :

Bed radius (m)

R p :

Size of the adsorbent particle (m)

S bed :

Bed cross-section (m2)

Sc :

Schmidt number

T :

Temperature (K)

t :

Time (s)

T w :

Wall temperature (K)

u :

Superficial velocity (m s−1)

v 0 :

Interstitial velocity (m s−1)

V D :

Plug-flow volume (m3)

V T :

Tank volume (m3)

x :

Dimensionless axial coordinate

x r :

Dimensionless radial coordinate

z :

Axial coordinate (m)

−∆H ads :

Adsorption enthalpy (J mol−1)

y :

Mole fraction in the gas phase

ε :

Bed voidage fraction between adsorbent particles

ε macro :

Pellet macroporosity

ε p :

Particle porosity

λ :

Axial heat dispersion coefficient (W m−1 K−1)

μ :

First moment of the pulse response, gas viscosity (Pa s)

ρ c :

Crystal density (kg m−3)

ρ g :

Gas density (kg m−3)

ρ p :

Particle density (kg m−3)

τ :

Tortuosity

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Authors and Affiliations

  1. Department of Chemical Engineering, Universidad Complutense de Madrid, 28040, Madrid, Spain

    J. A. Delgado, V. I. Águeda, M. A. Uguina, J. L. Sotelo & Paz Fernández

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  1. J. A. Delgado
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  2. V. I. Águeda
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  3. M. A. Uguina
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  4. J. L. Sotelo
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  5. Paz Fernández
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Correspondence to J. A. Delgado.

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Delgado, J.A., Águeda, V.I., Uguina, M.A. et al. Adsorption and diffusion of nitrogen, methane and carbon dioxide in aluminophosphate molecular sieve AlPO4-11. Adsorption 19, 407–422 (2013). https://doi.org/10.1007/s10450-012-9463-6

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