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Pure and mixture adsorption equilibria of methane and nitrogen onto clinoptilolite: effects of Cs+ and Fe3+ exchanged cations on separation performance

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Abstract

Cation exchanged clinoptilolite has emerged as an adsorbent that may be used for the treatment of natural gas type mixtures containing excess amounts of nitrogen. In this study, natural clinoptilolite was modified through Fe3+ and Cs+ cation exchange. The resultant mineral phase and elemental composition were verified and the extra framework cation type, charge, and distribution is shown to have a profound effect on the observed adsorptive properties. Single gas adsorption isotherms were conducted at 15 °C and/or 30 °C for CH4 and N2 using a microgravimetric adsorption analyser, and the ideal equimolar CH4/N2 selectivity values were determined for the natural and modified clinoptilolites. Natural clinoptilolite presents selectivity values close to 1. However, we demonstrate that clinoptilolite cation-exchanged with Cs+ and Fe3+ cations is rendered preferentially adsorptive for CH4 over N2 with a higher CH4/N2 selectivity than many adsorbents reported in the literature. The experimental CH4–N2 binary adsorption behavior was evaluated for the first time on raw clinoptilolite and was compared to the modified clinoptilolites with Cs+ and Fe3+ exchanged cations using the concentration pulse chromatographic technique. The experimental binary isotherms showed non-ideal behavior with competitive adsorption between CH4 and N2. In most cases, the theoretical models could not adequately describe the experimental adsorption behavior. Within the temperature range studied of 15 °C and 30 °C, the binary CH4/N2 separation factors range from 2.7 to 5.3, and 3.9 to 7.3 for Cs+ and Fe3+ exchanged clinoptilolite, respectively. These results are comparable or better than those found in literature for activated carbon which typically ranges from 2.1 to 5.5 and may serve as an alternative adsorbent for this type of separation which warrants further investigation.

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Abbreviations

ATR:

Attenuated total reflection

CPM:

Concentration pulse method

DS:

Dual site (Langmuir model)

DSL:

Dual site Langmuir

EDS:

Electron dispersive spectroscopy

ELM:

Extended Langmuir model

ETS-4:

Engelhard titanosilicate 4

FH-VSM:

Flory–Huggins vacancy solution model

FT-IR:

Fourier transform infra-red

GSE:

Gibbs surface excess

IAST:

Ideal adsorbed solution theory

LHS:

Left hand side (applies to Eq. 42)

PSA:

Pressure swing adsorption

RHS:

Right hand side (applies to Eq. 42)

sccm:

Standard cubic centimeters per minute at 1 atm total pressure and 0 °C

SEM:

Scanning electron microscopy

SSR:

Sum of square residuals

TCD:

Thermal conductivity detector

VSM:

Vacancy solution model

VV-CPM:

Van der Vlist and Van der Meijden—concentration pulse method

XRD:

X-ray diffraction

A 0, A 1, A 2, A 3 :

Parameters used for the MVV-CPM fit in Eq. 31

B 0, B 1, B 2 :

Parameters used for MVV-CPM fit describing the slope functions of the binary adsorption isotherms

b :

Equilibrium constant parameter (atm−1)

C 0, C 1, C 2 :

Parameters used for MVV-CPM fit describing the slope functions of the binary adsorption isotherms

c :

Adsorbate concentration at the outlet of the column (expressed as mV)

K :

Dimensionless Henry’s law constant

K p :

Dimensional Henry’s law constant (mmol g−1 atm−1)

L :

Length of column (m)

n :

Dimensionless Sips isotherm model parameter

P :

Pressure (atm)

P 0 :

Equilibrium vapor pressure of a pure component at the same temperature and spreading pressure as the adsorbed hypothetical mixture (atm)

q ∞ :

Limiting (maximum) amount adsorbed (mmol g−1)

q :

Amount adsorbed (mmol g−1)

q 0 :

Pure gas adsorption capacity (mmol g−1)

R :

Universal gas constant (atm m3mol−1 K−1)

t :

Time (s)

T :

Absolute temperature (K)

ν:

Interstitial fluid velocity (cm·s−1)

x i :

Mole fraction of component i in the adsorbed phase

\(X_{i}^{s}\) :

Mole fraction of component i in the solution representing the adsorbed phase predicted using the FH-VSM

y i :

Mole fraction of component i in the gas phase

Y i :

Mole fraction of component i in the gas phase predicted using the FH-VSM

0:

Pure component for IAST

∞:

Limiting (maximum) value

S :

Component in solution for FH-VSM

1:

Component 1

2:

Component 2

1/2:

Subscript used for expressing selectivity of component 1 over component 2

calc.:

Calculated

exp:

Experimental

i :

Component i

j :

Component j

m :

Maximum

t :

Total

v :

Vacancy

α1/2 :

Binary adsorption separation factor for component 1 over component 2

αo 1/2 :

Ideal adsorption selectivity for component 1 over component 2

αij :

Empirical constant of FH-VSM describing non-idealities cause by interactions of species i and j

ε:

Bed porosity

µ:

Mean retention time (s)

µD :

System dead time (s)

π:

Spreading pressure (atm)

\(\gamma _{1}^{s}\) :

Activity coefficient of component 1 in the surface phase for FH-VSM

\(\gamma _{2}^{s}\) :

Activity coefficient of component 2 in the surface phase

\(\gamma _{v}^{s}\) :

Activity coefficient of the vacancy in the surface phase

ρP :

Adsorbent density without the void space (kg/m3)

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Acknowledgements

Authors would like to acknowledge the financial support received from NSERC (Natural Sciences and Engineering Research Council) of Canada.

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  1. Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur, Ottawa, ON, K1N 6N5, Canada

    Dean A. Kennedy, Maja Mujčin, Tatum Alenko & F. Handan Tezel

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  1. Dean A. Kennedy
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Kennedy, D.A., Mujčin, M., Alenko, T. et al. Pure and mixture adsorption equilibria of methane and nitrogen onto clinoptilolite: effects of Cs+ and Fe3+ exchanged cations on separation performance. Adsorption 25, 135–158 (2019). https://doi.org/10.1007/s10450-018-0001-z

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