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Carbon adsorbents for methane storage: genesis, synthesis, porosity, adsorption

  • Catalysis, Reaction Engineering
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Abstract

Adsorbed natural gas (ANG) storage systems are based on nanoporous adsorbents with a tailored porous structure. Activated carbons are among the most promising and widely used candidates for this application, which is explained by the availability and abundance of raw material resources. In the present work, several series of activated carbons prepared from various precursors (coconut shell, peat, polymers, silicon carbide, and mineral coal) by different routes of physical and thermochemical activation were considered in the context of the adsorbed natural gas storage applications. Based on the Dubinin theory of volume filling of micropores and BET method, the porous structure of these adsorbents was evaluated from standard adsorption isotherms. The XRD, SAXS, and SEM measurements revealed variations in the textural and morphological properties of the adsorbents and their dependence on the precursor and synthesis procedure. The pore sizes evaluated from the adsorption and SAXS data were compared. Experimental data on methane adsorption at the temperature of 303 K and pressures of 0.1, 3.5, and 10 MPa made it possible to identify the most effective adsorbents. It was shown that the adsorption properties of ACs prepared from peat and mineral coal are determined by surface chemistry inherited from the precursor and activating agent. In contrast, the adsorption performance of ACs from polymer and coconut shell depends solely on the pore volume and pore dimensions. The adsorption effectiveness of each AC varies with pressure as a function of textural properties. Thus, a selection of an optimal adsorbent should be adjusted for thermodynamical coditions of ANG system.

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Abbreviations

A:

differential molar work of adsorption [kJ/mol]

a:

value of adsorption [mmol/g]

a0 :

limiting value of adsorption at the temperature T [K] [mmol/g]

E:

characteristic energy of gas adsorption [kJ/mol]

E0 :

characteristic energy of adsorption of standard vapor (benzene) [kJ/mol]

HCC :

distance between centers of carbon atoms of pore walls [nm]

HS :

average width of model slit-like micropores [nm]

I:

scattering intensity of x-rays at small angles [a.u.]

K:

coefficient of proportionality [dimensionless]

M:

molecular mass [g/mol]

m0 :

mass of regenerated adsorbent [g]

N:

total amount of gas introduced into the adsorption-measuring system [mmol]

n :

parameter in the Dubinin-Raduschkevich equation [dimensionless]

n:

exponent [dimensionless]

P:

pressure [Pa]

Pcr :

critical pressure [Pa]

P S :

pressureofsaturatedvapors[Pa]

PW :

maximal operational pressures of ANG system [Pa]

PX :

minimal residual pressure of methane in ANG system [Pa]

q:

scattering vector [nm−1]

R:

universal gas constant [J/(mol·K)]

RG :

radius of gyration of micropores [nm]

RGS :

radius of gyration of cross-section of a model cylindrical pore [nm]

RT :

radius of gyration of a model slit-like pore [nm]

r:

radius of a crystallite [nm]

SBET :

BET specific surface area [m2/g]

Sme :

specific surface area of mesopores [m2/g]

T:

temperature [K]

Tcr :

critical temperature [K]

T0 :

boiling point [K]

V:

total geometric volume of adsorption measuring system [cm3]

Vads :

volume of adsorbent with micropores [cm3]

VHe :

volume of adsorbent determined via helium pycnometry [cm3]

Wme :

specific mesopore volume [cm3/g]

W0 :

specific micropore volume [cm3/g]

Ws :

specific total pore volume [cm3/g]

x0 :

half-width of micropore [nm]

β :

coefficient of similarity for the gas under study [dimensionless]

γ :

ratio of crystallite radius to half-width of micropore [dimensionless]

δ gas :

density of gaseous phase [mmol/cm3]

θ :

angle of reflection (scattering) of X-rays in XRD (SAXS) [degrees]

λ :

wavelength of x-rays [nm]

λ Cu :

wavelength of monochromatic CuKα-radiation [nm]

ρ CH4 :

methane density in the slit-like pores with walls formed by graphene layers [g/cm3]

AC:

activated carbons

ANG:

adsorbed natural gas

EDX:

energy dispersive x-ray analysis

PVDC:

polyvinyl dichloride

PFR:

phenol-formaldehyde resin

SAXS:

small-angle x-ray scattering

SEC:

structural and energy characteristics

SEM:

scanning electron microscopy

TCA:

thermochemical activation

TD:

thermal decomposition

TVFM:

theory of volume filling of micropores

VGA:

vapor-gas activation

WVA:

water vapor activation

XRD:

x-ray diffraction

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Acknowledgements

The investigations were carried out with the use of equipment of the Center of Physical Methods of Investigations of the A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences.

Funding

The research was carried out within the State Assignment of the Russian Federation (Project No. 01201353185) and the plan of the RAS Scientific Council (Theme No. 20-03-460-01).

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Authors and Affiliations

  1. A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences (IPCE RAS), Leninskii Prospect, 31, Building 4, Moscow, 119071, Russia

    Ilya Men’shchikov, Andrey Shiryaev, Andrey Shkolin, Vladimir Vysotskii, Elena Khozina & Anatoly Fomkin

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  1. Ilya Men’shchikov
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Correspondence to Ilya Men’shchikov.

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Credit Author Statement

Ilya E. Men’shchikov: Conceptualization, Investigation; Visualization, Writing- Original draft preparation; Andrey A. Shiryaev: Methodology, Investigation; Writing — Review & Editing; Andrey V. Shkolin: Resources, Methodology, Investigation, Project administration; Vladimir V. Vysotskii: Investigation, Visualization; Elena V. Khozina: Writing-Original draft preparation, Writing-Reviewing and Editing; Anatoly A. Fomkin: Supervision, Project administration; Writing-Reviewing and Editing; Funding acquisition.

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Men’shchikov, I., Shiryaev, A., Shkolin, A. et al. Carbon adsorbents for methane storage: genesis, synthesis, porosity, adsorption. Korean J. Chem. Eng. 38, 276–291 (2021). https://doi.org/10.1007/s11814-020-0683-2

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