Spanning the molecular to industrial scale of the adsorption-based separation of CO2/CH4 by MIL-160(Al)

Marta Bordonhos; Maria Inês Severino Neves; Afsaneh Marandi; Farid Nouar; Miguel Jorge; José R.B. Gomes; Christian Serre; Moisés L. Pinto

doi:10.1016/j.cej.2025.169276

Spanning the molecular to industrial scale of the adsorption-based separation of CO₂/CH₄ by MIL-160(Al)

Marta Bordonhos
, Maria Inês Severino Neves
, Afsaneh Marandi
, Farid Nouar
, Miguel Jorge
, José R.B. Gomes^*
, Christian Serre^*
, Moisés L. Pinto^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

18 Downloads (Pure)

Abstract

The microporous bioderived MIL-160(Al) MOF has been investigated for CO₂/CH₄ separation in the context of biogas upgrading, by complementary experimental and computational studies, from the molecular to the industrial process levels. MIL-160(Al) has been synthesised and shaped into beads using silica, without loss of adsorption performance, beyond the expected loss in adsorption capacity due to the presence of nonporous silica. Experimental and GCMC-simulated adsorption isotherms for pure CO₂ and CH₄ align closely, validating the strategies used. The latter have been extended to binary CO₂:CH₄ mixtures, with results cross-validated with IAST. A detailed model has been developed in Aspen Adsorption that uses the LDF approach to describe adsorption kinetics, and the Extended Virial isotherm for multicomponent equilibrium, achieving close agreement between simulation and experimental results. Industrial PSA/VPSA process simulations based on the classic 2-bed, 4-step Skarstrom cycle and the validated model have shown the VPSA process offers better CH₄ recovery (ca. 82 vs. 52 %) and similar unit energy consumption when compared to the PSA process (ca. 12 vs. 11 Wh · mol^-1_CH4,Prod), despite having higher raw energy requirements due to vacuum regeneration (ca. 92 vs. 33 kWh per cycle). Considering only electricity, a main operation cost factor, the operation cost for the VPSA process is ca. 98 €·t^-1_{Upgraded biogas}, which gives an estimated economic return of ca. 725 €·t^-1_{Upgraded biogas}, based on the price of natural gas. Consequently, VPSA emerges as a promising industrial-scale process for biogas upgrading with MIL-160(Al) as a promising new adsorbent.

Original language	English
Article number	169276
Number of pages	17
Journal	Chemical Engineering Journal
Volume	524
Early online date	14 Oct 2025
DOIs	https://doi.org/10.1016/j.cej.2025.169276
Publication status	Published - 15 Nov 2025

Funding

This research is being developed in the scope of the Projects FCT-UIDB/04028/2025 and FCT-UIDP/04028/2025 (CERENA) and UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020 (CICECO), and being financed by Portuguese funds through FCT/MCTES, and when applicable co-financed by ERDF under the PT2020 Partnership Agreement. MB acknowledges FCT for the PhD Grant Ref. SFRH/BD/147239/2019, and the computer resources and technical support provided by EPCC, under the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme.

Keywords

MIL-160
CO2 capture
biogas upgrading
adsorption
breakthrough
molecular modelling
process simulation

Access to Document

10.1016/j.cej.2025.169276Licence: CC BY 4.0

Bordonhos-etal-CEJ-2025-Spanning-the-molecular-to-industrial-scale-of-the-adsorption-based-separationFinal published version, 4.47 MBLicence: CC BY 4.0

Cite this

@article{4056d521a2864fa3bae6e4a847c6004f,

title = "Spanning the molecular to industrial scale of the adsorption-based separation of CO2/CH4 by MIL-160(Al)",

abstract = "The microporous bioderived MIL-160(Al) MOF has been investigated for CO₂/CH₄ separation in the context of biogas upgrading, by complementary experimental and computational studies, from the molecular to the industrial process levels. MIL-160(Al) has been synthesised and shaped into beads using silica, without loss of adsorption performance, beyond the expected loss in adsorption capacity due to the presence of nonporous silica. Experimental and GCMC-simulated adsorption isotherms for pure CO2 and CH4 align closely, validating the strategies used. The latter have been extended to binary CO2:CH4 mixtures, with results cross-validated with IAST. A detailed model has been developed in Aspen Adsorption that uses the LDF approach to describe adsorption kinetics, and the Extended Virial isotherm for multicomponent equilibrium, achieving close agreement between simulation and experimental results. Industrial PSA/VPSA process simulations based on the classic 2-bed, 4-step Skarstrom cycle and the validated model have shown the VPSA process offers better CH4 recovery (ca. 82 vs. 52 \%) and similar unit energy consumption when compared to the PSA process (ca. 12 vs. 11 Wh · mol-1CH4,Prod), despite having higher raw energy requirements due to vacuum regeneration (ca. 92 vs. 33 kWh per cycle). Considering only electricity, a main operation cost factor, the operation cost for the VPSA process is ca. 98 €·t-1Upgraded biogas, which gives an estimated economic return of ca. 725 €·t-1Upgraded biogas, based on the price of natural gas. Consequently, VPSA emerges as a promising industrial-scale process for biogas upgrading with MIL-160(Al) as a promising new adsorbent.",

keywords = "MIL-160, CO2 capture, biogas upgrading, adsorption, breakthrough, molecular modelling, process simulation",

author = "Marta Bordonhos and Neves, \{Maria In{\^e}s Severino\} and Afsaneh Marandi and Farid Nouar and Miguel Jorge and Gomes, \{Jos{\'e} R.B.\} and Christian Serre and Pinto, \{Mois{\'e}s L.\}",

year = "2025",

month = nov,

day = "15",

doi = "10.1016/j.cej.2025.169276",

language = "English",

volume = "524",

journal = "Chemical Engineering Journal",

issn = "1385-8947",

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TY - JOUR

T1 - Spanning the molecular to industrial scale of the adsorption-based separation of CO2/CH4 by MIL-160(Al)

AU - Bordonhos, Marta

AU - Neves, Maria Inês Severino

AU - Marandi, Afsaneh

AU - Nouar, Farid

AU - Jorge, Miguel

AU - Gomes, José R.B.

AU - Serre, Christian

AU - Pinto, Moisés L.

PY - 2025/11/15

Y1 - 2025/11/15

N2 - The microporous bioderived MIL-160(Al) MOF has been investigated for CO₂/CH₄ separation in the context of biogas upgrading, by complementary experimental and computational studies, from the molecular to the industrial process levels. MIL-160(Al) has been synthesised and shaped into beads using silica, without loss of adsorption performance, beyond the expected loss in adsorption capacity due to the presence of nonporous silica. Experimental and GCMC-simulated adsorption isotherms for pure CO2 and CH4 align closely, validating the strategies used. The latter have been extended to binary CO2:CH4 mixtures, with results cross-validated with IAST. A detailed model has been developed in Aspen Adsorption that uses the LDF approach to describe adsorption kinetics, and the Extended Virial isotherm for multicomponent equilibrium, achieving close agreement between simulation and experimental results. Industrial PSA/VPSA process simulations based on the classic 2-bed, 4-step Skarstrom cycle and the validated model have shown the VPSA process offers better CH4 recovery (ca. 82 vs. 52 %) and similar unit energy consumption when compared to the PSA process (ca. 12 vs. 11 Wh · mol-1CH4,Prod), despite having higher raw energy requirements due to vacuum regeneration (ca. 92 vs. 33 kWh per cycle). Considering only electricity, a main operation cost factor, the operation cost for the VPSA process is ca. 98 €·t-1Upgraded biogas, which gives an estimated economic return of ca. 725 €·t-1Upgraded biogas, based on the price of natural gas. Consequently, VPSA emerges as a promising industrial-scale process for biogas upgrading with MIL-160(Al) as a promising new adsorbent.

AB - The microporous bioderived MIL-160(Al) MOF has been investigated for CO₂/CH₄ separation in the context of biogas upgrading, by complementary experimental and computational studies, from the molecular to the industrial process levels. MIL-160(Al) has been synthesised and shaped into beads using silica, without loss of adsorption performance, beyond the expected loss in adsorption capacity due to the presence of nonporous silica. Experimental and GCMC-simulated adsorption isotherms for pure CO2 and CH4 align closely, validating the strategies used. The latter have been extended to binary CO2:CH4 mixtures, with results cross-validated with IAST. A detailed model has been developed in Aspen Adsorption that uses the LDF approach to describe adsorption kinetics, and the Extended Virial isotherm for multicomponent equilibrium, achieving close agreement between simulation and experimental results. Industrial PSA/VPSA process simulations based on the classic 2-bed, 4-step Skarstrom cycle and the validated model have shown the VPSA process offers better CH4 recovery (ca. 82 vs. 52 %) and similar unit energy consumption when compared to the PSA process (ca. 12 vs. 11 Wh · mol-1CH4,Prod), despite having higher raw energy requirements due to vacuum regeneration (ca. 92 vs. 33 kWh per cycle). Considering only electricity, a main operation cost factor, the operation cost for the VPSA process is ca. 98 €·t-1Upgraded biogas, which gives an estimated economic return of ca. 725 €·t-1Upgraded biogas, based on the price of natural gas. Consequently, VPSA emerges as a promising industrial-scale process for biogas upgrading with MIL-160(Al) as a promising new adsorbent.

KW - MIL-160

KW - CO2 capture

KW - biogas upgrading

KW - adsorption

KW - breakthrough

KW - molecular modelling

KW - process simulation

U2 - 10.1016/j.cej.2025.169276

DO - 10.1016/j.cej.2025.169276

M3 - Article

SN - 1385-8947

VL - 524

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

M1 - 169276

ER -