skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

Abstract

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2/g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278 K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2, N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2/N 2 and CO 2/CH 4 was calculated based onmore » the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2/N 2 and CO 2/CH 4. The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.« less

Authors:
 [1];  [1];  [2];  [2]
  1. Widener Univ., Chester, PA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1394439
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Microporous and Mesoporous Materials
Additional Journal Information:
Journal Volume: 241; Journal Issue: C; Journal ID: ISSN 1387-1811
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Saha, Dipendu, Orkoulas, Gerassimos, Chen, Jihua, and Hensley, Dale K. Adsorptive separation of CO2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation. United States: N. p., 2017. Web. doi:10.1016/j.micromeso.2016.12.015.
Saha, Dipendu, Orkoulas, Gerassimos, Chen, Jihua, & Hensley, Dale K. Adsorptive separation of CO2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation. United States. doi:10.1016/j.micromeso.2016.12.015.
Saha, Dipendu, Orkoulas, Gerassimos, Chen, Jihua, and Hensley, Dale K. Wed . "Adsorptive separation of CO2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation". United States. doi:10.1016/j.micromeso.2016.12.015. https://www.osti.gov/servlets/purl/1394439.
@article{osti_1394439,
title = {Adsorptive separation of CO2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation},
author = {Saha, Dipendu and Orkoulas, Gerassimos and Chen, Jihua and Hensley, Dale K.},
abstractNote = {In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m2/g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278 K and pressures up to 760 torr. The gravimetric CO2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO2 in low uptake was 60-65 kJ/mol, which is the highest for CO2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO2, N2 and CH4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO2/N2 and CO2/CH4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO2/N2 and CO2/CH4. The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO2 separation.},
doi = {10.1016/j.micromeso.2016.12.015},
journal = {Microporous and Mesoporous Materials},
number = C,
volume = 241,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9works
Citation information provided by
Web of Science

Save / Share:
  • In this study, N-doping nanoporous carbons (NNCs) were prepared from polypyrrole (PPY) by ZnCl{sub 2} activation. The activation process was carried out under set conditions (PPY/ZnCl{sub 2}=1/4) at 300–800 °C for 2 h. With increasing activation temperature, the specific surface area and total pore volume of the NNCs increased significantly from 539 m{sup 2}/g (300 °C) to 1268 m{sup 2}/g (700 °C) and from 0.245 cm{sup 3}/g (300 °C) to 0.561 cm{sup 3}/g (700 °C), respectively. In addition, the use of PPY carbon precursors allowed the integration of high N content (9.28 wt%) and resulted in a large narrow microporemore » distribution (<1 nm) in the prepared NNCs. The CO{sub 2} adsorption isotherms showed that PZ-600 exhibited the best CO{sub 2} adsorption capacity of 167 mg/g at 1 bar and 25 °C when the activation temperature was 600 °C. - Graphical abstract: CO{sub 2}/298 K adsorption/desorption isotherms of the N-enriched porous carbons. - Highlights: • N-doping nanoporous carbons were prepared from polypyrrole by ZnCl{sub 2} activation. • Through ZnCl{sub 2} activation, the specific surface area and total pore volume increased. • PZ-600 exhibited the best CO{sub 2} adsorption capacity of 167 mg/g at 1 bar and 25 °C.« less
  • Postcombustion CO 2 capture has become a key component of greenhouse-gas reduction as anthropogenic emissions continue to impact the environment. In this paper, we report a one-step synthesis of porous carbon materials using a series of task-specific ionic liquids for the adsorption of CO 2. By varying the structure of the ionic liquid precursor, we were able to control pore architecture and surface functional groups of the carbon materials in this one-step synthesis process leading to adsorbents with high CO 2 sorption capacities (up to 4.067 mmol g -1) at 0 °C and 1 bar. Finally, added nitrogen functional groupsmore » led to high CO 2/N 2 adsorption-selectivity values ranging from 20 to 37 whereas simultaneously the interaction energy was enhanced relative to carbon materials with no added nitrogen.« less
  • Pitch is considered a promising low-cost carbon precursor. However, when pitch is pyrolyzed, it forms polycrystalline graphite, which is non-porous, and therefore, not useful for CO{sub 2} adsorption. In this work, pitch was chemically activated to obtain a large specific surface area and micropore volume. Varying weight ratios of KOH (i.e., 0, 1, 2, and 3) were used as the activating agent. The characteristics of the samples were investigated using scanning electron microscopy (SEM), N{sub 2}/77 K adsorption isotherms, and X-ray diffraction (XRD). The CO{sub 2} adsorption performance was studied by isothermal adsorption/desorption measurements. The results showed that an increasemore » in specific surface areas and total pore volumes of pitch-based nanoporous carbons, resulted in an enhancement of CO{sub 2} adsorption capacity. - Graphical abstract: This is the surface morphologies of pitch precursor and pitch-derived activated carbon (AC-2). - Highlights: • Pitch is considered a promising low-cost carbon precursor. • Specific surface area: 1442 m{sup 2}/g and micropore volume: 0.504 cm{sup 3}/g. • CO{sub 2} adsorption capacity showed 203 mg/g (@ RT/1 bar)« less
  • One-step carbonization to synthesize nitrogen-doped meso-macroporous graphene as a highly efficient adsorbent for CO 2capture.