CO2 capture using physical adsorbents such as activated carbon, zeolites, and metal-organic frameworks (MOFs) have attracted a lot of attention because of the technical capability of adsorption technology using such separation agents to retrofit the energy demanding liquid amine scrubbing process. Nevertheless, this will be conceivable only if the separation agents (adsorbents) in question fulfil many unambiguous attributes in terms of porosity, CO2 affinity, kinetics, energetics, stability, throughout the right capture mechanism, in addition to the adsorbents cost.
In this paper we report recent study about the evaluation of physical adsorbents for CO2 capture from simulated flue gas.
Extensive CO2/N2:10/90 mixed gas adsorption at 298 and 328 K, in the presence of water vapor and other impurities, were carried out using both temperature and pressure swing regeneration modes. For comparison purpose, absorption in liquid amines and adsorption on 13X zeolites are considered as the reference technologies for post-combustion CO2 capture

Belmabkhout, Youssef

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesCO2 Summit II: Technologies and Opportunities ProceedingsSpring 4-13-2016Evaluation of physical adsorbents for post-combustion CO2 captureYoussef BelmabkhoutKAUST, youssef.belmabkhout@kaust.edu.sFollow this and additional works at: http://dc.engconfintl.org/co2_summit2Part of the Environmental Engineering CommonsThis Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusionin CO2 Summit II: Technologies and Opportunities by an authorized administrator of ECI Digital Archives. For more information, please contactfranco@bepress.com.Recommended CitationYoussef Belmabkhout, "Evaluation of physical adsorbents for post-combustion CO2 capture" in "CO2 Summit II: Technologies andOpportunities", Holly Krutka, Tri-State Generation & Transmission Association Inc. Frank Zhu, UOP/Honeywell Eds, ECISymposium Series, (2016). http://dc.engconfintl.org/co2_summit2/33Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTAdvanced Membranes & Porous Materials Center (AMPM) 1Low CO2 Concentration Capture Using Physical Adsorbents. Are Metal-Organic Frameworks Becoming the New Benchmark Materials?Youssef BelmabkhoutFunctional Materials Design, Discovery and Development (FMD3), Advanced membranes and porous materials (AMPM)King Abdullah University of Science and Technology KAUST (KSA) Nugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84 Shekhah, O, Belmabkhout, Y et al (2014) Nature Commun. DOI: 10.1038/ncomms5228CO2 Summit II: Technologi s and Opportunities 2016, Albuquerque - NM, Santa Ana Pueblo, USA, 13th April 2016King Abdullah University of Science and Technology Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST2LocationBeginning of construction in 2007Inside one of the buildingsPart of the campus and LibraryResearch structure/strategy at KAUSTFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST311 Research Centerso Advanced Membranes and Porous Materials Center (AMPMC)o Catalysis (KCC)o Clean Combustion (CCRC)o Computational Bioscience (CBRC)o Center for Desert Agriculture (CDA)o Extreme Computing Research Center (ECRC)o Red Sea Research Center (RSRC)o Solar and Photovoltaics Engineering Research Center (SPERC)o Upstream Petroleum Engineering Research Center (UPERC) ( Not yet inaugurated )o Visual Computing Center (VCC)o Water Desalination and Reuse (WDRC)3 academic Divisionso Biological and Environmental Science and Engineering Division (BESE)o Computer, Electrical and Mathematical Science and Engineering Division (CEMSE)o Physical Science and Engineering Division (PSE)Quest of innovative advanced materials in collaboration with Industry (Aramco) Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST4Synthesis of MaterialsEvaluation of porosity  at the small scale Evaluation of Separation Properties at the small scale Scale-up of Materials2nd stage evaluation at large scale  Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST5Motivation Energy Consumption by sectors in Saudi Arabia  Saudi Residential power demand splitFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST6Evolution of CO2 Emissions in the Middle East-Asia# 793.6 MTCO2 Source:  http://www.globalcarbonatlas.org/?q=en/emissionsFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST7# 22169 MTCO2 Source:  http://www.globalcarbonatlas.org/?q=en/emissionsEvolution of CO2 Emissions in the Middle East-AsiaFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST8# 9519 MTCO2 Source:  http://www.globalcarbonatlas.org/?q=en/emissionsEvolution of CO2 Emissions in the Middle East-AsiaFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST9Y.Belmabkhout et al. 2016, Chemical Engineering Journal 296, 386-397It is not about a specific material, it is about new concept of separation that lead to new generation of materials OutlineFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST Understanding of structural- CO2 adsorption properties relationships  push the limit of  gas separation with the lowest energy input using physical adsorbents  Conclusions from the past works (2012-2013)10 New finding.  ConclusionsVSA/VTSA ProcessesPurity of commodities (CH4, H2, … RecoverySelectivityGas uptake Quest for materials for membranes fabrication Shift to membrane technology. Structural/chemical properties and adsorption properties relationships   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST11o What is the key  properties of an adsorbent to be suitable for CO2 removal at different concentrations ?o Which mechanism ? CO2 separation/capture in our lifeFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTCO2 SeparationHealth and Safety Environment Pre-purification before air Separation (PPU) Alkaline Fuel Cells (AFC)Syngas treatment (H2purification) EnergyConfined space(Space shuttles) Confined space(submarine)Anesthesia Machine Stationary  Rebreather  Natural gas upgrading (CH4 purification) Air Capture  On-Board  From the source  Important CO2 removal applications at various concentrationsFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST13Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)Important CO2 removal applications at various concentrationsFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST14Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)CO2 Bulk separation CO2purificationLow concentration and traces CO2 removalImportant CO2 removal applications at various concentrations and adsorbents properties relationship   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST15Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)Alternative technologies • Chemical absorption• High pressure waterscrubbing• Cryogenic distillation • Activated Alumina• Activated carbons• Zeolites Alternative technologies • Chemical absorption• membrane • Activated carbons• Zeolites Alternative technologies • Chemical absorption• membranes• Zeolites • Amine supported silica• Zeolites • Amine supported materialsAlternative technologies • Zeolite A• Amine supported materialsAlternative technologies • Chemical absorption• membranes• Chemical absorption• LiOHImportant CO2 removal applications at various concentrations and adsorbents properties relationship   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST16Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)0.5 bar10 bar0.15 bar5 bar0.005 bar0.0004 barImportant CO2 removal applications at various concentrations and adsorbents properties relationship   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST17Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)30-45 kJ/mol45-60 kJ/mol60-100 kJ/molImportant CO2 removal applications at various concentrations and adsorbents properties relationship   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST18Biogas upgrading(50% CO2)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2removal in confined spaces (5000 ppm)Air Capture(400 ppm)Uniformity of energetic CO2 adsorption sites in porous materials Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST19UptakeHeat of adsorption Pore filling Air Capture(400 ppm)Syngas processing(30% CO2)Flue gas  treatment(15% CO2)NG upgrading(5% CO2)CO2 removal in confined spaces (5000 ppm)Biogas upgrading(50% CO2)Uniformity of energetic CO2 adsorption sites Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST20Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST21Tunable Rare-Earth fcu-MOFs Platform  Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTXue, D. –X. et. al. J. Am. Chem. Soc. 2013, 135, 7660-7667. 223D fcu MOFsLa Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu YEase of tune using various rare earth12-connected SBU2-connected SBUEase of tune using various ligandsPorosity and CO2 AdsorptionsFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTXue, D. –X. et. al. J. Am. Chem. Soc. 2013, 135, 7660-7667. 23Compound (Metal) 1 (Tb) 2 (Y) 3 (Tb) 4 (Tb) 5 (Y) 6 (Tb) 7 (Tb)LigandBET (m2 g-1) 1220 1310 904 2200 2410 1940 1854P.V. (cm3 g-1) 0.51 0.56 0.39 0.86 0.94 0.78 0.72CO2 Uptake (mmol g-1)7.53, 5.86 and 3.548.33, 6.46 and 4.125.96, 4.53 and 2.503.93, 2.75 and 1.644.01, 2.81 and 1.593.50, 2.40 and 1.373.91, 2.63 and 1.36Qst for CO2 (kJ mol-1) 58.1-25.0 46.1-24.0 46.6-23.8 36.7-20.3 27.2-19.5 39.1-18.5 41.6-20.7Traces and Low CO2 concentration removal. Column Breakthrough Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTXue, D. –X. et. al. J. Am. Chem. Soc. 2013, 135, 7660-7667. 24CO2/N2 (0.1/99.9%): ca. 1051Column breakthrough tests using CO2/N2: 0.1/99.9% mixtureConical pockets decorated with –F, -OH moieties and tetrazolate groups (proximal to Oms)Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST25SiF6 MOF PlatformNugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84 Functional Materials Design, Discovery and DevelopmentFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST26pyrazine/Zn  2-D periodic 44 square grids pillared by SiF6 anions Nugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84, Patent Pending  Functional Materials Design, Discovery and DevelopmentFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST27Nugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84, Patent Pending  Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTCO2/N2  and CO2/H2 separation using SIFSIX-3-Zn MOFs- Effect of humidity  CO2/N2 (flue gas)and CO2/H2 (syngas) mixtures adsorption - column breakthrough adsorption tests in humid conditions 28Nugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84, Patent Pending  29Functional Materials Design, Discovery and DevelopmentFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTColumn breakthrough test: CO2/N2: 10/90 mixture  Nugent, P, Belmabkhout, Y et al (2013) Nature 494 (7439) ,80-84, Patent Pending  What we have learned so far ?   Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST30o What is the key  properties of an adsorbent to be suitable for CO2 removal at different concentrations ?o Which mechanism ? Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST31Same concept with other materials    16 OCTOBER 2015 • VOL 350 ISSUE 6258Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST32Same concept with other materials    Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST33Recent finding (2014)edpyCuSiF6ipyrazineNNCuSiF6 ZnSiF6SIFSIX-2-Cu SIFSIX-3-Cu/Zn SIFSIX-2-Cu-iM-SIF6 pillarsSIFSIX based MOFsShekhah, O, Belmabkhout, Y et al (2013). Nature Commun  2014, 5, 4228.Functional Materials Design, Discovery and DevelopmentFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTSIFSIX-3-Cu MOFs. Interatomic distances in SIFSIX based MOFs.   Shekhah, O, Belmabkhout, Y et al (2013). Nature Commun  2014, 5, 4228. MOF dM-N (Å) dM-F1 (Å) DSi-F1 (Å) DSi-F2 (Å)† reference Ligand SIFSIX-1-Zn 2.157 2.082 1.757 1.600 38  2.131 2.122 1.720 1.650 39 SIFSIX-1-Cu 2.007 2.379 1.703 1.672 40 2.009 2.357 1.698 1.609 41 1.966 2.336 1.692 1.685 42 SIFSIX-2-Zn 2.125 2.069 1.698 1.668 39  SIFSIX-2-Cu 2.027 2.300 1.684 1.684 43 SIFSIX-2i-Cu 2.015 2.353 1.693 1.679 43 SIFSIX-3-Zn 2.172 2.057 1.747 1.657 44  SIFSIX-3-Cu 1.958 2.119 1.834 1.651 this work SIFSIX-2D-Cu 2.061* 2.402 1.727 1.688 44 SIFSIX-2D-H2O-Cu 2.031 2.412 1.695 1.675 42 SIFSIX-4-Zn 2.117 2.062 1.712 1.653 39  SIFSIX-5-Cu 2.012 2.258 1.727 1.681 40   1.901.952.002.052.102.152.20SIFSIX-1 SIFSIX-2 SIFSIX-3 SIFSIX-4 SIFSIX-5Cu Zn1.801.902.002.102.202.302.40SIFSIX-1 SIFSIX-2 SIFSIX-3 SIFSIX-4 SIFSIX-5Zn CuSIFSIX-1 SIFSIX-2 SIFSIX-3 SIFSIX-4 SIFSIX-5SIFSIX-1 SIFSIX-2 SIFSIX-3 SIFSIX-4 SIFSIX-5dM-N(Å)dM-F1(Å)The rational is based on conventional coordination chemistry  suggesting that replacement of Zn(II) by Cu(II) to form an iso-structural SIFSIX-3-Cu will potentially induce an additional pore contraction due to Jahn-Teller distortions of the octahedral coordination geometry of Cu(II), CuN4F2. Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTEnhanced charge density by slight pore contraction High charge density  + suitable pore size Enhanced charge density by pore contraction SIFSIX-3-MpyrazineNNSIFSIX-3 (Cu, Zn)Shekhah, O, Belmabkhout, Y et al (2013). Nature Commun 2014, 5, 4228, Patent Pending.SIFSIX-3-Cu 43 cm3 STP/gSr2+ SAPO-34 15 cm3 STP/gCa2+ LTA  (5A) 9 cm3 STP/gUptake at 1300 ppmCO2 separation/capture in our lifeFunctional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTCO2 SeparationHealth and Safety Environment Pre-purification before air Separation (PPU) Alkaline Fuel Cells (AFC)Syngas treatment (H2purification) EnergyConfined space(Space shuttles) Confined space(submarine)Anesthesia Machine Stationary  Rebreather  Natural gas upgrading (CH4 purification) Air Capture  On-Board  From the source  Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUST38Conclusion  o Because of the high degree of tunability of MOFs we confirmed the discovery of new separation concept involving the combination of thermodynamics and Kineticso In-depth understanding of what are crucial measures for physical adsorbents to be used in CO2 captureo Synergetic effect between the presence of uniform charge density and suitable pore size allow to unveil physical adsorbents with high selectivity and uptake for CO2 (similar to MEA) but with much Lower heat and temperature for regeneration.    o Porosity- Channel based adsorbents are more suitable for separation in general and CO2 in particular- Suitable pore size is critical for gas separation in CO2 capture in particular  - Surface area is not crucial parameter to develop materials for CO2 capture  Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTAcknowledgment39Functional Materials Design, Discovery and DevelopmentKing Abdullah University  ofScience and Technology KAUSTThank you 40

Evaluation of physical adsorbents for post-combustion CO2 capture

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Evaluation of physical adsorbents for post-combustion CO2 capture

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