Porous systems for high performance CO 2 capture: The MATESA selective CO 2 capture materials

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Porous systems for high performance CO 2 capture: The MATESA selective CO 2 capture materials Alessio Masala Ph.D. student Prof. Silvia Bordiga Supervisor MATESA Dissemination Day, Jun. 16 th, 2016, OSLO, NORWAY 1

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 2

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 3

The adsorbers of MATESA TARGET: Performing CO2 adsorbers for Electric Swing Adsorption (ESA) REFERENCE ADSORBENTS (Selective CO2 capture adsorbent) 13-X zeolite NH4-ZSM5 zeolite Commercial materials ADVANCED ADSORBENTS (Selective CO2 capture adsorbent) CPO-27-Ni MOF UTSA-16 MOF Laboratory materials BIO CARBONS REAL PROCESS ADSORBERS Active phase + Static characterization of physical-chemical properties Conductive phase Dynamic characterization of physical-chemical properties Alessio Masala, MATESA Dissemination Day, Jun. 16th, 2016, OSLO, NORWAY 4

The adsorbers of MATESA Under the supervision of Prof. Alan Chaffee TARGET Synthesis and grafting of UTSA-16 over different types of carbonaceous supports 5

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 6

Characterization of the material SURFACE AREA P-XRD 5000 m 2 g -1 2000 800 100 20 N 2 @77 K adsorption TEM + EDX TGA Solid-State NMR IR SPECTROSCOPY+ PROBE MOLECULES Alessio Masala, MATESA Dissemination Day, Jun. 16 th, 2016, OSLO, NORWAY Heat Capacity 7

Characterization of the material Transmission Electron Microscopy + EDX analysis: Morphology and composition ZSM-5 UTSA-16 MOF P-XRD Intensity ZSM-5 UTSA-16 2θ ( ) Reference Adsorber Advanced Adsorber Surface Area and Total Volume of Pores Parallel study on CPO-27-Ni UTSA-16 CPO-27-Ni ZSM-5 13-X Surface Area (m 2 g -1 ) 814 1246 467 791 Total Volume of Pores (cm 3 g -1 ) 0.3 0.5 0.2 0.3 8

Characterization of the material Thermogravimetric analysis ZSM-5 UTSA-16 MOF Specific heat capacity Thermal stability of advanced adsorbers till 350 C Temperature ( C) Heat Capacity (J C -1 g -1 ) UTSA-16 60 1.0 CPO-27-Ni 60 1.2 ZSM-5 60 0.8 Cp of water: 4.18 J C -1 g -1 9

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 10

Adsorption of CO 2 STATIC adsorption isotherms of CO 2 ZSM-5 UTSA-16 The adsorption of CO 2 has been studied at relevant temperature and pressures 11

Adsorption of CO 2, N 2 and O 2 STATIC adsorption isotherms of CO 2,N 2 and O 2 ZSM-5 UTSA-16 60 C 60 C Adsorption at CO 2 partial pressure of 0.15 bar CO 2 uptake (mol kg -1 ) N 2 uptake (mol kg -1 ) O 2 uptake (mol kg -1 ) ZSM-5 0.33 0.08 0.02 UTSA-16 0.92 0.08 0.003 12

Adsorption of CO 2, N 2 and O 2 Strength of CO 2,N 2 and O 2 adsorption isotherms Isosteric heat of adsorption ZSM-5 UTSA-16 60 C 60 C Q st Q st CO 2 (kj mol -1 ) Q st N 2 uptake (kj mol 1 ) Q st O 2 uptake (kj mol -1 ) ZSM-5 35 15 18 UTSA-16 37 13 14 13

Adsorption of CO 2, N 2 and O 2 DYNAMIC adsorption of CO 2,N 2 and O 2 on UTSA-16 MOF Breakthrough experiment Pulsed chromatography Henry Constant K H for CO 2,N 2 and O 2 T ( C) CO 2 K H N 2 K H O 2 K H UTSA-16 60 112.6 3.3 3.0 14

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 15

Scale up of CO 2 capture adsorbents 5.5 liter batch reactor Properties: Volume: 1.5 gallon (~5.5 liters) Pressure up to 200 bar Temperature to 500 C Internal stirring Literally a heavy work

Scale up of CO 2 capture adsorbents UTSA-16 scaled-up successfully (>100g/batch)

Scale up of CO 2 capture adsorbents CPO-27-Ni was also scaled-up to > 100g/batch Synthesis was based on water (as seen in LCA results)

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 19

The conductive media bio carbon TARGET: Performing conductive carbon for Electric Adsorption (ESA) Bio carbon from lignin (nature s most abundant aromatic polymer) Carbonized lignin: CO 2 at 0 C Carbon content: 95.2 wt. % Surface area: 155 m 2 g -1 Chemically activated lignin Chemically activated lignin: Activation agent: K 2 CO 3 CO 2 uptake at 0 C and 0.2 bar: 2.6 mol kg -1 Surface area: 1099 m 2 g -1 Electrical conductivity is comparable with carbon black values. 20

Outline: the materials of MATESA project The adsorbers of MATESA Characterization of the materials MATESA selective CO 2 capture materials adsorbents Scale up of MATESA CO 2 capture materials adsorbents The conductive media bio carbon Final remarks 21

Final remarks ZEOLITE SELECTIVE CO 2 CAPTURE ADSORBENTS ZSM-5 zeolite can selectively adsorb CO 2 with respect to N 2 or O 2 Specific heat capacity of ZSM-5 is < 1 J g -1 C -1. ZSM-5 can bear high temperature treatments. MOF SELECTIVE CO 2 CAPTURE ADSORBENTS UTSA-16 and CPO-27-Ni are both very promising materials UTSA-16 CO 2 uptake at 0.15 bar and 60 C is 0.92 mol kg -1 (vs. ZSM5: 0.33 mol kg -1 ) UTSA-16 is thermally stable till 350 C. UTSA-16 specific heat capacity is 1 J C -1 g -1 at 60 C MORE DETAILS ARE AVAILABLE IN: Masala, A. et al., Phys. Chem. Chem. Phys. 2016, 18, 220 227 Masala, A. et al., J. Phys. Chem. C. 2016, 120, 12068 12074 22

Final remarks THE BIO CARBON Easily prepared from lignin a residue from the pulp industry. Good electrical conductivity comparable to carbon black. Fair adsorption CO 2 capacity that can be exploited for selective adsorbers SCALE UP Successful scale-up processes allowed to produce > 100 g of/batch in case of both MOF materials. 23

Acknowledgments Dr. Carlos Grande, Dr. Richard Blom, Ms. Giorgia Mondino Prof. Alan Chaffee, Dr. Gregory P. Knowles, Dr. Marc Marshall Dr. Hans-Jürgen Richter Dr. Jean-Jacques Theron Dr. Eva Björkman, Mr. Malte Lilliestråle Prof. Silvia Bordiga, Dr. Jenny G. Vitillo, Dr. Francesca C. Bonino, Dr. Maela Manzoli, Prof. Michele R. Chierotti, Prof. Gianmario Martra, Dr. Lorenzo Mino, Dr. Maria Botavina 24

25

Deliverable 7.3 Proceedings dissemination day A pdf document will be made and distributed among all the participants and put on the web page. Edited by: Prof. Silvia Bordiga and Jenny G. Vitillo 26

Preface Prof. Silvia Bordiga and Dr. Jenny G. Vitillo Table of contents MOF-based mixed matrix membranes for CO 2 capture. F. Kapteijn Project LEILAC: Low Emissions Intensity Lime and Cement. A. Vincent Overview of HiPerCap results so far. H. Kvamsdal Cost effective CO 2 capture in the Iron & Steel industry. P. Cobden Advanced Solid Cycles with Efficient Novel Technologies. P. Cobden IEAGHG Overview and recent activities. J. Kemper CCS in Norway CLIMIT, TCM and Full Scale Demonstration S. Bekken MATESA project. (1 page introduction + presentations from any speaker) The MATESA project & concept C. Grande Materials development A. Masala- H.J. Richter Proof of concept C. Grande ESA processing and cycle design M. Petkovska, B. Schurer Process economics and LCA 27

Alessio Masala, MATESA Dissemination Day, Jun. 16 th, 2016, OSLO, NORDE CO 2 capture: key points Carbon Capture Utilization and Sequestration technique (CCUS): A sustainable solution for the reduction of CO 2 emissions. Without CO 2 -capture system 15% CO 2 75% N 2 6% AIR H 2 O 3.5% O 2 Decarbonized Fuel-fire power plant - Combustion of fuel to generate heating - Post-combustion exhaust contains 15% of CO 2 that will be dispersed in the atmosphere With CO 2 -capture system - CO 2 is captured by adsorbers CCUS system - Only decarbonized AIR is dispersed in the atmosphere CO 2 is desorbed and stored for utilization/sequestration 28

The target of MATESA project TARGET 1. To capture the largest amount of CO 2 at the following conditions: Combustion Source composition N 2 75% CO 2 15% O 2 3% H 2 O 6% 1 bar 40-60 C Adsorbent for CO 2 N 2, H 2 O O 2 TARGET 2. To desorb the captured CO 2 by electricity and low-grade heat: High purity CO 2 is desorbed 70% low-grade heat 30% electricity (ESA) Adsorber Alessio Masala, MATESA Dissemination Day, Jun. 16 th, 2016, OSLO, NORDE 29

Alessio Masala, MATESA Dissemination Day, Jun. 15 th, 2016, OSLO, NORDE The adsorbers of MATESA REFERENCE ADSORBER ZEOLITES ADVANCED ADSORBER METAL-ORGANIC FRAMEWORKS 13X zeolite ZSM-5 zeolite UTSA-16 CPO-27-Ni benchmark Citrate ligand Commercial materials Laboratory materials, provided by: 30

Alessio Masala, MATESA Dissemination Day, Jun. 15 th, 2016, OSLO, NORDE The adsorbers of MATESA To perform Electric Swing Adsorption, adsorbers must be conductive! The mixture: 60-70% Active phase 30-40 % Conductive phase 500-800 C Carbonization process FOTO ZEOLITE Extrusion process Active + Phenolic resin Extruded monolith 31

Adsorption of CO 2 in steam environment Water vapour constitutes an important fraction (5-20%) of coal and NG-fired plant exhaust. Dynamic experiment UTSA-16 is able to uptake CO 2 in presence of water vapour. Static experiment UTSA-16 is stable and maintains 70% of the CO 2 working capacity in a steam environment at 40 C.

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