Emerging Tends in Adsorption Based CO 2 Capture. Alan L Chaffee School of Chemistry, Monash University

Transcription

1 Emerging Tends in Adsorption Based CO 2 Capture Alan L Chaffee School of Chemistry, Monash University Hypercap, Oslo, Sept 13, 2017

2 Outline What for? Sequestration Enhanced Oil Recovery Food grade Greenhouse use Chemical products Hydrocarbon fuels What from? Flue gas (coal or other) Natural gas Biofuel Industry processes (cement) Air What material? Carbons Zeolites MOFs Amines (composites) Oxides What approach? PSA VSA TSA ESA Hybrid approaches 2

3 Outline What for? Sequestration Enhanced Oil Recovery Food grade Greenhouse use Chemical products Hydrocarbon fuels What from? Flue gas (coal or other) Natural gas Biofuel Industry processes (cement) Air What material? Carbons Zeolites MOFs Amines (composites) Oxides What approach? PSA VSA TSA ESA Hybrid approaches 3

4 Adsorbent Materials Metal Oxides Metal Organic Frameworks (MOFs) Carbons Composites: mesoporous supports incorporating amines HMS SBA-15 KIL-2 MCF Pore Vol ~ 0.7 ml/g Pore Vol ~ 1.0 ml/g Pore Vol ~ 1.6 ml/g Pore Vol ~ 2.8 ml/g 4

5 Summary Comparison 5 Qi et al, Nat. Commun. 2014, 5, 5796

6 Materials multitude of variations Chmisorbents vs. Physisorbents Carbons Zeolites MOFs Amine composites Metal oxides / Carbonates Microporous, mesoporous, nanoporous, graphitic, Templated, MWNT, SWNT, carbon fibres,. C-molecular sieves, N-doped, Type X, Y, A, MOR, CHA, HZMS5, H-form, Na-form, Ca-form, Mg-form,.. Molecular sieves MOFs, ZIFS, COFs, HKUST, DMOF, UiO-66, UTSA, MIL-101, IRMOF-8,. Zn-DABCO, Co-DABCO, Mg/DOBDC, ZNBuBPDC,. mmem-mofs, IRMOF-8-NO2,. PEI, TEPA, linear-pei, br-pei,. Type 1, Type 2, Type 3. SBA-15, MCM-41, MCF, KIL-2,. Hydrotalcite, CaO, Mixed Metal Oxides, Mg/KO, CaO,. 6

7 Materials multitude of variations Chmisorbents vs. Physisorbents Carbons Zeolites MOFs Amine composites Metal oxides / Carbonates Microporous, mesoporous, nanoporous, graphitic, Templated, MWNT, SWNT, carbon fibres,. C-molecular sieves, N-doped, Type X, Y, A, MOR, CHA, HZMS5, H-form, Na-form, Ca-form, Mg-form,.. Molecular sieves MOFs, ZIFS, COFs, HKUST, DMOF, UiO-66, UTSA, MIL-101, IRMOF-8,. Zn-DABCO, Co-DABCO, Mg/DOBDC, ZNBuBPDC,. mmem-mofs, IRMOF-8-NO2,. PEI, TEPA, linear-pei, br-pei,. Type 1, Type 2, Type 3. SBA-15, MCM-41, MCF, KIL-2,. Hydrotalcite, CaO, Mixed Metal Oxides, Mg/KO, CaO,. 7

8 CO 2 Capture via Solid Composite Amine Sorbent Adsorbents for PC CO 2 capture Ideal Sorbent: Large CO 2 working capacity. Highly CO 2 selective. Fast sorption kinetics. Low energy (heat of adsorption) Water tolerant. Comparison of different adsorbents Type WC Select CO 2 /H 2 O Physisorbents Kinetics Energy Water Act Car ~ ~ Zeolite ~ X MOF ~ ~ ~ Chemisorbents Amine ~ ~ Met Ox ~ X PHYSISORBENTS Van der Waal s interactions Electrostatic Interactions Molecular Size CHEMISORBENTS Reactivity Stoichiometry Accessibility 8

9 Amine Behaviour - Neat vs Supported Initial structure Annealed structure 298K Annealed structure 378K Impregnated Neat Dendrimer diffusion: CO 2 diffusion: 1.19E-07 A 2 /ps 8.89E-06 A 2 /ps 1.49E-07 A 2 /ps 2.83E-05 A 2 /ps Dendrimer diffusion: CO 2 diffusion: 1.53E-05 A 2 /ps 6.49E-03 A 2 /ps 4.61E-05 A 2 /ps 1.02E-02 A 2 /ps Fadhel Hearne, Chaffee, MMM 123, 140 (2009)

10 Amine Composites: volume utilisation Amines for chemiselective capture, analogous to solvents Silica support to activate and contain the active agent and to facilitate vacuum swing adsorption (VSA) C H H22 H 22 C NN H Linear polyethyleneimine PEI PEI TEPA DETAPSi- PAA H 22 C C NN H22 H branched polyethyleneimine HH 2 2 N N HH HH NN N NN HH tetraethylenepent r a mi m n e NNH 2 2 HO HN Si HO N H NH 22 OH diethylenetriaminepropylsiloxy- HH 22 N polyallylamine Composites: mesoporous supports incorporating amines Chemisorption HMS SBA-15 KIL-2 MCF Pore Vol ~ 0.7 ml/g Pore Vol ~ 1.0 ml/g Pore Vol ~ 1.6 ml/g Pore Vol ~ 2.8 ml/g 10

11 Amine Composites: increasing capacity PEI/KIL2 KIL-2: Wormhole structures with high pore volume 11 Ojeda et al, Energy Procedia 114 (2017)

12 Amine Composites: volume utilisation CO 2 Sorption Note sorption dependence on: Temperature Amine loading as % of pore volume Water inhibits deactivation by urea formation: Eq 1: 2RNH 2 + CO 2 <-> RNHCOO - + RNH 3+. Adsorption (carbamate formation) Eq 2: RNCOO- + RNH3+ <-> RNCONR + H 2 O De-activation (urea formation) CO 2 Working Capacities: ~ 11 wt % CO 2 (TSA, C) ~5 wt % CO 2 (VSA, atm) C H H22 H 22 C NN H linear Polyethyleneimine (PEI). C H H22 H 22 C branched NN MCF Weight Change (%) Weight Change (%) MP90-a 2, 5, 15, 30, 50, 30, 15, 5, 2, 0 % CO 2 /Ar Time (min) Time (min) 90 C 105 C 115 C (105 C) MP80a MP85a 5 wt% MP90a 11 wt% TGA of CO 2 PPSA for MCF-PEI composites. CO2CRC. All rights reserved. 12 Knowles et al, Micro Meso Mat, 238, 14 (2017)

13 Amine Composites: volume utilisation MCF-PEI Pellets Production of MCF-PEI80 pellets via SPTP ~80 g MCF. ~200 g MCF-PEI (~80 % void vol. fill). Shaped as carbonated via SPTP. ~1 g amounts of MCF-PEI80b before (left) and after (right) shaping via SPTP 1. Automated Single Punch Tablet Press New shaping technology appears scalable for mass automated production 13 1 Carbon Capture Journal, Monash University develops new shaping technology to produce sorbents, 2015, July-Aug edition, pages 12-13,

14 Amine Composites: volume utilisation Simulated Flue Gas These improvements in PEI sorbents provide stability for PCC % Adsorption Desorption % Capacity (% 1st Desorption Cycle) % 80.00% 60.00% 40.00% 20.00% 0.00% Cycles CO 2 working capacity preserved over 60 cycles partial pressure swing adsorption (VSA) at 105 C 14 Knowles et al, 2016, unpublished results

15 Amine Composites: increasing capacity further Sponges Covalently bonded amines Highly linear attachment 15 Qi et al, Nat. Commun. 2014, 5, 5796

16 Amine Composites: The problem - urea formation: Improving the Stability of PEI adsorbents One solution cross linking with: butadiene diepoxide epichlorohydrin Capacity loss with cycling is reduced 16 H Jung et al, Chem Eng J 307 (2017)

17 Amine Composites: Building fundamental understanding Exhaustive study of effect of T and p(h 2 O) H 2 O adsorption isotherms CO 2 adsorption isotherms Water adsorbs at low T and promotes CO 2 adsorption at low T At higher T little water adsorbs and, so, doesn t make energy demands during Desoprtion. 17 H. Zhang et al, J CO 2 Utilization 19 (2017) Prakrash / Olah group

18 MCF-PEI Pellets: Applying this to Air Adsorption Breakthrough Apparatus Breakthrough Curves MFC-101 MFC-102 V MFC-103 MFC-104 TT 103 TT 102 TT 101 TT 104 C-101 0,8 36C 40C Gas supply 1 Gas supply 2 Gas Gas supply 3 supply 4 TC-101 F-101 V-102 C/C0 0,6 0,4 46C 52C 58C CS-101 A-101 0,2 66C 71C PC Simulated Air (400 ppm CO2 in N2) Flow rate: 270 ml/min Time (h) 81C Breakthrough time is very temperature dependent Saturation is achieved only above 60 C over the time scale studied. 18 Wijiseri et al, Chemeca, Melbourne (2017)

19 MCF-PEI Pellets for Air Adsorption Capacity vs Time (MP80) Capacity after 40h 1,20 1,2 1,00 1 Capacity (mmol/g) 0,80 0,60 0,40 0,20 36C 40C 46C 52C 58C 66C 71C Capacity at 40 h (mmol/g) 0,8 0,6 0,4 0,2 0, Time (h) 81C Temperature ( C ) Capacity is temperature dependent Optimal temperature is ~ 50 C (max CO 2 adsorption rate) Probably can be improved at lower PEI loadings CO 2 would be recovered with low grade heat 19 Wijiseri et al, Chemeca, Melbourne (2017)

20 Materials multitude of variations Chmisorbents vs. Physisorbents Carbons Zeolites MOFs Amine composites Metal oxides / Carbonates Microporous, mesoporous, nanoporous, graphitic, Templated, MWNT, SWNT, carbon fibres,. C-molecular sieves, N-doped, Type X, Y, A, MOR, CHA, HZMS5, H-form, Na-form, Ca-form, Mg-form,.. Molecular sieves MOFs, ZIFS, COFs, HKUST, DMOF, UiO-66, UTSA, MIL-101, IRMOF-8,. Zn-DABCO, Co-DABCO, Mg/DOBDC, ZNBuBPDC,. mmem-mofs, IRMOF-8-NO2,. PEI, TEPA, linear-pei, br-pei,. Type 1, Type 2, Type 3. SBA-15, MCM-41, MCF, KIL-2,. Hydrotalcite, CaO, Mixed Metal Oxides, Mg/KO, CaO,. 20

21 MOFS: New prospects with Phase Change Adsorbents Reversible Cooperative Insertion 21 Chem. Soc. Rev., 43, (2014) Long et al, Nature 519, (2015)

22 Phase Change Adsorbents CO 2 Adsorption Isotherms CO 2 Adsorption Isobars Mg Mn Fe Co Ni Zn Long et al, Nature 519, (2015)

23 Phase Change Adsorbents CO 2 Adsorption Isotherms CO 2 Adsorption Isobars Mg Mn Fe Co Ni Zn Switch occurs over a wide range of P and T, depending on metal 23 Long et al, Nature 519, (2015)

24 Phase Change Adsorbents CO 2 Adsorption Isotherms CO 2 Adsorption Isobars Mg Mn Fe Co Ni Zn Switch occurs over a wide range of P and T, depending on metal Appreciable CO2 adsorption from air 24 Long et al, Nature 519, (2015)

25 Phase Change Adsorbents CO 2 Adsorption Isotherms CO 2 Adsorption Isobars Mg Mn Fe Co Ni Zn TSA in pure CO 2 Switch occurs over a wide range of P and T, depending on metal Appreciable CO 2 adsorption from air 25 Long et al, Nature 519, (2015)

26 Phase Change Adsorbents These MOFs tolerate moisture! Exhibit some analgous behaviour to amine composites Can they be fabricated into industrial robust forms, eg pellets? 26 Long et al, Nature 519, (2015)

27 Materials multitude of variations Chmisorbents vs. Physisorbents Carbons Zeolites MOFs Amine composites Metal oxides / Carbonates Microporous, mesoporous, nanoporous, graphitic, Templated, MWNT, SWNT, carbon fibres,. C-molecular sieves, N-doped, Metal hydroxide-doped Type X, Y, A, MOR, CHA, HZMS5, H-form, Na-form, Ca-form, Mg-form,.. Molecular sieves MOFs, ZIFS, COFs, HKUST, DMOF, UiO-66, UTSA, MIL-101, IRMOF-8,. Zn-DABCO, Co-DABCO, Mg/DOBDC, ZNBuBPDC,. mmem-mofs, IRMOF-8-NO2,. PEI, TEPA, linear-pei, br-pei,. Type 1, Type 2, Type 3. SBA-15, MCM-41, MCF, KIL-2,. Hydrotalcite, CaO, Mixed Metal Oxides, Mg/KO, CaO,. 27

28 Active Carbon for CO 2 Capture: from brown coal Victorian brown coal (VBC): low S/P/N and low ash make this an excellent precursor for active carbons a very cheap resource enormous surface areas can be achieved (>1000m 2 /g) this results in excellent gas adsorption properties. CO 2 adsorption isotherms VBC Carbon Powder Benchmark Commercial Carbon Loy Yang Mine and Power Stations 28 L Ciddor, PhD Thesis, Monash University, 2016

29 Active Carbon Monoliths for CO 2 Capture A method has been developed to prepare active carbon monoliths from Victorian brown coal good surface area good electrical conductivity good CO 2 adsorption and selectivity Samples Cell density (cells/in 2 ) Wall thicknes s (mm) Electrical Conductivity (Ω -1 cm -1 ) Carbonised Activated Compressive hardness (MPa) 7 Formula A Formula B Australian Patent Application AU

30 Honeycomb Carbon Monoliths from VBC Regenerable Electrical conductive High surface area Easy to make Light weight and high-strength 1. Vergunst et al, Preparation of carbon-coated monolithic supports. Carbon, , Liu et al., Preparation of activated carbon honeycomb monolith directly from coal. Carbon, , 1598

31 Decomposition of H 2 O 2 O 3 /active carbon advance oxidation Applications Catalyst CO 2 Capture Methane purification and storage Dioxin removal Gas-Phase adsorption Carbon Monolith Liquid- Phase adsorptions Recovery of I 2 Adsorption of inorganic Blood cleansing Li secondary battery Supercapacitor Electrode material Catalyst support Selective reduction of NOx Automobile exhaust treatment

32 Active Carbon Monoliths for CO 2 Capture CO2 ads / des for pelletised CMK-3 carbon CO2 ads weight (%) CMK-3-NH2 CMK-3-NH2 pellet (powder) CMK-3-NH2 pellet (pellet) Temperature Temperature (celcius) Time (minutes) 0 We have previously demonstrated that monolithic carbons can capture CO 2 and then be regenerated by Electrical Swing Adsorption (ESA) This previous work involved expensive precursor materials and/or processing methods VBC derived adsorbents are now prospective for CO 2 capture and many other applications. Heat is not wasted in regeneration 32

33 Carbon Fibre Monoliths Made from: petroleum pitch carbon fibre and phenolic resin Preparation steps: moulding, drying and curing, carbonisation and activation. 33 Int J GHG Control 13 (2013) Int J GHG Control 42 (2015)

34 Carbon monoliths: beneficial heat conduction properties GP: Granular packing (Pica activated carbon) SCM: Straight open channel monolith (Air blown pitch/koh/expanded graphite) SCM conducts heat throughout better Gives more uniform T distribution Pure CO 2 breakthrough curves for both GP and SCM packings. Open symbols: GP, black symbols: SCM, with external heat transfer: ( ), near- adiabatic: ( ). 34 Menard et al, Chem Eng Proc 44 (2005) 1029

35 PEI Monoliths: 3D Printing Effects of Temperature In 10% CO 2 /N 2 at variable T, determined by TGA Effects of Moisture In 10% CO 2 /N 2 at 25C determined by TGA Breakthrough curves at 25C in 10% CO 2 /N 2, 30 ml/min 35 ACS Appl. Mater. Interfaces 2017, 9, 7489 Thakkar et al, Rezaei group

36 Low Density Structures: Nanofibrillated cellulose (NCF) aminated Applied to AIR CAPTURE TVS process Adsorption: 30C, 60%RH, 5 l/min, 600 min Desorption: 90C, 60 min, with moisture (as above), 1 l/min N2, moisture from adsorption, 36 Gebald et al, Env Sci & Tech, 2014, 47, 10063

37 Phase Change MOFs on Monoliths 37 Durante et al, ACS Appl Mat Interf, 9, (2017) Jones Group

38 Building Focus on Air Capture Solid Supported Amine Based on the work of Gebald and Wurzbacher ETH Zurich Aq. Metal Hydroxide Based on the work of Keith Solid Supported Amine Based on the work of Jones, Georgia Inst Tech Anionic Exchange Resin Based on the work of Lackner, Ariz State Uni Solid Supported Amine Based on work at VTT Combined with H 2 from electrolysis to produce FT hydrocarbons 38

39 Building Focus on Air Capture Based on the work done at VTT Technical Research Centre of Finland and Lappeenranta University of Technology (LUT) Sorbent amine functionalised polystyrene adsorbent Regeneration Heating to 80 C under vacuum Modular unit capturing ~1.5 t-co 2 /yr/module 39

40 Building Focus on Air Capture Spin-off of the work done by Christopher Jones group at Georgia Tech Sorbent - Amine bonded to a ceramic honeycomb monolith support Regeneration Stripping with low temperature steam ( C) CO 2 purity - 98% v/v Modular capture units capable of capturing 50,000 t-co 2 /yr/module 40

41 Building Focus on Air Capture Spin-off of the work done by Christoph Gebald and Jan Wurzbacher at ETH Zurich Sorbent- Solid supported amine Regeneration - heating the sorbent to 100 C at lowered pressure CO 2 purity 99% v/v Collaboration with Audi and Sunfire Converting the captured CO 2 to e-diesel 41

42 Summary MCF-PEI composite powders were prepared at various PEI loadings and shaped into dry robust pellets via a carbonation process. These chemisorbent materials have been demonstrated (lab scale) for multiple PCC cycles (105 C) and now need to be trialled at larger scale. MCF-PEI materials also work for air separation at lower T we are investigating process parameters/configurations to optimise this. Active carbons prepared from brown coal are also very good adsorbents (physisorbents). Brown coal has recently been extruded then carbonised/activated to form multichannelled monoliths that are electrically condutive. These can be used directly or functionalised then used in an ESA process to help minimise energy demands for CO 2 capture and recovery 42

43 Summary What one sees to be important emerging trends really depend on the precursor available, the product(s) forseen, the adsorbent applied and the process selected. It is not easy to glean the best way forward. Work on materials continues to strive for better capacities, higher selectivities, reduced energy demands, improved tolerance to impurities (including water), faster cycling, etc. This will support are markets / processes The chemoselectivity of amines (in varied forms) is attractive, as is the generalyl robust character and relatively lower cost of active carbons. Monoliths are attracting considerable interest due to new methods of fabrication and their inherent low pressure drop. Air capture is assuming prominence it can be done anywhere and, perhaps, combined with renewable H 2 for fuel production. 43

44 Acknowledgements Colleagues: Dr Greg Knowles, Dr Zhijian Liang for production of the MCF-PEI powder products. Dr Merhdad Parsa and Dr Emma Qi for production and procesing of VBC carbon monoliths. Romesh Wijesiri, Prof Andrew Hoadley Dr Hasina Yeasmin, for air capture studies Dr Seamus Delaney for initial ESA developments Dr Lachlan Ciddor for VBC derived active carbon powders Jack Sher, Corinna Henninger, Rahmam Rahad and Zoe Veldmann for laboratory assistance Prof Paul Webley, Dr Penny Xiao, Uni Melbourne, collaboration on processing routes Thank You!