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Towards Sunlight Driven CO2 Utilization
Benjamin R. BuckleyLecturer in Organic Chemistry
Department of Chemistry, Loughborough University
[email protected], 228752
Energy Expo, Loughborough University 14th Feb 2013
The Concept
Background:
a) A device to convert CO2 into
useful organic compounds powered
by solar energy.
b) A device that directly
converts CO2 into useful
organic compounds
through photocatalysis.
2
The Concept
CO2(g), 1 atm
Bu4NBr
MgCu
AnodeCathode
Supporting electrolyte
OOO
O
50ºC
Solvent
Current Technology:
B. R. Buckley, A. P. Patel and K. G. U, Wijayantha, Chem. Commun., 2011, 47, 11888.
CO2(g), 1 atm
AnodePhoto-Cathode
aqueous electrolyte
XOX
O
Sunlight
Electro-Catalyst
Proposed System:
X = NR or O
PolycarbonatesPolyurethanes
carbonatesoxalatesalkanesalcohols
Al
or othersustainable material
Acknowledgements
Dr K. G. Upul Wijayantha
and
Anish P. Patel
Developing Leaders
4
Dr Darren Walsh
and
Vanessa Silvestre
Simon Beaumont - Current Research Interests:
Bulk
chemicals
Fine
chemical
synthesis
Pressure
Temperature
Surface
Sensitivity
Time resolutionReadily tunable
Size-controlled
Composition
controlled
Clean/ free of
contaminants
Following reaction
mechanisms on solid catalysts’
surfaces, where and when all
the chemistry occurs, is key
to understanding the way
these processes work, and
how to improve them
Surface
organometallic
chemistry
Nano-materials
synthesisIn situ spectroscopy/
(/Catalyst ‘sensitive’)
In situ DRIFTS
Heterogeneous
Catalysis
Colloidal
nanoparticles
In situ X-ray
spectroscopy
In situ Raman / SFG
LDH clays
(trans-
esterification)
Fischer-Tropsch Ag-Cu selective
oxidation
(Epoxidation)
CO2 utilization
(hydroformylation,
hydrogenation)
C-C coupling
reactions
Pd-Ag selective
hydrogenations
Simon Beaumont – Past Areas of Work:
Desirable CO2 utilisation strategies we are investigating:
In situ synchrotron X-ray spectroscopy of
Fischer-Tropsch /CO2 hydrogenation catalysts.
Co catalyzed reduction – best current industrial present is Cu
catalyzed methanol production using CO2 in feedstock – also
produce Fischer Tropsch products using Cobalt.
Also currently exploring small Rh nanomaterials for use as
catalysts for CO2 hydroformylation
Iablokov, Nano Lett, 2012; Beaumont, Faraday Discuss. 2013
Gas and liquid phase electrochemical
reduction of CO2.Shi, 2014, in prep.
Mechanistic understanding of Pt promoted
Co catalysts for CO2 reduction.
Alayoglu,Top. Catal., 2012
In situ Raman Spectroscopy
monitoring of Solid Oxide
Electrolysis Cells (SOECs)
Jen Manerova
High Temperature Co-electrolysis
• Operating temperatures:
– 750 – 1000 oC
• Common materials:
– YSZ electrolyte
– Ni-YSZ cathode
– LSM anode
• Investigate reactions
occurring using in situ
Raman Spectroscopy
In situ Raman Spectroscopy
Carbon Deposits
Acknowledgement
Buckley Group: Current Activity
11
Org
anic
Synth
esis
Catalysis
CDU
Technology
TL 2013, 54, 843CC 2010, 46, 2274, CEJ 2010,
16, 6278, 2012,18, 3855, EJOC 2011, 770
GC 2012, 14, 2221
CC 2011, 47, 11888
SL 2013, eFirst
JOC 2013, 78, 1289
Buckley Group Recent Highlights: Carbon Dioxide Utilisation
B. R. Buckley, A. P. Patel and K. G. U, Wijayantha, Chem. Commun., 2011, 47, 11888.
Buckley Group Recent Highlights: Carbon Dioxide Utilisation
B. R. Buckley, A. P. Patel and K. G. U, Wijayantha, Synlett., 2013, DOI:s-0033-1340109
CO2 (1 atm)
Bu4NBr (1.0 eq.), MeCN60mA, 6 h 50 ºC + )))
Ph
OPh
Cu Mg
CO2 (1 atm)
Bu4NBr (1.0 eq.), MeCN60mA, 6 h 50 ºC
OO
Ph
O Cu Mg
96% 90%
This work:
Funding
Dr K. G. Upul Wijayantha
and
Anish P. Patel
Developing Leaders
Dr Darren Walsh
and
Vanessa Silvestre
Joey Walker
EngD
EPRSC Industrial Doctorate Centre in
Carbon Capture and Storage, and Cleaner Fossil Energy
IERT at Cranfield
Ben Anthony
Kumar Patchigolla
CO2 Capture-Ca/Chemical
looping
Combustion
Gasification
Circulating fluidised bed
Gas Turbines/Burner Rigs
CO2 Transport rig
HP Steam
High temperature/high
pressure corrosion furnaces
Gas engines-Perkins
Major Energy Facilities
Major Research
Activities
•Biomass and Bioenergy
• Advanced carbon Capture
• Carbon Transport
• Energy from Waste
• Gas Turbines for H2-rich IGCC Syngas
• Oxy-fuel Combustion
• Next Generation Coal Power Plants
• Advanced Materials for Low Emission Power Plants
PACT Chemical
Looping Facility at
Cranfield
• Approx. 50 KWth pilot scale chemical looping facility
• Cold model scaled to 1:1 to study solid flow characteristics
• 100 mm ID riser - (adjustable in height up to 7.3 m)
• Flexible in configuration, either as
Twin CFB legs or
Single entrained flow riser with bubbling bed (2nd reactor)
• Chemical looping mode-either for oxy-combustion or for H2
production
• Flexible controls to enable a range of operating modes
• Rig supplied with different bulk gas mixtures--O2, CO2, N2, H2 and
CO
• Dedicated MFCs for each bulk gas
New UKCCSRC Project on Chemical
Looping for Low Cost Oxygen
Production
PACT CO2 Flow Loop
Facility at Cranfield E.ON-EPSRC strategic partnership
(EP/G061955/1)
Flow rig operates above 90 bar, 40 deg (capable for up to 700 bar & -50 to 150
deg) in flow mode (fluid flow rates up to 5l/min)
High pressure observation window-provide detailed information on phase
separation, hydrodynamic flows, contamination etc.
Runs for several hundred hours depends on material corrosion and environment
Continuous monitoring of corrosion by electro chemical noise & Linear
polarization resistance
Measurement and monitoring of physical properties- density, pH, temp,
pressure
SC3 include several coupon geometry (accommodate materials up to 2” in
diameter and up to 1 m in length)—plates, tubes, bar, charpy and tensile
coupons
Impurities– H2O, H2, H2S, NOx, SO2and O2 etc..; dedicated MFCs to maintain
the proportions
Materials– X60, X70, X100, 316, duplex steel etc..
Non-metallic materials degradation— flow through seals, lubricants
Tested for 150 bar
21/03/2014 © The University of Sheffield
21
Research in heterogeneous catalysis
• Range from traditional petrochemical processing
to biorenewables and novel materials
• Particular interests in, e.g., coke deposition /
extending catalyst lifetime, metal oxides in
catalysis, utilisation of waste materials
5
nm
21/03/2014 © The University of Sheffield
22
Experimental capabilities - reactors
• Stirred reactor (Hastelloy)
• 450 °C; 220 bar; batch or semi-batch
• Packed bed reactor
• Can also operate in trickle-flow; 1000 °C
• Diffuse Reflectance Infrared Cell
• in situ reaction studies at high T/P
Research in heterogeneous catalysis
21/03/2014 © The University of Sheffield
25
CO2 to “fuels” via catalysis
• Hydrothermal synthesis of ethanol
(and higher hydrocarbons) over
iron catalysts (G/S/L)
• Hydrogenation of CO2 to CH4
(G/S), collaboration with Dr. J.S.
Dennis, University of Cambridge
• CO2 as an oxidant in catalytic
dehydrogenation (G/S)
• Glycerol carbonate synthesis
(G/L/S)
Fe/Al2O3Fe/zeolite (1)Fe/zeolite (2) Fe/C
phenol
26
• Gas/liquid/solid processes, e.g. produce
fuels and chemicals without going through
syn-gas (and without hydrogen)
• Glycerol carbonate makes use a waste
product of biodiesel synthesis
CO2 to “fuels” via catalysis
27
• Gas/solid processes, e.g.
methanation of CO2
• CO2 as an oxidant in catalytic
dehydrogenation, e.g. synthesis of
styrene from ethylbenzene over
chromium or vanadium
CO2 to “fuels” via catalysis
What are Ionic Liquids?
• Ionic liquids (ILs) are organic salts with low melting points
and includes salts that are solid at room temperature but
that melt below around 120°C
• As salts, they cannot evaporate, have high stability and
excellent recyclability
• The strength of interaction can be tailored to
application: Separation, Reaction and Catalysis
4CU ionic liquid activities (SP3)
• Our research currently looks at a variety of ionic materials,
both liquid and solid with several avenues being explored:
• CO2 uptake at high pressure using ionic solids
• Low viscosity ionic liquids for gas stripping/sweetening
• Novel liquid-gas contacting methods
• Scale-up work (1 tonne CO2 /day)
• Fuels synthesis is being investigated from late 2014, with
first-stage CO2 to liquid fuels and plastics experimentation
underway
CO2 Capture & Utilisation Interests
About Pera Technology
and
Pera Technology Services
For progressive medium-
sized companiesFor large corporations
Pera Technology Services
• Large contact base – 26k manufacturing
SMEs & 91k broader SMEs
• About 65 current projects
• Concept development
• Proposal writing
• Funding & finance
• Technical R&D services – range of
science & engineering disciplines
• Project Management
• Commercialisation
Projects cover materials,
chemistry, biotechnology,
energy, process, monitoring &
control
About 15 current projects
Partnering - iNet
“If we can’t do it ourselves, chances are we know someone who can.”
The iNET industrial partner network comprises over 600 SMEs, all of which have expressed an interest in collaborating & building relationships with European RTOs. Target to expand this to over 2000 before the end of 2015.
iNet FP7 statistics:
• Built a network of 80 research partners across 19 European Countries.
• iNET partners submitted over 500 funding proposals to EC calls.
• iNET supported/had involvement in over 200 funding proposals annually during FP7.
• iNET members had/have 100+ live projects at any one time.
Cradle to CradleCM Products Innovation Standard
Main UK Assessment Body
CO2 Capture & Utilisation Interests
Low & zero carbon fuels – just completed an extensive study for major client
Synthetic methane (CO2 + H2O), including use of carbonic anhydrase
CO2-based materials
Particular expertise in ionic liquids
Process engineering, particularly for cost reduction
Business intelligence to support IP protection and stages to commercialisation
About Viridor
Viridor is at the forefront of transforming waste
Part of the FTSE 250 Pennon Group
Supporting >100 UK local authorities
and >45,000 customers through a
network of 327 facilities
Over 2.4m tonnes recycled or recovered
each year
Responsibly managing c.8m tonnes of
waste each year
760 GigaWatt hours of renewable energy
generated (136 MW capacity)
>3000 employees, with a turnover of £761m
Accredited to ISO14001, ISO 9001, ISO50001
& OHSAS18001 environmental, quality, energy
and health and safety standards
25 Materials Recycling Facilities
5 Anaerobic Digestion Facilities
37 Collection Service Depots
43 Transfer Stations
15 Composting/Organics Recycling Facilities
3 Energy from Waste Facilities
6 Energy from Waste Facilities in development
22 Operational Landfills
The many ways we transform waste
Energy from WasteOperations and investment
Under construction/in development
Runcorn CHP - Under construction. 750K tpa; 70 MW power; 50 MW heat
(Phase 1 JV with Laing and INEOS Chlor; Phase 2 Viridor).
Due online 2014
Ardley - Under construction. 300K tpa; 24 MW. Due online 2014
Cardiff - Under construction. 350K tpa; 30MW. Due online 2014
Exeter - Under construction. 60K tpa; 3MW. Due online 2014
Peterborough - Planning approved. 85K tpa; 7MW. Due online 2016
Glasgow - Gasification plant, construction 2013. 200K tpa; 15MW. Due online
2016
Energy from WasteOperations and investment
Consented/proposed
Dunbar - Planning approved. 300K tpa; 25MW
Avonmouth - Planning approved. 350K tpa; 30MW
Beddington - Awaiting planning decision. 300K tpa; 26MW
Our environment: Viridor and the bigger picture
Sustainability:
Challenging performance targets for environmental, social and economic
sustainability. Open reporting annually
Carbon management and energy efficiency
– Pennon within leading group of FTSE 250 for Carbon Disclosure Project
– Carbon Reduction Commitment and Carbon Gold Standard
– 5 year Energy Efficiency and Carbon Management Plan
Any questions?
A Coordinated, Comprehensive approach to Carbon Capture and Utilization
Professor Peter Styring, The University of SheffieldUK Centre for Carbon Dioxide Utilization• Consortium of four UK universities: Sheffield, UCL,
Queens Belfast, Manchester
• £5.7M Programme Grant over 4 years
• 9 Post-doctoral positions and Project Manager
• Four year programme of research
• Whole System approach:• Life Cycle Analysis
• Carbon Capture Reagents, ionic liquids & polymers
• Flue Gas & AD Off-gas conversion
• Fuels from CO2
• Molecular Modelling
Bringing people interested in CO2 utilization together
SP3 & SP4
SP5 & SP6
SP7
![[Habilitações Académicas] Sunlight-driven CO Conversion](https://img.pdfslide.net/doc/110x75/62c7beca46e52e4342709a74/habilitaes-acadmicas-sunlight-driven-co-conversion-.jpg)
