Concert Hall - Aarhus
21 June 2012
8:30-10:00
Gabriele CENTI
European Research Institute of Catalysis (ERIC)
Dip di Chimica Industriale ed Ingegneria dei Materiali, Univ. Messina,
and CASPE (INSTM Lab of Catalysis for Sustainable Prod and Energy)
e:mail: centi@unime.it
Univ. Messina
INSTM
European Research Institute of Catalysis
....
Solvay
Industrial
Total Council
eni
Linde
CO2 initiative
Sasol
BASF
A Virtual (non-profit) Institute, based in Belgium,
gathering together 14 EU research and academic
Institutions in the field of catalysis. Deriving from the
EU Network of Excellence IDECAT
Mission
Bridge the gap between ideas and innovation
Reinforce academia@industry symbiosis
Develop common actions/projects to open to
new areas/applications opening market
opportunities
......
European Structured Research Area
on Catalysis and Magnetic Nanomaterials
http://www.eric-aisbl.eu/
2
Green Carbon Dioxide
3
A changing scenario
• Increase competitiveness in a global market whilst
drastically reducing resource and energy inefficiency
and environmental impact of industrial activities.
Competitiveness
FULLY
BALANCED
INTEGRATED
G. Centi et al.
AND
MUTUALLY REINFORCED
Sustainable
Development
Security of
supply
4
European strategy towards 2020
5
Roadmap 2050: cost-efficient
pathway and milestones
Reducing greenhouse gas emissions by 80-95% by 2050 compared to 1990
Energy efficiency
Renewables
Biomass
http://ec.europa.eu/clima/roadmap2050/
Sustainable Process Industry
by 2030, from current levels
• 30% reduction in fossil energy intensity
• 20% reduction in non-renewable, primary raw material intensity
Reduce CO2 footprint reduction across the value chain
Increased use in renewable feedstock
Reduction in primary energy consumption
Reduction in raw materials usage
Doubling of average recycling rate across the value chain
7
How?
High
P
R
I
O
Medium
R
I
T
Y
Process
intensification.
Resource efficiency
benchmarking.
High efficiency small
scale production
Composite materials
for automotive and
wind blades.
Life Cycle Cost
Analysis.
Water Footprint
Insulation. Inorganic PV. Biopolymers/
lubricants. New bio-based processes.
Bio facility of the future. New
resource efficient agrochemical
processes. Chemo-biocatalytic and
thermo-chemical processes for biochemicals. Batteries. Fuel cells. CO2 as
chemical building block. Chemical
Energy Storage. New catalysts.
New chemical pathways to hybrid
materials for electronic membranes.
smart windows. Fuel Cells CO2 as C1
source Water and Environment New
Dream Reactions. Innovative Fuels. 2nd
Gen. Bio refinery. Efficient biomass
drying. Algea based bio feedstock.
Alternative fossil feedstock
New nontoxic, non
noble metal catalysts.
PV Technology for
organic synthesis
reactions
Low
1-5y
Short
term
CO2 valorisation.
Valorisation of waste.
Advanced Electrolysis.
Organic PV.
5-10y
Mid term
Lighting technology.
CCS for plug in fossil
plants.
>10y
Long term
Time line
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Cefic CO2 Initiative
CO2 initiative
• New breakthrough solutions need to be developed that will
address the balance of CO2 in the Earth atmosphere and at the
same time provide us with the needed resources.
• A visionary way to go would be to achieve full circle recycling of
CO2 using renewable energy sources. Capture and conversion of
CO2 to chemical feedstock could provide new route to a circular
economy.
• Europe with it´s excellent research and industrial landscape
can be a key player for such a visionary approach in which
joints academia and industry efforts.
1st
task force
Expert WS
March 28th 2012
initial gap analysis
and roadmap outline
2nd Expert WS
July 19th 2012
.....
9
Multi-generation plan (MGP)
Preliminary draft
CO2 initiative
A multi-generation plan (MGP) by defining both the ‘ideal’ final
state and the key intermediate steps to reach it, and clustering the
current constraints into group.
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1/2
Resource and Energy Efficiency
in process industry
 a major issue not well addressed, but a critical element to
decrease the carbon and environmental footprint
 all methods based on the use of renewable energy source
produce electrical energy as output (except biomass) in a
discontinuous way
 Electrical energy does not well integrate into chemical
production, except as utility.
• chemical processes: based on the use of heat as the source of energy
for the chemical reaction, apart few processes
• In the chemical sector, on the average only 20% of the input energy is
used as electrical energy (including that generated on-site) to power
the various process units and for other services.
11
2/2
Resource and Energy Efficiency
in process industry
• Petroleum refining: only about 5% of the of the input energy is
used as electrical energy; less considering the raw materials.
• Solar thermal energy can be in principle used coupled with a
chemical reaction to provide the heat of reaction,
 but many technical problems to scaling-up this technology, between all
the impossibility to maintain 24h production and to guarantee uniform
temperature also are during the day.
• Discontinuity of renewable electrical energy production is also a
major drawback for the use of renewable energy in the chemical
production which requires constant power supply.
• To introduce renewable energy in the chemical production
chain it is necessary to convert renewable to chemical energy
and produce raw materials for chemical industry
12
Light olefin produc. and impact on CO2
• On the average, over 300 Mtons CO2 are produced to
synthetize light olefins worldwide
Specific Emission Factors (Mt CO2 /Mt Ethylene) in ethylene production
from different sources in Germany.
Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
13
Current methods of olefin production
Crude Oil
Gas Oil
Natural Gas
Naphtha
Butanes
Propane
Ethane
Coal
CO2
Biomass
Methane
H2
renewable
FCC
Steam Crackers
Dehydrogenation
ODH
Syngas
modified FT
Methanol
Ethanol
MTO
Butylenes
Butadiene
Propylene
Ethylene
• widen the possible sources to produce these base chemicals (moderate the
increase in their price, while maintaining the actual structure of value chain)
• In front of a significant increase in the cost of carbon sources for chemical
production in the next two decades, there are many constrains limiting the
use of oil-alternative carbon sources  use CO2 as carbon source
Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
14
CO2 to olefin (CO2TO) process
• Feedstock costs accounts for 70-80% of the
production costs
 the difference to 100% is the sum of fixed costs, other variable
costs (utilities such as electricity, water, etc.), capital depreciation
and other costs.
• In the CO2TO process the feedstock cost is related to
renewable H2
• CO2 is a feedstock with a negative cost (avoid C-taxes)
• Current ethylene and propylene prices range on the
average between 1200-1400 US$/ton
 for a renewable H2 cost ranging in the 2-3 US$/kg H2 range, the
CO2TO process may be
to current
production methods, in addition to advantages in terms of a better
sustainability.
Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
15
H2 from renewable energy sources
H2 production cost, US$/gge
10
4
6
1
Natural gas reforming
Ethanol reforming
Electrolysis
Central wind electrolysis
Biomass gasification
Nuclear
but strong
dependence on
local costs
H2 threshold cost
2
0
2005
•
•
•
•
•
3
5
2 6
1
2
3
4
5
6
2010
2015
year
2020
CH4 steam reforming: 8.9 kg CO2/kg H2
H2 from biomass: average 5-6 kg CO2/kg H2 (depends on many factors)
Wind/electrolysis: < 1 kg CO2/kg H2
Hydroelectric/electrolysis or solar thermal: around 2 kg CO2/kg H2
Photovoltaic/electrolysis: around 6 CO2/kg H2 (but lower for new technol.)
16
Hydrogen Production Cost Analysis
cost of producing
electrical energy in
some remote area
Electrical energy (wind) ($/kWh)
NREL
(actual data, April 2012)
0,12
0,08
0,04
breakthrough level
to become attracting produce chemicals
(olefins, methanol) from CO2
0,00
0
1
2
3
4
5
6
H2 production cost ($/kg)
For a cost of ee of 0,02 $/kWh (estimated production cost in remote areas which cannot
use locally ee, neither transport by grid) estimated production CH3OH cost is <300 €/ton
(current market value 350-400 €/ton)
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CO2 re-use scenario: produce CH3OH
using cheap ee in remote areas
An alternative (and more effective for chem. ind.) way to CCS
H2
CH3OH
H2
CH3OH
An efficient (and economic) way to introduce
renewable energy in the chemical production chain
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A CO2 roadmap
2012
2020
2030
excess electrical
energy (discont.,
remote,...)
ee
PEC
H2 prod.
(Conc. solar,
bioH2,...)
ee
electrolyzers
(PEM)
H2
inverse
(methanol)
FC
H2
G. Centi, S. Perathoner et al.,
ChemSusChem, 2012
catalysis
catalysis
CH3OH, DME,
olefins, etc.
artificial
leaves
CH3OH, DME,
olefins, etc.
CH3OH, DME,
olefins, etc.
distributed energy
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Inverse fuel cells
ee
Very limited studies
Specific (new) electrocatalysts have to be developed
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H2 solar cells
Co-oxygen
evolution catalyst
1 mm thickness
commercial triple
junction amorphous
silicon wafer
Ni mesh
Pt
3M
H2SO4
Ohmic contact
4H+ 
2H2
70 nm layer of
Indium Tin Oxide
2H2O 
O2 + 4H+
p-GaInP2
stainless
steel support
H2
O2
n-GaAs
1 M potassium
borate electrolyte
I
p-GaAs
NiMoZn
catalyst
Interconnet
Turner et al, Science 1998
12.4%.efficiency:
cost, stabiliy
Nocera et al, Science 2011
4-5%.efficiency
direct integration of a photovoltaic (PV) cell (operating in solution) with a modified
electrolysis device operating in acid medium (the device is not stable in basic medium)
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Toward artificial leaves
• 1st generation cell
• 2nd generation cell
active research, but still several
fundamental issues have to be solved
G. Centi, S. Perathoner et al.,
ChemSusChem, 2012
22
Conversion of CO2 through the use of
renewable energy sources
• CO2 chemical recycle
 key component for the strategies of chemical and energy industries
(exp. in Europe), to address resource efficiency
 CO2 to light olefins (C2=,C3=): possible reuse of CO2 as a valuable
carbon source and an effective way to introduce renewable energy
in the chemical industry value chain, improve resource efficiency and
limit GHG emissions;
 CO2 to methanol: an opportunity to use remote source of cheap
renewable energy and transport for the use in Europe (as raw
material) to increase resource and energy efficiency
 CO2 conversion in artificial leaves: still low productivity, but the way
to enable a smooth, but fast transition to a more sustainable energy
future, preserving actual energy infrastructure
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Further reading
Review on
CO2 uses
ChemSusChem,
2011, 4(9), 1265
Review on
artificial
leaves
ChemSusChem,
2012, 5(3), 500
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Current methods of light olefin product.
• Building blocks of petrochemistry
 but their production is the single most energy-consuming process
• Steam cracking accounted for about 3 ExaJ (1018)
primary energy use (inefficient use of energy, 60%)
Global ethylene + propylene market, MTons
300
250
200
other*
Syngas
150
ODH
Dehydrogenation
100
FCC
Steam cracking
50
0
2010
2020
Year
25
CO2 to light olefins - catalysts
rWGS
CO2 + ren. H2
Methanol
CO/H2 catalyst
Acid cat.
CH3OH (DME)
MTO
C2-C3 olefins
Modified FT catalysts
Hybrid catalysts for multisteps
• Ethylene and propylene have a positive standard energy of formation with
respect to H2, but water forms in the reaction (H2O(g) = -285.8 kJ/mol) and the
process do not need extra-energy with respect to that required to produce H2.
20 bar, 340°C, H2/CO=1; 64 h on stream
Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
Science 335, 835 (2012)
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PEM water electrolysis (for H2 product.)
• PEM water electrolysis
 Safe and efficient way to produce electrolytic H2
and O2 from renewable energy sources
 Stack efficiencies close to 80% have been obtained operating at
high current densities (1 A·cm-2) using low-cost electrodes and
high operating pressures (up to 130 bar)
 Developments that leaded to stack capital cost reductions:
• (i) catalyst optimization (50% loading reduction on anode, >90% reduction on
cathode), (ii) optimized design of electrolyzer cell, and (iii) 90% cost reduction
of the MEAs (membrane-electrode assembling) by fabricating
• Stability for over 60,000 hours of operation has been demonstrated in a
commercial stack.
Fixed O&M
 Electricity/feedstock is the key cost
component in H2 generation
Electrolyzer
stack
BOP
System
assembly
labor
Feedstock costs
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New routes for producing renewable H2
• bio-route using cyanobacteria or green algae
• high temperature thermochemical one using concentrated
solar energy
• photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
gH2/h.m2
0,3
The low temperature approach (PEC solar cell) has a greater
potential productivity in solar fuels per unit of area
illuminated AND may be used also for C-based energy vector
0,2
productivities in H2
formation from water
splitting per unit of surface
area irradiated
0,1
0
Bio-route
Conc. Thermal
Low-temp. (TiO2,
PEC reactor)
Centi,, Perathoner, ChemSusChem, 3 (2010) 195.
28
Solar fuels (energy vectors)
Greenhouse Gases: Science and Technology
(CO2-based energy vectors for the storage of solar energy)
Vol 1, Issue 1, (2011) 21
29
CO2 catalytic hydrogenation
• Formic acid is the simpler chemical produced by
hydrogenation of CO2 and that requiring less H2
 relevant parameter to consider is the ratio between
intrinsic energy content and amount of H2 incorporated
in the molecule, as well as safety aspects, storage,
etc.
Heat comb.,
kJ/mol
Heat comb/
mol H2
energy
density
vol, kJ/l
energy
density
wt., kJ/g
CO2 + H2
HCOOH
255
255
10,6
15,9
CO2 + 2H2
CH3OH + H2O
723
361
17,8
22,6
CO2 + 3H2
CH4 + 2H2O
892
297
16,0
13,1
use in chem. prod. is another parameter
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Energy vectors
• have both a high energy density by volume and by weight;
• be easy to store without a need for high pressure at room
temperature;
• be of low toxicity and safe to handle, and show limited risks in
their distributed (non-technical) use;
• show a good integration in the actual energy infrastructure
without the need of new dedicated equipment; and
• have a low impact on the environment in both their production
and their use.
• e-, H2, NH3, CO2-base energy vectors
CONCEPT Paper (Solar Fuels)
ChemSusChem, 2/2010 , 195-208
31