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Green CO2Green CO2
Univ Messina INSTM
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)
email centiunimeit
Gabriele CENTI
a key Element for Resource and Energy Efficiency in Process Industry
Industrial Symbiosis
Concert Hall - Aarhus21 June 2012
830-1000
CO2 initiative
2
IndustrialCouncil
European Research Institute of CatalysisEuropean Research Institute of CatalysisA 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
httpwwweric-aisbleu
Solvay
Total
eni Linde
BASF
Sasol
Mission
Bridge the gap between ideas and innovation Reinforce academiaindustry symbiosis
Develop common actionsprojects to open to new areasapplications opening market
opportunities
European Structured Research Areaon Catalysis and Magnetic Nanomaterials
CO2 initiative
3
Green Carbon DioxideGreen Carbon Dioxide
CO2 not a waste neither a resource for niche applications
but a key enabling element for the strategy towards resource and
energy efficiency in process industry
4
A changing scenarioA changing scenario
bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities
Towards a low-carbon economy
Responding to the triple challenge
FULLY
BALANCED
INTEGRATED
AND
MUTUALLY REINFORCED
Sustainable DevelopmentSustainable
Development
CompetitivenessCompetitiveness
Security of supply
Security of supply
G Centi et al
5
European strategy towards 2020European strategy towards 2020
Towards a low-carbon economy
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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 economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
2
IndustrialCouncil
European Research Institute of CatalysisEuropean Research Institute of CatalysisA 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
httpwwweric-aisbleu
Solvay
Total
eni Linde
BASF
Sasol
Mission
Bridge the gap between ideas and innovation Reinforce academiaindustry symbiosis
Develop common actionsprojects to open to new areasapplications opening market
opportunities
European Structured Research Areaon Catalysis and Magnetic Nanomaterials
CO2 initiative
3
Green Carbon DioxideGreen Carbon Dioxide
CO2 not a waste neither a resource for niche applications
but a key enabling element for the strategy towards resource and
energy efficiency in process industry
4
A changing scenarioA changing scenario
bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities
Towards a low-carbon economy
Responding to the triple challenge
FULLY
BALANCED
INTEGRATED
AND
MUTUALLY REINFORCED
Sustainable DevelopmentSustainable
Development
CompetitivenessCompetitiveness
Security of supply
Security of supply
G Centi et al
5
European strategy towards 2020European strategy towards 2020
Towards a low-carbon economy
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
3
Green Carbon DioxideGreen Carbon Dioxide
CO2 not a waste neither a resource for niche applications
but a key enabling element for the strategy towards resource and
energy efficiency in process industry
4
A changing scenarioA changing scenario
bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities
Towards a low-carbon economy
Responding to the triple challenge
FULLY
BALANCED
INTEGRATED
AND
MUTUALLY REINFORCED
Sustainable DevelopmentSustainable
Development
CompetitivenessCompetitiveness
Security of supply
Security of supply
G Centi et al
5
European strategy towards 2020European strategy towards 2020
Towards a low-carbon economy
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
4
A changing scenarioA changing scenario
bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities
Towards a low-carbon economy
Responding to the triple challenge
FULLY
BALANCED
INTEGRATED
AND
MUTUALLY REINFORCED
Sustainable DevelopmentSustainable
Development
CompetitivenessCompetitiveness
Security of supply
Security of supply
G Centi et al
5
European strategy towards 2020European strategy towards 2020
Towards a low-carbon economy
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
5
European strategy towards 2020European strategy towards 2020
Towards a low-carbon economy
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
Roadmap 2050 cost-efficientpathway and milestonesRoadmap 2050 cost-efficientpathway and milestones
httpeceuropaeuclimaroadmap2050
Energy efficiency
Renewables
Biomass
Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
7
Sustainable Process IndustrySustainable Process Industry
Industrial Competiveness through Resource and Energy Efficiency
bull 30 reduction in fossil energy intensity
bull 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
by 2030 from current levels
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
8
HowHow
Short term1-5y Mid term5-10y Long termgt10y
High
Medium
Low
Process intensification
Resource efficiency benchmarking
High effi ciency small scale production
Composite materials for automotive and
wind bladesLife Cycle Cost
Analysis Water Footprint
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 Effi cient biomass drying Algea based bio feedstock
Alternative fossil feedstock
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 bio-
chemicals Batteries Fuel cells CO2 as chemical building block Chemical
Energy Storage New catalysts
Lighting technologyCCS for plug in fossil
plants
New nontoxic non noble metal catalysts
PV Technology for organic synthesis
reactions
CO2valorisation Valorisation of waste Advanced Electrolysis
Organic PV
PRIORITY
Time line
Strategic technology roadmap
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
9
Cefic CO2 InitiativeCefic CO2 Initiative
bull 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
bull 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
bull Europe with itacutes excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts
March 28th 2012
1st Expert WStask force
initial gap analysis and roadmap outline
July 19th 2012
2nd Expert WS
CO2 initiative
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
10
Multi-generation plan (MGP) Multi-generation plan (MGP)
Preliminary draft
A multi-generation plan (MGP) by defining both the lsquoidealrsquo final state and the key intermediate steps to reach it and clustering the
current constraints into group
CO2 initiative
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
11
Resource and Energy EfficiencyResource and Energy Efficiency
bull How to introduce renewable energy in the energy and chemical production chain (30 target ) 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 bull chemical processes based on the use of heat as the source of energy
for the chemical reaction apart few processes bull 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
in process industry
12
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
12
Resource and Energy EfficiencyResource and Energy Efficiency
bull Petroleum refining only about 5 of the of the input energy is used as electrical energy less considering the raw materials
bull 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
bull 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
bull 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
in process industry
22
CO2 as raw material to introduce renewable energy in chem product chain
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
13
Light olefin produc and impact on CO2Light olefin produc and impact on CO2
bull 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
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
14
Current methods of olefin productionCurrent methods of olefin production
Butylenes
Coal
MethaneEthaneButanesNaphtha
Methanol
Natural GasCrude Oil
Biomass
CO2
Gas Oil
FCC Steam Crackers
Butadiene EthylenePropylene
Dehydrogenation Syngas modified FT
Propane
ODH
MTO
H2
renewable
Ethanol
bull widen the possible sources to produce these base chemicals (moderate the increase in their price while maintaining the actual structure of value chain)
bull 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
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
15
CO2 to olefin (CO2TO) processCO2 to olefin (CO2TO) process
bull 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
bull In the CO2TO process the feedstock cost is related to renewable H2
bull CO2 is a feedstock with a negative cost (avoid C-taxes)
bull 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$kg H2 range the CO2TO process may be economically competitive to current production methods in addition to advantages in terms of a better sustainability
Centi Iaquaniello Perathoner ChemSusChem 2011
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
16
H2 from renewable energy sourcesH2 from renewable energy sources
2005 2010 2015 2020
1
1 Natural gas reforming2 Ethanol reforming3 Electrolysis4 Central wind electrolysis5 Biomass gasification6 Nuclear2
3
4
56
10
6
2
0year
H2
prod
uctio
n co
st U
S$g
ge
H2 threshold cost
Carbon footprint (LCA analysis) for H2 production
bull CH4 steam reforming 89 kg CO2kg H2 bull H2 from biomass average 5-6 kg CO2kg H2 (depends on many factors) bull Windelectrolysis lt 1 kg CO2kg H2 bull Hydroelectricelectrolysis or solar thermal around 2 kg CO2kg H2
bull Photovoltaicelectrolysis around 6 CO2kg H2 (but lower for new technol)
but strong dependence on
local costs
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
17
Hydrogen Production Cost Analysis Hydrogen Production Cost Analysis
H2 production cost ($kg)
0 1 2 3 4 5 6
Ele
ctri
cal e
nerg
y (w
ind)
($
kW
h)
000
004
008
012
breakthrough levelto become attracting produce chemicals
(olefins methanol) from CO2
cost of producingelectrical energy in some remote area
For a cost of ee of 002 $kWh (estimated production cost in remote areas which cannot use locally ee neither transport by grid) estimated production CH3OH cost is lt300 euroton
(current market value 350-400 euroton)
ee + PEM electrolyzersNREL
(actual data April 2012)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
CO2 re-use scenario produce CH3OH using cheap ee in remote areasCO2 re-use scenario produce CH3OH using cheap ee in remote areas
CO2
CH3OH
An efficient (and economic) way to introduce renewable energy in the chemical production chain
H2
H2
CH3OH
CH3OH
An alternative (and more effective for chem ind) way to CCS
18
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
A CO2 roadmapA CO2 roadmap
19
2012 2020 2030
ee
excess electricalenergy (discont remote)
H2
CH3OH DME olefins etc
electrolyzers(PEM)
catalysis
in chemical industry to increase use of renewable energy
PECH2 prod(Conc solarbioH2)
H2
CH3OH DME olefins etc
catalysis
ee
inverse(methanol)
FC
CH3OH DME olefins etc
distributed energy
artificialleaves
G Centi S Perathoner et al ChemSusChem 2012
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
20
Inverse fuel cellsInverse fuel cells
ee
Very limited studiesSpecific (new) electrocatalysts have to be developed
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
21
H2 solar cellsH2 solar cells
stainlesssteel support
1 mm thicknesscommercial triple junction amorphous silicon wafer
70 nm layer of Indium Tin Oxide
Co-oxygenevolution catalyst
Ni mesh
NiMoZncatalyst
1 M potassium borate electrolyte
2H2O O2 + 4H+
4H+ 2H2
Nocera et al Science 2011
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)
I
Pt
p-G
aAs
n-G
aAs
p-G
aIn
P 2
Ohmic contact Interconnet
H2O2
3 M H2SO4
124efficiency cost stabiliy
Turner et al Science 1998
4-5efficiency
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
22
Toward artificial leavesToward artificial leavesbull 1st generation cell
bull 2nd generation cell
G Centi S Perathoner et al ChemSusChem 2012
active research but still several fundamental issues have to be solved
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
23
Conversion of CO2 through the use of renewable energy sourcesConversion of CO2 through the use of renewable energy sources
bull 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
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
24
Further readingFurther reading
ChemSusChem 2012 5(3) 500
ChemSusChem 2011 4(9) 1265
Review on CO2 uses
Review on artificial leaves
Green CO2Green CO2
Going to artificial leaves
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
25
Current methods of light olefin productCurrent methods of light olefin product
bull Building blocks of petrochemistry but their production is the single most energy-consuming process
bull Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy 60)
2010 20200
50
100
150
200
250
300
other
Syngas
ODH
Dehydrogenation
FCC
Steam cracking
Year
Glo
bal e
thyl
ene
+ pr
opyl
ene
mar
ket
MTo
ns
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
26
CO2 to light olefins - catalystsCO2 to light olefins - catalysts
bull Ethylene and propylene have a positive standard energy of formation with respect to H2 but water forms in the reaction (H2O(g) = -2858 kJmol) and the process do not need extra-energy with respect to that required to produce H2
CO2 + ren H2 COH2 CH3OH (DME)MTO
C2-C3 olefinsrWGS Methanol
catalyst
Acid cat
Modified FT catalysts
Hybrid catalysts for multisteps
Centi Iaquaniello Perathoner ChemSusChem 2011
Science 335 835 (2012)20 bar 340degC H2CO=1 64 h on stream
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
27
PEM water electrolysis (for H2 product) PEM water electrolysis (for H2 product)
bull 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 Acm-2) using low-cost electrodes and high operating pressures (up to 130 bar)
Developments that leaded to stack capital cost reductions bull (i) catalyst optimization (50 loading reduction on anode gt90 reduction on
cathode) (ii) optimized design of electrolyzer cell and (iii) 90 cost reduction of the MEAs (membrane-electrode assembling) by fabricating
bull Stability for over 60000 hours of operation has been demonstrated in a commercial stack
Electricityfeedstock is the key cost component in H2 generation
Feedstock costs
System assemblylabor
BOP
Electrolyzer stack
Fixed OampM
preferable current technology
Still space for electrode improvement but cost is depending on electricity cost
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
28
New routes for producing renewable H2New routes for producing renewable H2
bull bio-route using cyanobacteria or green algaebull high temperature thermochemical one using concentrated solar
energybull photo(electro)chemical water splitting or photoelectrolysis
using semiconductors
0
01
02
03
Bio-route Conc Thermal Low-temp (TiO2PEC reactor)
gH2hm2
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
Centi Perathoner ChemSusChem 3 (2010) 195
productivities in H2 formation from water
splitting per unit of surface area irradiated
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
29
Solar fuels (energy vectors) Solar fuels (energy vectors)
CO2
DR
CO + H2FT
CH3OH
HCOOH
+ H2
RWGS
+ CH4
+ H2
+ e- H+
FT Fischer TropschDR Dry reformingRWGS Reverse water gas shiftSR Sabatier reaction
Electrochemical routesChemical routes
-[CH2]n-
- H2O
- H2O
+ H2O
CH3OCH3
+ CH3OH- H2O
CH4
+ H2
- H2O
-[CH2]nOm-
gtC1 hydrocarbons
gtC1 alcohols
Diesel
Gasoline
SNG
Fuel cells
Fuel cells
Solar thermal routes(catalytic)
bioroutes
Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)
Vol 1 Issue 1 (2011) 21
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
CO2 catalytic hydrogenation CO2 catalytic hydrogenation
bull 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 kJmol
Heat comb mol H2
energy density vol kJl
energy density
wt kJg
CO2 + H2 HCOOH 255 255 106 159
CO2 + 2H2 CH3OH + H2O 723 361 178 226
CO2 + 3H2 CH4 + 2H2O 892 297 160 131
use in chem prod is another parameter
30
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)
Energy vectorsEnergy vectors
bull have both a high energy density by volume and by weightbull be easy to store without a need for high pressure at room
temperaturebull be of low toxicity and safe to handle and show limited risks in
their distributed (non-technical) usebull show a good integration in the actual energy infrastructure
without the need of new dedicated equipment andbull have a low impact on the environment in both their production
and their use
bull e- H2 NH3 CO2-base energy vectors
31ChemSusChem 22010 195-208
CONCEPT Paper (Solar Fuels)