Univ Messina INSTM

Dip di Chimica Industriale ed Ingegneria dei Materiali Univ Messina and CASPE (INSTM Lab of Catalysis for Sustainable Prod and Energy)

email centiunimeit perathonunimeit

Gabriele CENTI e Siglinda PERATHONER

CO2 DA PROBLEMA A RISORSA Lrsquoesperienza italiana

ENEA ndash Sede Centrale 18 Giugno 2012

GHG is the only motivation for CO2 The 450 ppm scenario

Use of CO2 may give a significant contribution

2

severe concerns in several countries about CCS

CO2 use (CCU) vs CCS GHG impact factor 3

A Quadrelli G Centi et al ChemSusChem 2011 4 1194 ndash 1215

Impact value on GHG over 20 years

0 2 4 6 8 10 12 14 16 18 20

CCS

CO2 mineralization

CO2 polymers

CO2 to olefins

CO2 to fuels

The effective potential of CCU (carbon capture and use) technologies in GHG control is at least similar to that of CCS technologies and estimated to be around around 250ndash

350 Mt∙y-1 in the short- to medium-term

1

CCU vs CCS bull Lutilizzo della CO2 (CCU) rispetto allo stoccaggio (CCS)

non egrave alternativo ma complementare quando le sorgenti di emissioni sono distanti da quelle di

stoccaggio (od esistono altre motivazioni quali sociali ecc per evitare lo stoccaggio)

le sorgenti di emissioni non hanno volumi compatibili con lo stoccaggio

sono disponibili sorgenti pure concentrate (ad es da CPO NH3 sintesi bioetanolo ecc) di cui puograve essere utile lutilizzo

bull senza conv ( microalghe) bull con conv (chimica)

4

5

Pathways for CO2 use E

nerg

y

CO2

CO3=

formation C-O bond

inorg carbonate

CO

C (Hx)

rupture C-O bonds

supply energy or react with high energy molecules

- materials (epoxides monomers) - fuels base chemicals

(H2 energy renew)

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

GHG is the only motivation for CO2 The 450 ppm scenario

Use of CO2 may give a significant contribution

2

severe concerns in several countries about CCS

CO2 use (CCU) vs CCS GHG impact factor 3

A Quadrelli G Centi et al ChemSusChem 2011 4 1194 ndash 1215

Impact value on GHG over 20 years

0 2 4 6 8 10 12 14 16 18 20

CCS

CO2 mineralization

CO2 polymers

CO2 to olefins

CO2 to fuels

The effective potential of CCU (carbon capture and use) technologies in GHG control is at least similar to that of CCS technologies and estimated to be around around 250ndash

350 Mt∙y-1 in the short- to medium-term

1

CCU vs CCS bull Lutilizzo della CO2 (CCU) rispetto allo stoccaggio (CCS)

non egrave alternativo ma complementare quando le sorgenti di emissioni sono distanti da quelle di

stoccaggio (od esistono altre motivazioni quali sociali ecc per evitare lo stoccaggio)

le sorgenti di emissioni non hanno volumi compatibili con lo stoccaggio

sono disponibili sorgenti pure concentrate (ad es da CPO NH3 sintesi bioetanolo ecc) di cui puograve essere utile lutilizzo

bull senza conv ( microalghe) bull con conv (chimica)

4

5

Pathways for CO2 use E

nerg

y

CO2

CO3=

formation C-O bond

inorg carbonate

CO

C (Hx)

rupture C-O bonds

supply energy or react with high energy molecules

- materials (epoxides monomers) - fuels base chemicals

(H2 energy renew)

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

CO2 use (CCU) vs CCS GHG impact factor 3

A Quadrelli G Centi et al ChemSusChem 2011 4 1194 ndash 1215

Impact value on GHG over 20 years

0 2 4 6 8 10 12 14 16 18 20

CCS

CO2 mineralization

CO2 polymers

CO2 to olefins

CO2 to fuels

The effective potential of CCU (carbon capture and use) technologies in GHG control is at least similar to that of CCS technologies and estimated to be around around 250ndash

350 Mt∙y-1 in the short- to medium-term

1

CCU vs CCS bull Lutilizzo della CO2 (CCU) rispetto allo stoccaggio (CCS)

non egrave alternativo ma complementare quando le sorgenti di emissioni sono distanti da quelle di

stoccaggio (od esistono altre motivazioni quali sociali ecc per evitare lo stoccaggio)

le sorgenti di emissioni non hanno volumi compatibili con lo stoccaggio

sono disponibili sorgenti pure concentrate (ad es da CPO NH3 sintesi bioetanolo ecc) di cui puograve essere utile lutilizzo

bull senza conv ( microalghe) bull con conv (chimica)

4

5

Pathways for CO2 use E

nerg

y

CO2

CO3=

formation C-O bond

inorg carbonate

CO

C (Hx)

rupture C-O bonds

supply energy or react with high energy molecules

- materials (epoxides monomers) - fuels base chemicals

(H2 energy renew)

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

CCU vs CCS bull Lutilizzo della CO2 (CCU) rispetto allo stoccaggio (CCS)

non egrave alternativo ma complementare quando le sorgenti di emissioni sono distanti da quelle di

stoccaggio (od esistono altre motivazioni quali sociali ecc per evitare lo stoccaggio)

le sorgenti di emissioni non hanno volumi compatibili con lo stoccaggio

sono disponibili sorgenti pure concentrate (ad es da CPO NH3 sintesi bioetanolo ecc) di cui puograve essere utile lutilizzo

bull senza conv ( microalghe) bull con conv (chimica)

4

5

Pathways for CO2 use E

nerg

y

CO2

CO3=

formation C-O bond

inorg carbonate

CO

C (Hx)

rupture C-O bonds

supply energy or react with high energy molecules

- materials (epoxides monomers) - fuels base chemicals

(H2 energy renew)

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

5

Pathways for CO2 use E

nerg

y

CO2

CO3=

formation C-O bond

inorg carbonate

CO

C (Hx)

rupture C-O bonds

supply energy or react with high energy molecules

- materials (epoxides monomers) - fuels base chemicals

(H2 energy renew)

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

The energy value of CO2 conv products 6

0

-100

-200

-300

-400

-500

∆H

deg (k

J m

ol-1

)

CO2

CH3OH H2O

H2

CO

CH4

Break C-O bond

renewable H2

Formation of a C-O bond

Inorganic carbonate ExNaCO3

Fuels chemicals

paper industry paint products building

materials hellip

ethene carbonate

Ethene oxide

Materials (CO2 polymers)

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Roadmap 2050 cost-efficient pathway and milestones

httpeceuropaeuclimaroadmap2050

Energy efficiency

Renewables

Biomass

Reducing greenhouse gas emissions by 80-95 by 2050 compared to 1990

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Sustainable Process Industry

8

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

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

How

9

Short term1-5y Mid term5-10y Long termgt10y

High

Medium

Low

Process intensification

Resource efficiency benchmarking

High efficiency 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 Efficient 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

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Cefic 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

10

March 28th 2012 1st Expert WS

task force

initial gap analysis and roadmap outline

July 19th 2012

2nd Expert WS

CO2 initiative

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Multi-generation plan (MGP)

11

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

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Resource and Energy Efficiency

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

12

in process industry

12

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Resource 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

13

in process industry

22

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Light olefin produc and impact on CO2

bull On the average over 300 Mtons CO2 are produced to synthetize light olefins worldwide

14

Specific Emission Factors (Mt CO2 Mt Ethylene) in ethylene production from different sources in Germany

Centi Iaquaniello Perathoner ChemSusChem 2011

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Current methods of olefin production

15

Butylenes

Coal

MethaneEthaneButanesNaphtha

Methanol

Natural GasCrude Oil

Biomass

CO2

Gas Oil

FCC Steam Crackers

Butadiene EthylenePropylene

Dehydrogenation Syngas modified FT

Propane

ODH

MTO

H2renewable

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

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

CO2 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

16

CO2 + ren H2 COH2 CH3OH (DME) MTO C2-C3 olefins

rWGS 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

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

CO2 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 to current production methods in addition to advantages in terms of a better sustainability

17 Centi Iaquaniello Perathoner ChemSusChem 2011

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

H2 from renewable energy sources

18

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

H 2pr

oduc

tion

cost

US$

gge

H2 threshold cost

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

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Hydrogen Production Cost Analysis

19

H2 production cost ($kg)

0 1 2 3 4 5 6

Elec

trica

l ene

rgy

(win

d) ($

kW

h)

000

004

008

012

breakthrough level to become attracting produce chemicals

(olefins methanol) from CO2

cost of producing electrical 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)

NREL (actual data April 2012)

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Solar fuels (energy vectors)

20

Greenhouse Gases Science and Technology (CO2-based energy vectors for the storage of solar energy)

Vol 1 Issue 1 (2011) 21

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

CO2 re-use scenario produce CH3OH using cheap ee in remote areas

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

21

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

A CO2 roadmap

22

2012 2020 2030

ee

excess electrical energy (discont remote)

H2

CH3OH DME olefins etc

electrolyzers (PEM)

catalysis

PEC H2 prod (Conc solar bioH2)

H2

CH3OH DME olefins etc

catalysis

ee

inverse (methanol)

FC

CH3OH DME olefins etc

distributed energy

artificial leaves

G Centi S Perathoner et al ChemSusChem 2012

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Inverse fuel cells

23

ee

Very limited studies Specific (new) electrocatalysts have to be developed

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

H2 solar cells

24

stainlesssteel support

1 microm 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 rarrO2 + 4H+

4H+ rarr2H2

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-Ga

As

n-Ga

As

p-Ga

InP 2

Ohmic contact Interconnet

H2O2

3 M H2SO4

124efficiency cost stabiliy

Turner et al Science 1998

4-5efficiency

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Toward artificial leaves bull 1st generation cell

bull 2nd generation cell

25 G Centi S Perathoner et al

ChemSusChem 2012

active research but still several fundamental issues have to be solved

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Conversion 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

26

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Further reading

27

ChemSusChem 2012 5(3) 500

ChemSusChem 2011 4(9) 1265

Review on CO2 uses

Review on artificial leaves

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

A changing scenario

bull Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities

28

FULLY BALANCED

INTEGRATED AND

MUTUALLY REINFORCED

Sustainable Development

Competitiveness

Security of supply

G Centi et al

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

European strategy towards 2020

29

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Green Carbon Dioxide

30

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Current 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)

31

0

50

100

150

200

250

300

2010 2020

Glo

bal e

thyl

ene

+ pr

opyl

ene

mar

ket

MTo

ns

Year

other

Syngas

ODH

Dehydrogenation

FCC

Steam cracking

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

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

32 Feedstock costs

System assemblylabor

BOP

Electrolyzer stack

Fixed OampM

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

New routes for producing renewable H2

bull bio-route using cyanobacteria or green algae bull high temperature thermochemical one using concentrated

solar energy bull photo(electro)chemical water splitting or photoelectrolysis

using semiconductors

33

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

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

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

34

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors

Energy vectors

bull have both a high energy density by volume and by weight bull be easy to store without a need for high pressure at room

temperature bull be of low toxicity and safe to handle and show limited risks in

their distributed (non-technical) use bull show a good integration in the actual energy infrastructure

without the need of new dedicated equipment and bull have a low impact on the environment in both their production

and their use

bull e- H2 NH3 CO2-base energy vectors

35 ChemSusChem 22010 195-208

CONCEPT Paper (Solar Fuels)

• Strategie e motivazioni allrsquouso della CO2
• 450 ppm energy scenario
• CO2 use (CCU) vs CCS GHG impact factor
• CCU vs CCS
• Pathways for CO2 use
• The energy value of CO2 conv products
• Roadmap 2050 cost-efficientpathway and milestones
• Sustainable Process Industry
• How
• Cefic CO2 Initiative
• Multi-generation plan (MGP)
• Resource and Energy Efficiency
• Resource and Energy Efficiency
• Light olefin produc and impact on CO2
• Current methods of olefin production
• CO2 to light olefins - catalysts
• CO2 to olefin (CO2TO) process
• H2 from renewable energy sources
• Hydrogen Production Cost Analysis
• Solar fuels (energy vectors)
• Diapositiva numero 21
• A CO2 roadmap
• Inverse fuel cells
• H2 solar cells
• Toward artificial leaves
• Conversion of CO2 through the use of renewable energy sources
• Further reading
• A changing scenario
• European strategy towards 2020
• Green Carbon Dioxide
• Current methods of light olefin product
• PEM water electrolysis (for H2 product)
• New routes for producing renewable H2
• CO2 catalytic hydrogenation
• Energy vectors