Concert Hall - Aarhus 21 June 2012 8:30-10:00 Industrial Symbiosis Green CO2 a key Element for Resource and Energy Efficiency in Process Industry Gabriele CENTI EuropeanResearchInstitute of Catalysis (ERIC) Dipdi Chimica Industriale ed Ingegneria dei Materiali, Univ. Messina, and CASPE (INSTM Lab of Catalysis for SustainableProd and Energy)e:mail: firstname.lastname@example.org Univ. Messina INSTM
EuropeanResearchInstitute of Catalysis A Virtual (non-profit) Institute, based in Belgium, gatheringtogether 14 EU research and academicInstitutions in the field of catalysis. Deriving from the EU Network of Excellence IDECAT Industrial Council .... Solvay Sasol Mission Total BASF Bridge the gap betweenideas and innovation Reinforceacademia@industrysymbiosis Develop common actions/projects to open to new areas/applications opening market opportunities eni Linde ...... CO2 initiative EuropeanStructuredResearch Area on Catalysis and MagneticNanomaterials http://www.eric-aisbl.eu/
Green Carbon Dioxide CO2 not a waste, neither a resource for niche applications, but a key enabling element for the strategy towards resource and energy efficiency in process industry
Towards a low-carbon economy A changing scenario Responding to the triple challenge Competitiveness FULLY BALANCED INTEGRATED AND MUTUALLY REINFORCED G. Centi et al. Sustainable Development Security of supply Increase competitivenessin a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities.
European strategy towards 2020 Towards a low-carbon economy
Roadmap 2050: cost-efficientpathway and milestones Reducing greenhouse gas emissions by 80-95% by 2050 compared to 1990 Energy efficiency Renewables Biomass http://ec.europa.eu/clima/roadmap2050/
SustainableProcessIndustry • Industrial Competivenessthrough Resource and Energy Efficiency • by 2030, from current levels • 30% reduction in fossil energy intensity • 20% reduction in non-renewable, primary raw material intensity • Reduce CO2footprint 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
Cefic CO2 Initiative CO2 initiative task force 2nd Expert WS 1st Expert WS ..... initial gap analysis and roadmap outline March 28th 2012 July 19th2012 New breakthrough solutions need to be developed that will address the balance of CO2 in the Earth atmosphere and at the same time provide us with the needed resources. A visionary way to go would be to achieve full circle recycling of CO2 using renewable energy sources. Capture and conversion of CO2 to chemical feedstock could provide new route to a circular economy. Europe with it´s excellent research and industrial landscape can be a key player for such a visionary approach in which joints academia and industry efforts.
Multi-generation plan (MGP) CO2 initiative Preliminary draft A multi-generation plan (MGP) by defining both the ‘ideal’ final state and the key intermediate steps to reach it, and clustering the current constraints into group.
1/2 Resource and Energy Efficiency in process industry • How to introduce renewable energy in the energy and chemical production chain (30% target ?) • a major issue not well addressed, but a critical element to decrease the carbon and environmental footprint • all methods based on the use of renewable energy source produce electrical energy as output (except biomass) in a discontinuous way • Electrical energy does not well integrate into chemical production, except as utility. • chemical processes: based on the use of heat as the source of energy for the chemical reaction, apart few processes • In the chemical sector, on the average only 20% of the input energy is used as electrical energy (including that generated on-site) to power the various process units and for other services.
2/2 Resource and Energy Efficiency in process industry CO2 as raw material to introduce renewable energy in chem. product. chain • Petroleum refining: only about 5% of the of the input energy is used as electrical energy; less considering the raw materials. • Solar thermal energy can be in principle used coupled with a chemical reaction to provide the heat of reaction, • but many technical problems to scaling-up this technology, between all the impossibility to maintain 24h production and to guarantee uniform temperature also are during the day. • Discontinuity of renewable electrical energy production is also a major drawback for the use of renewable energy in the chemical production which requires constant power supply. • To introduce renewable energy in the chemical production chain it is necessary to convert renewable to chemical energy and produce raw materials for chemical industry
Light olefinproduc. and impact on CO2 Specific Emission Factors (Mt CO2 /Mt Ethylene) in ethylene production from different sources in Germany. Centi, Iaquaniello, Perathoner, ChemSusChem, 2011 On the average, over 300 Mtons CO2 are produced to synthetize light olefinsworldwide
Current methods of olefin production • widen the possible sources to produce these base chemicals (moderate the increase in their price, while maintaining the actual structure of value chain) • In front of a significant increase in the cost of carbon sources for chemical production in the next two decades, there are many constrains limiting the use of oil-alternative carbon sources use CO2 as carbon source Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
CO2 to olefin (CO2TO) process • Feedstock costs accounts for 70-80% of the production costs • the difference to 100% is the sum of fixed costs, other variable costs (utilities such as electricity, water, etc.), capital depreciation and other costs. • In the CO2TO process the feedstock cost is related to renewable H2 • CO2is a feedstock with a negative cost (avoid C-taxes) • Current ethylene and propylene prices range on the average between 1200-1400 US$/ton • for a renewable H2 cost ranging in the 2-3 US$/kg H2 range, the CO2TO process may be economically competitive to current production methods, in addition to advantages in terms of a better sustainability. Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
H2 from renewable energy sources but strong dependence on local costs Carbon footprint (LCA analysis) for H2 production • CH4 steam reforming: 8.9 kg CO2/kg H2 • H2from biomass: average 5-6 kg CO2/kg H2(depends on many factors) • Wind/electrolysis: < 1 kg CO2/kg H2 • Hydroelectric/electrolysis or solar thermal: around 2 kg CO2/kg H2 • Photovoltaic/electrolysis: around 6 CO2/kg H2(but lower for new technol.)
Hydrogen Production Cost Analysis NREL (actual data, April 2012) ee + PEM electrolyzers 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 0,02 $/kWh (estimated production cost in remote areaswhichcannotuse locallyee, neithertransport by grid) estimated production CH3OH costis <300 €/ton (current market value 350-400 €/ton)
CO2 re-use scenario: produce CH3OH using cheap ee in remote areas An alternative (and more effective for chem. ind.) way to CCS CH3OH CO2 H2 CH3OH H2 An efficient (and economic) way to introduce renewable energy in the chemical production chain CH3OH 18
A CO2roadmap 2012 2020 2030 excesselectrical energy (discont., remote,...) artificial leaves PEC H2prod. (Conc. solar, bioH2,...) ee ee electrolyzers (PEM) inverse(methanol) FC H2 H2 G. Centi, S. Perathoner et al., ChemSusChem, 2012 catalysis catalysis CH3OH, DME, olefins, etc. CH3OH, DME, olefins, etc. CH3OH, DME, olefins, etc. distributedenergy in chemicalindustryto increase use of renewableenergy
Inverse fuel cells ee Verylimitedstudies Specific (new) electrocatalystshave to be developed
H2 solar cells Turner et al, Science 1998 12.4%.efficiency: cost, stabiliy Nocera et al, Science 2011 4-5%.efficiency directintegration of a photovoltaic (PV) cell (operating in solution) with a modifiedelectrolysisdeviceoperating in acid medium (the deviceisnotstable in basicmedium)
Toward artificial leaves active research, but still several fundamental issues have to be solved G. Centi, S. Perathoner et al., ChemSusChem, 2012 1st generation cell 2nd generation cell
Conversion of CO2 through the use of renewable energy sources • CO2 chemical recycle • key component for the strategies of chemical and energy industries (exp. in Europe), to address resource efficiency • CO2 to light olefins (C2=,C3=): possible reuse of CO2 as a valuable carbon source and an effective way to introduce renewable energy in the chemical industry value chain, improve resource efficiency and limit GHG emissions; • CO2 to methanol: an opportunity to use remote source of cheap renewable energy and transport for the use in Europe (as raw material) to increase resource and energy efficiency • CO2 conversion in artificial leaves: still low productivity, but the way to enable a smooth, but fast transition to a more sustainable energy future, preserving actual energy infrastructure
Further reading Review on artificial leaves Review on CO2 uses ChemSusChem, 2012, 5(3), 500 ChemSusChem, 2011, 4(9), 1265 Green CO2 Going to artificialleaves
Current methods of light olefin product. • Building blocks of petrochemistry • but their production is the single most energy-consuming process • Steam cracking accounted for about 3 ExaJ (1018) primary energy use (inefficient use of energy, 60%)
CO2 to light olefins - catalysts Acid cat. rWGS Methanol catalyst MTO C2-C3 olefins CO2 + ren. H2 CO/H2 CH3OH (DME) Modified FT catalysts Hybridcatalysts for multisteps 20 bar, 340°C, H2/CO=1; 64 h on stream Science 335, 835 (2012) Ethylene and propylene have a positive standard energy of formation with respect to H2, but water forms in the reaction (H2O(g) = -285.8 kJ/mol) and the process do not need extra-energy with respect to that required to produce H2. Centi, Iaquaniello, Perathoner, ChemSusChem, 2011
PEM water electrolysis (for H2product.) preferablecurrenttechnology Stillspace for electrodeimprovement, but costisdepending on electricitycost • PEM water electrolysis • Safe and efficient way to produce electrolytic H2and O2 from renewable energy sources • Stack efficiencies close to 80% have been obtained operating at high current densities (1 A·cm-2) using low-cost electrodes and high operating pressures (up to 130 bar) • Developments that leaded to stack capital cost reductions: • (i) catalyst optimization (50% loading reduction on anode, >90% reduction on cathode), (ii) optimized design of electrolyzer cell, and (iii) 90% cost reduction of the MEAs (membrane-electrode assembling) by fabricating • Stability for over 60,000 hours of operation has been demonstrated in a commercial stack. • Electricity/feedstock is the key cost component in H2 generation
New routes for producingrenewable H2 The low temperature approach (PEC solar cell) has a greater potential productivity in solar fuels per unit of areailluminatedANDmay be usedalso for C-basedenergyvector productivities in H2 formation from water splitting per unit of surface area irradiated bio-route using cyanobacteria or green algae high temperature thermochemical one using concentrated solar energy photo(electro)chemical water splitting or photoelectrolysis using semiconductors Centi,, Perathoner, ChemSusChem, 3 (2010) 195.
Solar fuels (energyvectors) Greenhouse Gases: Science and Technology (CO2-based energy vectors for the storage of solar energy) Vol 1, Issue 1, (2011) 21
CO2 catalytic hydrogenation use in chem. prod. is another parameter • 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. 30
Energy vectors CONCEPT Paper (Solar Fuels) have both a high energy density by volume and by weight; be easy to store without a need for high pressure at room temperature; be of low toxicity and safe to handle, and show limited risks in their distributed (non-technical) use; show a good integration in the actual energy infrastructure without the need of new dedicated equipment; and have a low impact on the environment in both their production and their use. e-, H2, NH3, CO2-base energy vectors ChemSusChem, 2/2010 , 195-208