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Univ. Messina INSTM European Research Institute of Catalysis (ERIC) Dip di Chimica Industriale ed Ingegneria dei Materiali, Univ. Messina, and CASPE (INSTM.

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Presentation on theme: "Univ. Messina INSTM European Research Institute of Catalysis (ERIC) Dip di Chimica Industriale ed Ingegneria dei Materiali, Univ. Messina, and CASPE (INSTM."— Presentation transcript:

1 Univ. Messina INSTM European Research Institute of Catalysis (ERIC) Dip di Chimica Industriale ed Ingegneria dei Materiali, Univ. Messina, and CASPE (INSTM Lab of Catalysis for Sustainable Prod and Energy) e:mail: Gabriele CENTI Concert Hall - Aarhus 21 June 2012 8:30-10:00

2 Industrial Council Industrial Council European Research Institute of Catalysis 2 A Virtual (non-profit) Institute, based in Belgium, gathering together 14 EU research and academic Institutions in the field of catalysis. Deriving from the EU Network of Excellence IDECAT Solvay Total eni Linde BASF Sasol.... Mission Bridge the gap between ideas and innovation Reinforce academia@industry symbiosis Develop common actions/projects to open to new areas/applications opening market opportunities European Structured Research Area on Catalysis and Magnetic Nanomaterials...... CO 2 initiative

3 Green Carbon Dioxide 3

4 A changing scenario Increase competitiveness in a global market whilst drastically reducing resource and energy inefficiency and environmental impact of industrial activities. 4 FULLYBALANCEDINTEGRATEDAND MUTUALLY REINFORCED Sustainable Development Competitiveness Security of supply G. Centi et al.

5 European strategy towards 2020 5

6 Roadmap 2050: cost-efficient pathway and milestones Energy efficiency Renewables Biomass Reducing greenhouse gas emissions by 80-95% by 2050 compared to 1990

7 Sustainable Process Industry 7 30% reduction in fossil energy intensity 20% reduction in non-renewable, primary raw material intensity Reduce CO 2 footprint reduction across the value chain Increased use in renewable feedstock Reduction in primary energy consumption Reduction in raw materials usage Doubling of average recycling rate across the value chain by 2030, from current levels

8 How? 8

9 Cefic CO 2 Initiative New breakthrough solutions need to be developed that will address the balance of CO 2 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 CO 2 using renewable energy sources. Capture and conversion of CO 2 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. 9 March 28 th 2012 1 st Expert WS task force initial gap analysis and roadmap outline July 19 th 2012 2 nd Expert WS..... CO 2 initiative

10 Multi-generation plan (MGP) 10 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. CO 2 initiative

11 Resource and Energy Efficiency 11 in process industry 1/2

12 Resource and Energy Efficiency Petroleum refining: only about 5% of the of the input energy is used as electrical energy; less considering the raw materials. Solar thermal energy can be in principle used coupled with a chemical reaction to provide the heat of reaction,  but many technical problems to scaling-up this technology, between all the impossibility to maintain 24h production and to guarantee uniform temperature also are during the day. Discontinuity of renewable electrical energy production is also a major drawback for the use of renewable energy in the chemical production which requires constant power supply. To introduce renewable energy in the chemical production chain it is necessary to convert renewable to chemical energy and produce raw materials for chemical industry 12 in process industry 2/2

13 Light olefin produc. and impact on CO 2 On the average, over 300 Mtons CO 2 are produced to synthetize light olefins worldwide 13 Specific Emission Factors (Mt CO 2 /Mt Ethylene) in ethylene production from different sources in Germany. Centi, Iaquaniello, Perathoner, ChemSusChem, 2011

14 Current methods of olefin production 14 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 CO 2 as carbon source Centi, Iaquaniello, Perathoner, ChemSusChem, 2011

15 CO 2 to olefin (CO 2 TO) process 15 Centi, Iaquaniello, Perathoner, ChemSusChem, 2011

16 H 2 from renewable energy sources 16 CH 4 steam reforming: 8.9 kg CO 2 /kg H 2 H 2 from biomass: average 5-6 kg CO 2 /kg H 2 (depends on many factors) Wind/electrolysis: < 1 kg CO 2 /kg H 2 Hydroelectric/electrolysis or solar thermal: around 2 kg CO 2 /kg H 2 Photovoltaic/electrolysis: around 6 CO 2 /kg H 2 (but lower for new technol.) but strong dependence on local costs

17 Hydrogen Production Cost Analysis 17 breakthrough level to become attracting produce chemicals (olefins, methanol) from CO 2 cost of producing electrical energy in some remote area For a cost of ee of 0,02 $/kWh (estimated production cost in remote areas which cannot use locally ee, neither transport by grid) estimated production CH 3 OH cost is <300 €/ton (current market value 350-400 €/ton) NREL (actual data, April 2012)

18 CO 2 re-use scenario: produce CH 3 OH using cheap ee in remote areas An efficient (and economic) way to introduce renewable energy in the chemical production chain H2H2 H2H2 CH 3 OH An alternative (and more effective for chem. ind.) way to CCS 18

19 A CO 2 roadmap 19 2012 2020 2030 ee excess electrical energy (discont., remote,...) H2H2 CH 3 OH, DME, olefins, etc. electrolyzers (PEM) catalysis PEC H 2 prod. (Conc. solar, bioH 2,...) H2H2 CH 3 OH, DME, olefins, etc. catalysis ee inverse (methanol) FC CH 3 OH, DME, olefins, etc. distributed energy artificial leaves G. Centi, S. Perathoner et al., ChemSusChem, 2012

20 Inverse fuel cells 20 ee Very limited studies Specific (new) electrocatalysts have to be developed

21 H 2 solar cells 21 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) 12.4%.efficiency: cost, stabiliy Turner et al, Science 1998 4-5%.efficiency

22 Toward artificial leaves 1 st generation cell 2 nd generation cell 22 G. Centi, S. Perathoner et al., ChemSusChem, 2012 active research, but still several fundamental issues have to be solved

23 Conversion of CO 2 through the use of renewable energy sources CO 2 chemical recycle  key component for the strategies of chemical and energy industries (exp. in Europe), to address resource efficiency  CO 2 to light olefins (C 2 =,C 3 = ): possible reuse of CO 2 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;  CO 2 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  CO 2 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 23

24 Further reading 24 ChemSusChem, 2012, 5(3), 500 ChemSusChem, 2011, 4(9), 1265 Review on CO 2 uses Review on artificial leaves

25 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 (10 18 ) primary energy use (inefficient use of energy,  60%) 25

26 CO 2 to light olefins - catalysts Ethylene and propylene have a positive standard energy of formation with respect to H 2, but water forms in the reaction (H 2 O(g) = -285.8 kJ/mol) and the process do not need extra-energy with respect to that required to produce H 2. 26 CO 2 + ren. H 2  CO/H 2 CH 3 OH (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, 340°C, H 2 /CO=1; 64 h on stream

27 PEM water electrolysis (for H 2 product.) PEM water electrolysis  Safe and efficient way to produce electrolytic H 2 and O 2 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 H 2 generation 27

28 New routes for producing renewable H 2 bio-route using cyanobacteria or green algae high temperature thermochemical one using concentrated solar energy photo(electro)chemical water splitting or photoelectrolysis using semiconductors 28 AND 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 H 2 formation from water splitting per unit of surface area irradiated

29 Solar fuels (energy vectors) 29 Greenhouse Gases: Science and Technology (CO 2 -based energy vectors for the storage of solar energy) Vol 1, Issue 1, (2011) 21

30 CO 2 catalytic hydrogenation Formic acid is the simpler chemical produced by hydrogenation of CO 2 and that requiring less H 2  relevant parameter to consider is the ratio between intrinsic energy content and amount of H 2 incorporated in the molecule, as well as safety aspects, storage, etc. Heat comb., kJ/mol Heat comb/ mol H 2 energy density vol, kJ/l energy density wt., kJ/g CO 2 + H 2  HCOOH255 10,615,9 CO 2 + 2H 2  CH 3 OH + H 2 O72336117,822,6 CO 2 + 3H 2  CH 4 + 2H 2 O89229716,013,1 use in chem. prod. is another parameter 30

31 Energy vectors have both a high energy density by volume and by weight; be easy to store without a need for high pressure at room temperature; be of low toxicity and safe to handle, and show limited risks in their distributed (non-technical) use; show a good integration in the actual energy infrastructure without the need of new dedicated equipment; and have a low impact on the environment in both their production and their use. e -, H 2, NH 3, CO 2 -base energy vectors 31 ChemSusChem, 2/2010, 195-208 CONCEPT Paper (Solar Fuels)

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