Electrofuels Electrochemistry as a tool for a sustainable biofuel synthesis
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1 Electrofuels Electrochemistry as a tool for a sustainable biofuel synthesis Uwe Schröder, Nachhaltige Chemie und Energieforschung, Institut für ökologische Chemie Uwe Schröder, Institut für Ökologische und Nachhaltige Chemie, Technische Universität Braunschweig 4th TMFB Conference, , Aachen
2 Electrochemistry today
3 Operation range / km Electrochemistry and mobility 500 > 500 Wh/kg 150 Li-Ion technology 200 Wh/kg Wh/kg Wh/kg 30 Wh/kg Lead battery Energy density Gasoline / diesel fuel: Wh/kg XY
4 Electrochemistry and energy storage e - e - Electrochemical energy storage
5 Electrochemistry and energy storage e - e - Fuels for combustion engines?
6 Electrochemistry and fuels H 2 O electrolysis H 2 C x H y CO 2 Power-to-gas/liquid Biomass components electrolysis C x H y This talk CO 2 electrolysis C x H y Microbial electrosynthesis
7 Electrosynthesis why? e - e - - No chemical oxidiser / reducer (e.g., H 2 ) - Electrons as immaterial agent - Room temperature conversion - Water as reaction medium - Direct energy storage into chemical bonds
8 Electrosynthesis - Possibilities e - e - Reduction Deoxygenation Hydrogenation Oxidation Dimerisation Decarboxylation
9 Electrofuels - Precursors Carbohydrate based platform chemicals Triglycerides 5-HMF Furfural Levulinic acid
10 Electrofuels Levulinic acid Levulinic acid +4H + + 4e - Valeric acid -H 2 O +2H + + 2e - g-valerolactone -H 2 O P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
11 [%] Electrofuels Levulinic acid g-valerolactone Valeric acid 80 Conversion Selectivity VA Selectivity gvl Coulombic efficiency C (a) Cu (a) Fe (a) Fe (b) Ni (a) Pb (a) Pb (b) T. R. dos Santos, P. Nilges, W. Sauter, F. Harnisch, U. Schröder; Electrochemistry for generation of renewable chemicals: Electrochemical conversion of levulinic acid; RSC Advances 5 (2015)
12 Electrofuels Levulinic acid Levulinic acid +4H + + 4e - Valeric acid -H 2 O Room temperature; lead electrode; aqueous, 0.5M H 2 SO 4 J. Tafel & B. Emmert, Z. Elektrochem.1911, 17, P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
13 Current denstiy (ma cm -2 ) Electrofuels Levulinic acid Hydrogen evolution is the main side reaction! 10 electrolyte 0-10 electrolyte + levulinic acid j reduction Potential / V Potential (V) P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
14 [%] Electrofuels Levulinic acid Hydrogen evolution is the main side reaction! 100 Conversion Selectivity VA Selectivity gvl Coulomb efficiency Valeric acid separation Initial concentration LA [M] T. R. dos Santos, P. Nilges, W. Sauter, F. Harnisch, U. Schröder; Electrochemistry for generation of renewable chemicals: Electrochemical conversion of levulinic acid; RSC Advances 5 (2015)
15 Electrofuels Levulinic acid Valeric acid 2-2H + - 2e - Octane -2CO 2 Room temperature; Pt electrode; ph 5.5 H. Kolbe, Justus Liebigs Ann. Chem., 1849, 69, P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
16 j (ma cm -2 ) Stromdichte (ma cm -2 ) Electrofuels Levulinic acid Solvents for the Kolbe-reaction: Methanol Water Potential (V) Potential (V) P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
17 Electrofuels Levulinic acid Water as reaction medium Organic product phase Aqueous reaction phase P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
18 Electrofuels Levulinic acid Side products 2-2e - -2CO 2-4e - -2CO 2-2e - -CO 2 +2OH - 2 P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
19 Electrofuels Levulinic acid 2 C (-2e -, -2H + -2CO 2 ) A (+8e -, +8H +, -2H 2 O) D (+8e -, +8H +, -2H 2 O) B 2 (-2e -, -2H + -2CO 2 ) P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
20 Electrofuels Levulinic acid T. R. dos Santos, P. Nilges, W. Sauter, F. Harnisch, U. Schröder; Electrochemistry for generation of renewable chemicals: Electrochemical conversion of levulinic acid; RSC Advances 5 (2015)
21 Electrofuels - Precursors Carbohydrate based platform chemicals Triglycerides 5-HMF Furfural Levulinic acid
22 Electrofuels - Furans
23 Electrofuels - Furans P. Nilges & U. Schröder; Electrochemistry for biofuel generation: Production of furans by electrocatalytic hydrogenation of furfurals; Energy and Environmental Science 6 (2013)
24 Electrofuels - Furans Furfural: Side reaction: P. Nilges & U. Schröder; Electrochemistry for biofuel generation: Production of furans by electrocatalytic hydrogenation of furfurals; Energy and Environmental Science 6 (2013)
25 Product selectivity Electrofuels - Furans Cu Ni Pt C Fe Pb Al Electrode material pinacol product furoic acid furfuryl alcohol methylfuran P. Nilges & U. Schröder; Electrochemistry for biofuel generation: Production of furans by electrocatalytic hydrogenation of furfurals; Energy and Environmental Science 6 (2013)
26 Electro-Fuels P. Nilges & U. Schröder; Electrochemistry for biofuel generation: Production of furans by electrocatalytic hydrogenation of furfurals; Energy and Environmental Science 6 (2013)
27 Electrofuels - Furans Lower heating value /kj mol -1 Average Furfural Furan Difference in molar heating values / kj mol -1 electrode potential / V* Number of electrons per mol (z) Molar electric energy / kj mol - 1 at 100% (and 50%) Coulomb Efficiency Furfural to MF Furfural MF V (656) 5-HMF to DMF 5-HMF DMF V (984) P. Nilges & U. Schröder; Electrochemistry for biofuel generation: Production of furans by electrocatalytic hydrogenation of furfurals; Energy and Environmental Science 6 (2013)
28 Electrofuels - Precursors Carbohydrate based platform chemicals 5-HMF Furfural Levulinic acid Triglycerides
29 Electrofuels Glycerol W. Sauter, O. Bergmann, U. Schröder; in preparation
30 Electrofuels Fatty acids Kolbe reaction -CO 2 9,25-Tetratriacontadiene Oleic acid -e - -2e - -CO 2 non-kolbe reaction T.R. dos Santos, F. Harnisch, P. Nilges, U. Schröder; Electrochemistry for biofuel generation: Transformation of fatty acids and triglycerides to diesel like olefin/ether mixture and olefins, ChemSusChem ,
31 Electrofuels Fatty acids Electrochemical decarboxylation in methanol T.R. dos Santos, F. Harnisch, P. Nilges, U. Schröder; Electrochemistry for biofuel generation: Transformation of fatty acids and triglycerides to diesel like olefin/ether mixture and olefins, ChemSusChem ,
32 Electrofuels Fatty acids Electrochemical decarboxylation in water Ultrasound electrochemistry T.R. dos Santos, F. Harnisch, P. Nilges, U. Schröder; Electrochemistry for biofuel generation: Transformation of fatty acids and triglycerides to diesel like olefin/ether mixture and olefins, ChemSusChem ,
33 Electrofuels Fatty acids Energetic evaluation of the electrochemical decarboxylation Method Products energy input / kj g -1 fuel energy output / kj g -1 NER c Biodiesel production Hydrotreating Fatty acid methyl-esters Alkanes Electroorganic synthesis 5V b (Aq_TG) 15V b (Org_FA) Alkenes Alkenes/ ethers (70:30) b cell voltage; c net energy ratio T.R. dos Santos, F. Harnisch, P. Nilges, U. Schröder; Electrochemistry for biofuel generation: Transformation of fatty acids and triglycerides to diesel like olefin/ether mixture and olefins, ChemSusChem ,
34 NEV (kj g -1 ) Electrofuels Fatty acids Energetic evaluation of the electrochemical decarboxylation 30 CE U R (V) T.R. dos Santos, F. Harnisch, P. Nilges, U. Schröder; Electrochemistry for biofuel generation: Transformation of fatty acids and triglycerides to diesel like olefin/ether mixture and olefins, ChemSusChem ,
35 Electrofuels Cell designs and operation N 2 WE RE CE
36 Electrofuels Cell designs and operation 2 2 P. Nilges, T. R. dos Santos, F. Harnisch, U. Schröder; Electrochemistry for biofuel generation: Electrochemical conversion of levulinic acid to octane; Energy and Environmental Science 5 (2012)
37 Matthias Pieschekck Tom P. Heins Robert Wagner Niklas Heiland Nicolar Schlüter Shuai Li Tatiane dos Santos Olaf Bergmann Dr. Olusola James Camilla Rohr Sebastian Riedl Robert Brown Jonas M. S. Andrich André Baudler Hilke S. Wiedenroth Microbial Electrochemistry Team Anode Cathode H +,CO 2 H 2O Air e - e - Substrate (Fuel) H + H + O 2 Christopher Moß Igor Schmidt Biofuel & Electrosynthesis Team Waldemar Sauter BatteryTeam Nina Bruchmann
38 Seite 38 Thank you!
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