CERTH DIESEL SUSTAINABILITY IMPROVEMENT PERSPECTIVES BY INCORPORATION OF WASTE COOKING OIL IN EXISTING REFINERY OF THESSALONIKI Stella Bezergianni, Athanasios Dimitriadis, Loukia Chrysikou Laboratory of Environmental Fuels and Hydrocarbons (LEFH) Chemical Processes and Energy Sources Institute (CPERI) Centre for Research and Technology Hellas (CERTH) 5th International Scientific Conference on "Energy and Climate Change", Athens, October 11, 2012

Biomass for Biofuels Renewable Low H/C ratio Contains water Corrosion problems High oxygen content (aldehydes, acids, cetones) Reduced heating value Reduced oxidation stability Increased acidity Engine performance problems Biomass requires H/C and removal of Ο and Η2Ο

Why Catalytic Hydrotreating? Widespread conversion technology for diesel and gasoline upgrading H/C ratio increase Heteroatom (S, N, O) and metals removal High conversion Feedstock variability No by-products Application in numerous refineries globally Utilization for green diesel production from vegetable oils NExBTL, Ecofining, Vegan 3

Why Waste Cooking Oil (WCO)? Available feedstock from restaurants and households 280,000m3 (conservative estimation) Problematic disposal Sewage, sanitary landfills Part of WCO used for biodiesel production via transesterification technology Reduces biodiesel (FAME) quality Potential to cover a significant portion of Greek biodiesel production in Greece Currently FAME requirements ~ 150,000m3 FAME (6.5% diesel) 5

Waste Cooking Oil  Diesel-2G 2nd Innovation Award Better combustion (increased cetane) More economic (high HHV) More stable (no TAN, high IP) Sustainable  + Η2 catalyst ? Large-scale units require large investments Potential to cover 9,5% of Greek diesel demand Τηγανέλαιο Πυκνότητα = 0,89 gr/ml H/C = 0,15 O = 12%wt Βιοντίζελ-2G Πυκνότητα = 0,7904 gr/ml H/C = 0,18 O = 0,3%wt Θείο = 1.54 wppm Δείκτης κετανίου = 77.23 Σημείο ανάφλεξης = 116ºC Ιξώδες (40ºC)=3.54 cst H2O = 0.0013% wt ΤΑΝ = 0 mg KOH/g Οξειδωτική σταθ. > 22hr CFPP = 20ºC Σύσταση υδρ/κων Παραφίνες (C15 – C18) Κύκλο-παραφίνες Ολεφίνες = 0%wt Αρωματικά=0%wt www.biofuels2g.gr

SustainDiesel Project Aim: Improvement of diesel sustainability by incorporating WCO and RES in existing refinery Project duration: 23.3.2011 – 22.3.2014 Partners: Coordinator: Centre for Research & Technology Hellas (CERTH) Academic partners: Aristotle University of Thessaloniki & National Technical University of Athens Industrial partners: Hellenic Petroleum & Sunlight S.A. Financing: Program Competitiveness (ESPA) with funds from EU and Greek Government

SustainDiesel Technology Overview Emissions Evaluate technical feasibility of incorporating WCO as alternative feedstock for diesel production Same infrastructure & operation Assess carbon footprint and GHG emissions improvement versus current market diesel Emissions Refinery Other products Crude oil Diesel WCO H2 from RES FAME Energy

A. Technical Feasibility Evaluation of hydrotreating catalyst Determine optimal operating conditions T, P, Η2/oil, LHSV Determine max WCO mixing ratio Evaluate emissions & engine performance   9

 Evaluation of Catalyst Two catalyst types examined NiMo & CoMo For HDT of fossil feedstocks optim CoMo For HDT fossil + WCO feedstocks optim NiMo

 Determine Optimal Conditions All operating parameters examined T, P, H2/oil, LHSV Operating window as defined by the refinery Optimal operating parameters defined based on maximum diesel yield and quality

Effect of WCO on HDT WCO affects positively HDT of fossil fractions (HAGO) Diesel yield is favored for increasing WCO Effect of WCO in diesel quality is positive Product sulfur is unaffected by WCO presence Denitrogenation is favored by WCO

B. Sustainability Analysis Aims: Evaluation of carbon foot-print and GHG emissions of current diesel production technology Evaluation of sustainability improvements by incorporating WCO and H2 from RES Tools: GEMIS software (edition 4.7) Refinery data for GHG emissions, origin of feedstocks and energy requirements Experimental data for proposed integration of WCO and H2 from RES

Current Diesel Production Pathway FAME (biodiesel) production Energy crops cultivation Transportation to biorefinery Transportation to refinery Biodiesel Production Crude oil extraction Crude oil transportation Refining process Diesel transportation to gas stations Fuel combustion

Preliminary Results Current Diesel Production Proposed WCO incorporation* Diesel emissions 0.556 kg eq-CO2/kg 0.438 kg eq-CO2/kg Total refinery emissions 2,057 Mt eq-CO2/yr 1,617 Mt eq-CO2/yr * Calculations are based on substituting 30% of fossil fraction (HAGO) with WCO Expected reduction of GHG emissions by 21.4%

Next Steps Evaluation of maximum WCO ratio that can be incorporated in existing refinery Assessment of maximum potential GHG emission benefits by incoporating WCO and H2 from RES Economic feasibility analysis

«...ἐν τῷ γνωστῷ τελευταία ἡ τοῦ ἀγαθοῦ ἰδέα καὶ μόγις ὁρᾶσθαι, ὀφθεῖσα δὲ συλλογιστέα εἶναι ὡς ἄρα πᾶσι πάντων αὕτη ὀρθῶν τε καὶ καλῶν αἰτία,...» [Πλάτων, Πολιτεία 514-521] (427-347 BC) “...in the sphere of knowledge, the ultimate and most difficult idea is that of virtue, but if this becomes visible it can be the cause of everything right and benign affecting our lives…” [Plato, The Republic 514-521]

Thank you for your attention CERTH Thank you for your attention Dr. Stella Bezergianni sbezerg@cperi.certh.gr Tel: 2310498315 | Fax:2310498380 Biofuels for Sustainable Development of Southern Europe International Conference on Thessaloniki, 19-20 November 2012 www.bio4sud.gr