1. 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

2. 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

3. 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

5. 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

6. 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 = % 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

7. SustainDiesel Project
Aim: Improvement of diesel sustainability by incorporating WCO and RES in existing refinery
Project duration: –
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

8. 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

9. 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

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

11.  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

12. 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

13. 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

14. 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

15. 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%

16. 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

17. «...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 ]
( 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 ]

18. Thank you for your attention
CERTH
Thank you for your attention
Dr. Stella Bezergianni
Tel: | Fax:
Biofuels for Sustainable Development of Southern Europe
International Conference on
Thessaloniki, November 2012