Co-processing Bio-crude at Petroleum Refineries: Fractional distillation and deoxygenation of HTL bio-crude to evaluate the potential as co-processing feed
Authors
Jensen, Claus Uhrenholt ; Rasmussen, Kristine Møllenbach
Term
4. term
Education
Publication year
2014
Submitted on
2014-06-03
Pages
106
Abstract
This thesis examines whether hydrothermal liquefaction (HTL) bio-crude can be co-processed in existing petroleum refineries as a gradual pathway to drop-in biofuels without major plant modifications. To assess its suitability, the bio-crude was fractionated using a 15 theoretical plate true boiling point (TBP) distillation, and the fractions were analyzed for elemental composition (O, N, S), higher heating value (HHV), and FT-IR spectra. The distillation suggests approximately 6 wt.% gasoline-range, 26 wt.% jet fuel-range, 22 wt.% diesel-range, and below 30 wt.% residue. A key issue is that the heteroatom distribution differs from petroleum crude. An experimental deoxygenation setup was therefore designed and tested; catalyst crushing was found to affect repeatability. Under mild deoxygenation conditions (330°C, 95 bar, 2 hours, 2:1 H2:oil, NiMo/Al2O3), oxygen and sulfur were reduced to 2.38 wt.% and 0.04 wt.% respectively. The product exhibited an HHV of 44.3 kJ/g and FT-IR features similar to petroleum crude. Remaining oxygenates are expected to be cyclic and polycyclic compounds located in the residue fraction. Overall, the results indicate that a mild deoxygenation step may be sufficient to enable co-processing of HTL bio-crude in petroleum refineries without major modifications.
Dette speciale undersøger, om bio-olie fra hydrotermisk liquefaktion (HTL) kan sambehandles (co-processes) i eksisterende petroleumsraffinaderier som en trinvis vej til drop-in biobrændsler uden større anlægstilpasninger. For at vurdere egnetheden blev HTL-bio-olien fraktioneret ved 15 teoretiske plader (TBP-destillation), og fraktionerne blev analyseret for elementarsammensætning (O, N, S), brændværdi (HHV) og FT-IR-signatur. Destillationen indikerer omtrent 6 vægt-% i benzinområdet, 26 vægt-% i jetbrændstofområdet, 22 vægt-% i dieselområdet og under 30 vægt-% rest. En central udfordring er, at fordelingen af heteroatomer afviger fra råolie. Der blev derfor designet og testet et eksperimentelt deoxygeneringsopstilling; det blev observeret, at knusning af katalysator påvirkede gentageligheden. Ved mild deoxygenering (330°C, 95 bar, 2 timer, 2:1 H2:olie, NiMo/Al2O3) blev indholdet af oxygen og svovl reduceret til henholdsvis 2,38 vægt-% og 0,04 vægt-%. Produktet havde en HHV på 44,3 kJ/g og en FT-IR-profil, der ligner petroleumsråolie. Resterende oxygenater forventes hovedsageligt at være cykliske/polysykliske forbindelser lokaliseret i restfraktionen. Resultaterne peger på, at et mildt deoxygeneringstrin kan være tilstrækkeligt til at muliggøre synergi ved sambehandling af HTL-bio-olie i petroleumsraffinaderier uden større modifikationer.
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Keywords