Engineering Conferences International ECI Digital Archives Pyroliq 2019: Pyrolysis and Liquefaction of Proceedings Biomass and Wastes
6-19-2019 Upgrading of wheat/barley and miscanthus bio-oil over a sulphided catalyst Bogdan Shumeiko University of Chemistry and Technology, Czech Republic, [email protected]
Miloš Auersvald University of chemistry and technology, Prague
David Kubička University of chemistry and technology, Prague
Petr Straka University of chemistry and technology, Prague
Pavel Šimáček University of chemistry and technology, Prague
See next page for additional authors
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Recommended Citation Bogdan Shumeiko, Miloš Auersvald, David Kubička, Petr Straka, Pavel Šimáček, and Dan Vrtiška, "Upgrading of wheat/barley and miscanthus bio-oil over a sulphided catalyst" in "Pyroliq 2019: Pyrolysis and Liquefaction of Biomass and Wastes", Franco Berruti, ICFAR, Western University, Canada Anthony Dufour, CNRS Nancy, France Wolter Prins, University of Ghent, Belgium Manuel Garcia-Pérez, Washington State University, USA Eds, ECI Symposium Series, (2019). https://dc.engconfintl.org/pyroliq_2019/24
This Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in Pyroliq 2019: Pyrolysis and Liquefaction of Biomass and Wastes by an authorized administrator of ECI Digital Archives. For more information, please contact [email protected]. Authors Bogdan Shumeiko, Miloš Auersvald, David Kubička, Petr Straka, Pavel Šimáček, and Dan Vrtiška
This abstract and presentation is available at ECI Digital Archives: https://dc.engconfintl.org/pyroliq_2019/24 Upgrading of wheat/barley straw bio-oil over a sulphided catalyst
Shumeiko Bogdan, David Kubička, Miloš Auersvald, Petr Straka, Dan Vrtiška, Pavel Šimáček Cork, Ireland 19/06/2019
Department of Petroleum Technology and Alternative Fuels BIOMATES SCHEME
Source: www.biomates.eu
Department of Petroleum Technology and Alternative Fuels 2 OUR AIM
Hydrogenation AIM unit • Straw and miscanthus • Use advanced analytical techniques to shed light bio-oils • one-step fixed-bed • Low-cost petroleum- on product nature • Sulphided x transition reactor refinery-compatible metals feedstock • Optimization of T and P Bio-oil and Products catalysts characterisation
Department of Petroleum Technology and Alternative Fuels 3 WHEAT/BARLEY STRAW BIO-OIL
Wheat/barley straw bio-oil
• Tcond 2-5 °C • Tcond 75 °C • Aqueous phase yield = 27.9 wt% • Bio-oil yield = 23.3 wt% • Bio-oil yield = 20.9 wt%
S 0.06 S 0.05
O 38.6 O 36.2 C 52.4 C 55.1 C O
H2O 22.6 Yield 20.5
N 0.7 N 0.6 H 8.2 H 8.1
Department of Petroleum Technology and Alternative Fuels 4 HYDROGENATION UNIT
• Fixed-bed, co-current flow R
• Wheat/barley straw bio-oil 2-5 °C and 75 °C F
• 340 °C, 40 bar, TOS 80 h, LHSV 1h-1 C
• Presulphided NiMoS/Al O C 2 3 Based on our previous experiments
2 -1 SBET: 86.5 m ·g 3.9% Ni and 15% Mo 0.8-1.2 mm particle size
Department of Petroleum Technology and Alternative Fuels 5 Hydrogenation of wheat/barley bio-oil 2-5 °C
Part 1: effect of thermoprofile
Department of Petroleum Technology and Alternative Fuels 6 EFFECT OF TERMOPROFILE ON PRODUCTS QUALITY
Hydrogenation of bio-oil (2-5 °C) at two different thermoprofiles: fast increase to 340 °C and smooth increase to 340 °C
420 "Fast"
340
C ° 260
180 "Smooth" Temperature, Temperature,
100
20 80 140 200 260 320 380 440 500 560 Reactor length, mm
Department of Petroleum Technology and Alternative Fuels 7 EFFECT OF TERMOPROFILE ON PRODUCTS QUALITY
All hydrogenated products were separated at two phases: organic and aqueous phase (OP and AP)
„Fast“ „Smooth“ 100 100420
80 36080
C ° 60 30060
40 24040
Yields, wt% Yields, Yields, wt% Yields,
Temperature, Temperature, Fast 48h 20 18020 Fast 4h
0 1200 4 8 12 36 48 60 80 80 4 8200 12 32036 48 44060 80 560 TOS, h AP OP GAS ReactorTOS,length h , mm AP OP GAS
Department of Petroleum Technology and Alternative Fuels 8 PHYSICOCHEMICAL PROPERTIES
• High catalytic activity loss after 12 hours TOS leads to decrease of products properties („Fast“)
Feed: 1.13 g⸳cm-3 Feed: 123 mm2⸳s-1
1.04 90
1
- s
1.02 ⸳ 75
2
3
- cm
⸳ 1.00 60
C, mm C,
° C, g C,
° Smooth 0.98 45
15 15 Fast at 0.96 30
Smooth
tic viscosity 40 viscosity tic a Density 0.94 15 Fast
0.92 Kinem 0 0 16 32 48 64 80 0 16 32 48 64 80 TOS, h TOS, h
Department of Petroleum Technology and Alternative Fuels 9 PHYSICOCHEMICAL PROPERTIES
Significant increasing MCR value can be assumed as the most negative point of „Fast“ products even with other better properties
8 2.0 Feed: 15 wt% Diesel
6 1.8 TOS 4 1.6
2 H/C ratio Atomic 1.4 Smooth Fast
Micro Conradson residue, wt% residue, Conradson Micro Bio-oil 0 1.2 0 16 32 48 64 80 0.00 0.05 0.10 0.15 0.20 0.25 TOS, h Atomic ratio O/C
Department of Petroleum Technology and Alternative Fuels 10 PHYSICOCHEMICAL PROPERTIES – TITRATION METHODS
Corrosivity of bio-oil products can cause huge problems in refinery – should be blended with crude-oil/distillates
50 6 1
- -1
g Feed: 56 mg KOH⸳g Feed: 22.6 wt% ⸳ 40
, mg KOH mg , 4
30 number 20
acid 2
Smooth wt% content, Water 10 Fast Smooth Fast Carboxylic 0 0 0 16 32 48 64 80 0 16 32 48 64 80 TOS, h TOS, h
Department of Petroleum Technology and Alternative Fuels 11 CHEMICAL COMPOSITION – GC/MS
In all products were found alkanes, cycloalkanes/-alkenes that have not been observed in the raw bio-oil
30 Alcohols Acids Ketones Furanes Aromatics
25 Alkanes Cycloalkanes Cycloalkenes Phenols
20
15 “Smooth" “Fast"
Content, wt% wt% Content, 10
5
0 80 48 24 12 8 4 Bio-oil 4 8 12 24 48 80
Department of Petroleum Technology and Alternative Fuels 12 Hydrogenation of wheat/barley bio-oil 75 °C
Part 2: application of „smooth“ thermoprofile
Department of Petroleum Technology and Alternative Fuels 13 HYDROGENATION OF STAGED CONDENSATED BIO-OIL
• „Smooth“ thermoprofile mode was applied for the hydrogenation of staged condensate bio-oil (75 °C) for 64 hours experiment • After 40 h TOS organic phase density increased and all further products were not separated so well on two phases 100420 4h TOS 40h TOS 64h TOS
34080
C ° 26060
18040
Yield, wt% Yield, "Smooth" Temperature, Temperature, 10020
20 0 80 140 200 260 320 380 440 500 560 4 8 12 24 36 48 60 64 Reactor length, mm TOS, h AP OP Gas
Department of Petroleum Technology and Alternative Fuels 14 HYDROGENATION OF STAGED CONDENSED BIO-OIL
• Higher loss of the catalytic activity during hydrogenation of staged condensed bio-oil was dominantly caused by higher CAN of feed (80 mg KOH⸳g-1)
1.04 7
Feed 1.18 and 1.13 g⸳cm-3 6 Feed 20.5 and 22.6 wt%
3 5
- 1.02 cm
⸳ 4
C, g C, ° 3 1.00 2
Bio-oil 2-5 °C Bio-oil 2-5 °C Water content, wt% content, Water
Bio-oil 75 °C 1 Bio-oil 75 °C Density at 15 15 at Density
0.98 0 0 16 32 48 64 80 0 16 32 48 64 80 TOS, h TOS, h
Department of Petroleum Technology and Alternative Fuels 15 CONCLUSION
• Raw bio-oil is a complex mixture with unacceptable properties that should be upgraded to fulfil limits for transport fuels • Hydrotreatment is a suitable technology for bio-oil upgrading in the fixed-bed reactor for producing low- cost petroleum-refinery-compatible feedstock • Hydrotreatment thermoprofile play significant role in the upgrading process: „Smooth“ mode is preferred due to: • stable products properties • convenient unit operation • Upgrading of bio-oil condensed at 2-5 °C gave more valuable products with similar properties at all TOS
Future plans: test two thermoprofiles for the hydrtotreatment of miscanthus bio-oil (2-5 and 75 °C) and beech- wood bio-oil
Department of Petroleum Technology and Alternative Fuels 16 Thank you for your attention!
The results were obtained in the BioMates project. This project has received funding from the European Union`s Horizon 2020 research and innovation program under grant agreement No 727463. The publication reflects only the authors' view; the Commission and its responsible executive agency INEA are not responsible for any use that may be made of the information it contains.
Department of Petroleum Technology and Alternative Fuels