Catalytic hydropyrolysis for sustainable aviation fuel

Catalytic hydropyrolysis for sustainable aviation fuelMagnus Zingler Stummann1, Martin Høj1, Jostein Gabrielsen2, Peter Arendt Jensen1, Lasse Røngaard Clausen3, Anker Degn Jensen1

1 DTU Chemical Engineering, Technical University of Denmark2 Haldor Topsøe A/S3 DTU Mechanical Engineering, Technical University of Denmark

DTU Chemical Engineering, Technical University of Denmark

Sustainable carbon based fuels

• Generally accepted that carbon based fuels will be needed at

least in the short to medium time frame

• Sustainable carbon sources:

–CO2 from point sources (power plants, cement, biogas etc.)

–Biomass

2


Biofuels

Biomass

Syngas

Engine-fuels

HigherAlcohols

Methanol

Hydrogen

Bio-oil Engine-fuels

Sugar

Ethanol

Hydro-carbons

Hydrogen

Lignin Hydro-carbons

Hydrodeoxygenation

Dehydration

Hydrogenation

3


Biomass to green fuels

BiomassPyrolysis oilHHV ~ 16-19 MJ/kg28-40 wt. % oxygen

Fuel + water~ 45 MJ/kg<0.1 wt. % oxygen

Vapor phase

Fast pyrolysisHydrode-oxygenation

Hydrogen assisted catalytic pyrolysis+HDO

Mortensen et al., Appl. Catal. A 407 (2011) 1-19

N2, ~500 °C H2, 300-400 °C

Condensation

4


Proposed catalytic hydropyrolysis process

400-500 °C15-35 bar H2

350-400 °C15-35 bar H2 COx

CH4C2H6C3H8

SNG

5


Hydropyrolysis processes

• b) RTI (Dayton et al.

Energ. Fuels, 2013)

• c) Phillips 66 (Zhang et

al. Green Chem. 2017)

• c) H2Bioil – Purdue

University (Agrawal and

Singh, AIChE J. 2009)

• d) IH2 – GTI/Shell

(Marker et al. Environ.

Prog. Sus. Energ. 2012)

Fig: Resende, Catal. Today 20166


Setup at DTU Chemical Engineering

7

H2

Fluid bedCatalyst: CoMoS/MgAl2O4H2 pressure: 3-36 barTemp:365-510oC

Char

HDOCatalyst: NiMoS/Al2O3Temp: 370-400oC

Oil and water

Gas

GC

Screw feederBiomass: Beech woodFeeding rate: 150-400 g/h

Filter


Hydropyrolysis of beech wood (25 bar)- Yield of oil as function of temperature

360 380 400 420 440 460 480 500 5200

5

10

15

20

25

Con

dens

ed o

rgan

ics

+ C

4+ y

ield

(wt.%

daf

)

Fluid bed Temp. (oC)

HDO temp: 350 oC HDO temp: 375 oC HDO temp: 400 oC No HDO

8


Oil analysis- Oil composition

Oxygen <0.1 wt.%Nitrogen: 0.6 - 24 ppmSulphur : 0.06-0.3 wt.%

360 380 400 420 440 460 480 500 52010

12

14

86

88

90


Con

cent

ratio

n (w

t.%)


Carbon

Hydrogen

9


Oil analysis- Simulated distillation

0 50 100 150 200 250 300 350 4000

20

40

60

80

100

DieselDis

tilla

te v

olum

e fr

actio

n (v

ol. %

)

Temperature (oC)

Exp. #1 Exp. #2 Exp. #3 Exp. #4 Exp. #5 Exp. #6 Exp. #7 Exp. #8 Exp. #9 Exp. #10 Exp. #11

Naphtha

10


Oil analysis- GCxGC-MS/FID

Increasing boiling point

Incr

easi

ng p

olar

ity

11


Oil analysis- Aromatics

360 380 400 420 440 460 480 500 5200

10

20

30

40

50

60

70

80

Are

a-FI

D (%

)

Fluid bed temp. (oC)


Aromatics

Naphthenes

Measured concentration Concentration at equilibrium

The concentration of aromatics is controlled by kineticsat low temperature and equilibrium at high temperature

12

300 350 400 450 500 5500

20

40

60

80

100

Hyd

roge

n fr

ee m

ole

frac

tion

(%)

Temp. (oC)

99 % H2

80 % H2

60 % H2

Monoaromatics

Diaromatics

Naphthenes


Hydropyrolysis of beech wood- Yield of gas and char as function of temperature

360 380 400 420 440 460 480 500 5200

5

10

15

20

25

30

35

Gas

yie

ld (w

t.% d

af)



Sum

CO+CO2

C1-C3

360 380 400 420 440 460 480 500 5200

4

8

12

16

20

Cha

r yie

ld (w

t.% d

af)


13


Hydropyrolysis of beech wood- Energy recovery

Energy added in the form of H2: 0.26-0.34 MJ/MJ biomass

0

20

40

60

80

100

120

40%

Pressure (barg)HDO T. (oC)

400

Ener

gy re

cove

ry (%

)

Oil+C4+ Gas Char

40%

365 430400 468 511470451 453 449 450345 370400 395 363390371 370 370 -25 2525 25 252525 15 35 25

Fluid bed T. (oC)39525

40% 40% 40% 40% 40% 40% 40% 40%40%

36% 37% 44% 41% 43% 45% 42% 48% 38% 41% 38%

40% 46% 51% 48% 51% 51% 51% 53% 46% 50% 47%

19% 19%

20% 19% 16% 16% 17% 14%

14%

17%

17%

14

Energy integration with SNG and renewable wind and solar power

Tuong-Van Nguyen & Lasse Røngaard Clausen, Energy Conversion and Management, 171 (2018) 1617–1638


5 MWth15 MWth5 MWthCo-production of SNG

PSAH2

CH4 synthesis

SNG

100 MWth

61 MWth

Energy efficiency:biomass to oil + SNG = 66%

Energy ratio:biomass to oil + SNG = 66%

16


5 MWth15 MWth59 MWthIntegrating electrolysis. Co-production of SNG

PSAH2

CH4 synthesis

SNG

100 MWth

61 MWth

Energy efficiency:biomass + hydrogen to oil + SNG = 80%

storage49 MWth(H2)


17


5 MWth15 MWth85 MWth

PSAH2

CH4 synthesis

SNG

Char gasifier

Steam

100 MWth

15 MWth

61 MWth

storage63 MWth(H2)

Energy efficiency:biomass + hydrogen to oil + SNG = 89%

Integrating electrolysis. Co-production of SNGWith char gasification


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Summary

• Catalytic hydropyrolysis efficiently converts biomass into oxygen-free

HC fuels with a significant fraction in the aviation fuel BP range

• Co-production of natural gas

• Up to 25 wt. % oil yield ~60 % energy recovery in the oil

• Light gases can be used to generate the required H2 and some SNG:

Total energy efficiency of 66 %

• When coupled with electrolysis to produce the required H2:

– Total energy efficiency of 80 % (energy ratio of 120 %)

• Exploiting also the char and coupled with electrolysis:

– Total energy efficiency of 89 % (energy ratio of 146 %)

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Thank you for your attention

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Catalytic hydropyrolysis for sustainable aviation fuel