Production of advanced biofuels: Co-refining upgraded pyrolysis oil

Production of advanced biofuels:Co-refining upgraded pyrolysis oil

F. de Miguel Mercader, Kees Hogendoorn (University of Twente)

C. Geantet, G. Toussaint (IRCELYON)

Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 2

Contents

Introduction

Energy scenario

Co-refining pyrolysis oil (BIOCOUP concept) Advanced bio-fuels, advantages co-refining Biomass route

Pyrolysis oil upgrading – Hydrodeoxygenation Product yields/properties

Co-refining upgraded pyrolysis oil

Conclusions


Contents

Introduction

Energy scenario




Conclusions


Energy scenario

Expected increase in bio-fuels demand

Ref: Shell energy scenarios to 2050 (Shell International BV, 2008)

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2000 2025 2050

EJ

/ ye

ar

Biofuels

Electricity

Gaseous hydrocarbon fuels

Liquid fuels fossil-derived


Co-refining pyrolysis oil


Biomass route

Pyrolysis oil~ 50 wt.% oxygen~20-30 wt.% water

Ligno-cellulosicBiomass (waste)

Refinery

Co-refining

Pyrolysis

400-550 ºC2 seconds

Inert atmosphereOil yield: 60-70 wt.%

Energy yield:~ 60-70 %

Upgrading

HydrodeoxygenationReduction Oxygen and Water content

Improve miscibility fossil fuelReduce acidity…


Advanced bio-fuels

Contribute to secure the supply of fuels

The reduction of green-house-gas emissions

Do not compete with the food chain

Produced from a wider range of ligno-cellulosic biomass

agricultural waste,

wood,

forest residues

…


Advantages of co-refining upgraded pyrolysis oil

The use of decentralised pyrolysis plants that can be near the biomass

production site. This means that only the oil is transported, reducing

transportation costs due to the increase of the volumetric energy of the oil

compared to the original biomass.

After pyrolysis, large part of the minerals from biomass is not transferred to

the oil but remain as ash. Thus, pyrolysis oil contains less inorganic

material that could poison subsequent catalytic processes. Moreover, the ash

can be returned to the soil as fertiliser.

As the upgrading plant would be next to (or inside) the refinery, all the

necessary utilities would be already available and the product obtained after

co-refining could use the existing distribution network.


Is co-refining possible?

What should the upgrading severity be?

How much oxygen removal?

How much hydrogen is need for upgrading?

In which refinery unit should the oil be co-refined?


Contents

Introduction

Energy scenario




Conclusions


Active catalyst (Ru/C)

High H2 pressure

Upgrading treatment – Hydrodeoxygenation (HDO)

Long residence time (>4h)

200-400 °C, >200 bar.

Batch autoclave 5L

N2 – Low pressure supply line (10 bar)

Vent

H2 supply vessel400 bar

Rupture disc

Gas sample

TI PI TIC

TI

PI


Upgrading Products

Oil Phasedry yield: 47-50 wt.%

Energy yield: 55-68 % (MJ HDO oil / MJ PO+H2)

Pyrolysis oil

+ H2

Gas Phasedry yield: 3-9 wt.%

Aqueous Phasedry yield: 39-14 wt.%

Produced waterdry yield: 9-19 wt.%

HDO

Final T: 230-340 °C

P: 290 bar

F. De Miguel Mercader et al. Applied Catal. B 96 (2010) 57-66


Oil properties and H2 consumption

Feed oil HDO oils

C dry (wt.%) 54 63-74

H dry (wt.%) 7 9-10

O dry (wt.%) 39 28-16

Water (wt.%) 25 16-2

HHV (MJ/kg) 17 25-35

MCRT dry (wt.%) 27 14-2

Temperature (°C) 230 260 300 330 340

NL H2/kg feed oil 232 237 290 297 326

NL H2/MJ of product 21.6 22.0 22.3 21.8 23.6


Contents

Introduction

Energy scenario




Conclusions


Where should HDO oil be co-refined?

Two refinery units have been evaluated

Fluid catalytic cracking (FCC)

Used to treat heavy refinery feedstocks to lighter more useful fractions

such as gasoline, LCO,…

Pyrolysis oil contains heavy molecules

Hydrodesulphurisation

Used to remove sulphur from fossil fuel to meet environmental

specifications

Similar to HDO process


Catalytic cracking

Lab-scale FCC reactor – MAT-5000 - 520 ºC

Equilibrium catalyst from Shell’s FCC units

Co-refining 20 wt.% HDO oils + 80 wt.% Long Residue

Complete solubility

Successful processing without plugging of lines

Product near oxygen free (some phenolics remaining)

Product analysed by true boiling point fractions


Co-refining product yields

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Long residue 20% HDO oil (230 C) 20% HDO oil (300 C) 20% HDO oil (340 C)

Cat

alyt

ic c

rack

ing

yie

lds

(wt.

%)

Other

Coke yield

Drygas yield

LCO yield

Gasoline yield

LPG yield

Product yields (corrected by water production) independent of HDO severity

F. De Miguel Mercader et al. Applied Catal. B 96 (2010) 57-66


Influence of blending

Coke yields much higher when HDO oil processed undiluted

Hydrogen transfer from long residue required for good product distribution

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HDO 300 °Cextrapolated

HDO 300 °Cmeasured

Ca

taly

tic c

rack

ing

yie

lds

(wt.

%)

Others Coke Dry gas LCO Gasoline LPG

Long residuereference


Quality parameters

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230 °C 260 °C 300 °C 330 °C 340 °C

O dry (wt.%)

MCRT (wt.%)

MCRT blend (wt.%)

0.6

0.8

1

1.2

1.4

1.6

1.8

230 °C 260 °C 300 °C 330 °C 340 °C

H/Ceff blend

H/Ceff

H/Ceff = H - 2*O


Biomass route

Biomass Pyrolysis oil HDO oilGasoline,

LPG & LCO

Mass (g) 100 65 26 20

Average yields (%) 65 40 75

Biomass Pyrolysis oil HDO oilGasoline,

LPG &LCO

Carbon (g) 100 61 38 32

Average yields (%) 61 63 85

1.5 g H2 / 100 g biomass


Hydrodesulphurisation unit (HDS)

Lab-scale HDS reactor – Co-refining model compounds

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280 300 320 340 360

reaction temperature (°C)

co

nv

ers

ion

(%

) crude GO

5000 ppmguaiacol

Inhibition at low temperature

Bui V. N., Toussaint G., Laurenti D., Mirodatos,

C. Geantet C., Catal. Today 143 (2009) 172. Pinheiro A., Hudebine D., Dupassieux N. and Geantet C.Energy Fuels 2009, 23(2) 1007.

Constant Oxygen content 0.5 wt%WGS, methanation competitionCompetition HDS/HDO


Hydrodesulphurisation unit (HDS)

Lab-scale HDS reactor – Co-refining HDO oils

SRGO/HDO oil/i-propanol80/10/10Two phases obtainedCo-refining only soluble part

360 °C, 4 MPa, LHSV 2h-1

Initial catalyst activity recovered after co-processing

C. Geantet, G. Toussaint, L. Braconnier, C. Mirodatos, F. De Miguel Mercader, J. A. Hogendoorn et al. (IRCELYON and University of Twente): Co-processing of SRGO and hydrotreated bio-oils.The 5th International symposium of molecular aspects of catalysis by sulphides (MACS V). 30 May to 3 June 2010. Copenhagen

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crudeSRGO

SRGO 10%HDO 318

SRGO 10%HDO 527T

SRGO 10%HDO 529B

S c

on

ten

t af

ter

HD

S,

O c

on

ten

t an

d H

2O c

on

ten

t o

f b

ioo

ils

BIO OIL O%w

BIO OIL H2O %w

S*10 m/kg after HDS

HDO 330 C HDO 300 C HDO 270 C


Contents

Introduction

Energy scenario




Conclusions


Conclusions

Increasing HDO severity

Increases carbon/energy recovery Reduces oxygen and water content

Successful catalytic cracking co-refining of HDO oil (with high oxygen content)

with Long Residue

Gasoline, LCO and LPG yields remain similar to reference

The presence of fossil feed appears to be very important

HDS inhibition is detected for certain oxygenated model compounds and for

HDO oils

The molecular composition or water content of the HDO oils do not drastically

affect the performances of the catalysts.


Acknowledgments

All BIOCOUP partners

Special thanks to N.W.J. Way & C.J. Schaverien from Shell Global Solutions International BV.

Thank you for you attention!

Documents

Production of advanced biofuels: Co-refining upgraded pyrolysis oil