1|Date 28.06.2010

Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/δ-Al2O3 catalystsAgnes Ardiyanti1, Sofia Khromova2, Robbie Venderbosch3, Vadim Yakovlev2, Erik Heeres1

1University of Groningen, Groningen, The Netherlands2Boreskov Institute of Catalysis, Novosibirsk, Russia3BTG Biomass Technology Group, Enschede, The Netherlands

2|Date 28.06.2010

Introduction

Catalytic HydrotreatmentP, T

Pyrolysis oil (high O) Upgraded oil (low O)

Pyrolysis (+ VGO)

Catalyst, H2

Lignocellulosic biomass Existing refinery

3|Date 28.06.2010

Novel hydrotreatment catalystsCatalyst requirement• strong hydrogenation

activity• stable at hydrotreatment

condition (aqueous, acidic)

Conventional catalysts• sulfided NiCu or CoMo on

γ-Al2O3

• leaching and sulfur contamination

Novel NiCu/δ-Al2O3 catalysts • Developed by BIC • Cu as reduction aid• δ-Al2O3 is more stable than γ-Al2O3

4|Date 28.06.2010

Approach› Various catalyst

compositionsCatalyst Ni (wt

%)Cu (wt

%)24.5Cu 24.5 -

5.92Ni18.2Cu 5.92 18.2

13.3Ni11.8Cu 13.3 11.8

13.8Ni6.83Cu 13.8 6.83

16Ni2Cu 16 2

20.8Ni 20.8 -

› Catalyst testing HDO of Anisole Hydrotreatment of

pyrolysis oil

› Catalyst characterisation TPR, XRD, ICP

5|Date 28.06.2010

HDO of Anisole (1)Flow reactor (BIC)

Anisole

H2 + Ar

Products

Furnace

300 oC, 10 barLHSV 6 h-1

CH3

OMe OH

OH

CH3

+HDO

HDO

HDO

other products

Anisole

Mechanism1

desired products

6|Date 28.06.2010

HDO of Anisole (2)› Yield of oxygen-free products

0

10

20

30

40

50

60

70

80

24.5Cu 5.92Ni18.2Cu 13.3Ni11.8Cu 13.8Ni6.83Cu 16Ni2Cu 20.8Ni

Catalyst

Yiel

d of

oxy

gen

free

prod

ucts

, mol

%

16Ni2Cu gives the highest HDO yield

7|Date 28.06.2010

XRD analysis13.8Ni6.83Cu

20.8Ni

NiO

Ni

• No Ni(0) was found at 20.8Ni after reduction at 300 oC (reduction temperature of Ni is > 500 oC)

•Ni(0) was formed on 13.8Ni6.83Cu after reduction

Cu does not have HDO activity, but supports the reduction of Ni

Reduction was performed at 300 oC and 10 bar of H2

8|Date 28.06.2010

Hydrotreatment of pyrolysis oil• Reactor: 100 ml autoclave, in-situ catalyst reduction possible • Feed: pine pyrolysis oil (provided by VTT, Finland)• Condition: 150 oC (1h), 350 oC (3h), pressure 200 bar at 350 oC.• 25 g pyrolysis oil and 1.25 g (5 wt%) of catalyst was used

Pyrolysis oil compositionC (wt%) 40.1H (wt%) 7.6O (wt%) 52.1Moisture (wt%) 23.9

Autoclave (RuG)

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Upgraded oil

0

10

20

30

40

50

PO blank 20.8Ni 16Ni2Cu 13.8Ni6.83Cu

13.3Ni11.8Cu

5.92Ni16.82Cu

24.5Cu

catalyst

dry

oxyg

en c

onte

nt (w

t %)

Phase separation occurred Deoxygenation, even without catalyst

Not the only criterium!

10|Date 28.06.2010

Hydrogenation activities› Van Krevelen plot is used to calculate the hydrogenation

activities, blank experiment as the reference

16Ni2Cu

PO

20.8Ni13.8Ni 6.83Cu

13.3Ni 11.8Cu

5.92Ni 16.82Cu24.5Cublank

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6

atomic H/C (dry)

atom

ic O

/C (d

ry)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

20.8Ni 16Ni2Cu 13.8Ni6.83Cu

13.3Ni11.8Cu

5.92Ni16.82Cu

24.5Cu

catalyst

hydr

ogen

atio

n ac

tivity

(g-1

)

16Ni2Cu and 13.8Ni6.83Cu are the most active

11|Date 28.06.2010

Upgraded oil – physical properties

0

5

10

15

20

25

30

35

40

45

50

Py-oil blank 20.8Ni 16.2Ni 2Cu 13.8Ni6.83Cu

13.3Ni11.8Cu

5.92Ni18.2Cu

24.5Cu

catalyst

TG re

sidu

e (w

t %)

0

100

200

300

400

500

600

700

800

900

Mw

(mol

/g)

TG residue

Mw

16Ni2Cu and 13.8Ni6.83Cu give products with the best physical properties

› TGA and GPC analyses

12|Date 28.06.2010

HRTEM

Active metal particle size: 10 nm (fresh) 100 nm (spent).ICP showed leaching of Ni, Cu, and Al

Fresh 16.8Ni6.83Cu Spent 16.8Ni6.83Cu

Dissolution and recrystallisation of NiCu seem to occur

13|Date 28.06.2010

Conclusions› Non-sulfided Ni-based catalysts have been developed

and tested.› NiCu catalysts are active in HDO of anisole.› Cu is not active, but supports the reduction of Ni at

lower temperature (300 oC).› NiCu catalysts are active in hydrotreatment of pyrolysis

oil.› Most active catalysts: 16Ni2Cu and 18.6Ni6.83Cu

(highest hydrogenation activity, lowest products Mw and TG residue).

› Catalyst stability is not optimal (improvement of the catalysts stability is in progress).

14|Date 28.06.2010

Thank you!

UICUIC

Boreskov Institute of Catalysis – SB RAS

Financial support: