catalytic hydrotreatment of pyrolysis oil with nicu/ δ - al 2 o 3 catalysts
DESCRIPTION
Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/ δ - Al 2 O 3 catalysts. Agnes Ardiyanti 1 , Sofia Khromova 2 , Robbie Venderbosch 3 , Vadim Yakovlev 2 , Erik Heeres 1 1 University of Groningen, Groningen, The Netherlands 2 Boreskov Institute of Catalysis, Novosibirsk, Russia - PowerPoint PPT PresentationTRANSCRIPT
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)
9|Date 28.06.2010
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: