Transcript Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/δ

Date 28.06.2010 | 1
Catalytic Hydrotreatment of
Pyrolysis Oil with
NiCu/δ-Al2O3 catalysts
Agnes Ardiyanti1, Sofia Khromova2, Robbie Venderbosch3, Vadim
Yakovlev2, Erik Heeres1
1University
of Groningen, Groningen, The Netherlands
2Boreskov Institute of Catalysis, Novosibirsk, Russia
3BTG Biomass Technology Group, Enschede, The Netherlands
Date 28.06.2010 | 2
Introduction
Lignocellulosic biomass
Existing refinery
Catalyst,
Pyrolysis
H2
(+ VGO)
Upgraded oil (low O)
Pyrolysis oil (high O)
Catalytic Hydrotreatment
P, T
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Novel hydrotreatment catalysts
Catalyst requirement
• strong hydrogenation
Conventional catalysts
• sulfided NiCu or CoMo on
activity
• stable at hydrotreatment
condition (aqueous, acidic)
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
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Approach
› Various catalyst
compositions
Catalyst
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
16
2
20.8
-
16Ni2Cu
20.8Ni
› Catalyst testing
 HDO of Anisole
 Hydrotreatment of
pyrolysis oil
› Catalyst characterisation
 TPR, XRD, ICP
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HDO of Anisole (1)
Flow reactor (BIC)
Mechanism1
H2 + Ar
OMe
OH
desired products
HDO
Anisole
Anisole
HDO
+
o
300 C, 10 bar
LHSV 6 h-1
other products
OH
CH3
Furnace
HDO
Products
CH3
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HDO of Anisole (2)
› Yield of oxygen-free products
Yield of oxygen free products, mol %
80
70
60
50
40
30
20
10
0
24.5Cu
5.92Ni18.2Cu
13.3Ni11.8Cu
13.8Ni6.83Cu
16Ni2Cu
20.8Ni
Catalyst
16Ni2Cu gives the highest HDO yield
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XRD analysis
13.8Ni6.83Cu
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
20.8Ni
NiO
Cu does not have HDO activity,
but supports the reduction of Ni
Reduction was performed at 300 oC and
10 bar of H2
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Hydrotreatment of pyrolysis oil
• Reactor: 100 ml autoclave, in-situ
I-2
V1
Feed line
V2
Bomb
N2
V3
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
H2
Gas outlet
Pyrolysis oil composition
Reactor
Autoclave (RuG)
C (wt%)
40.1
H (wt%)
7.6
O (wt%)
52.1
Moisture (wt%)
23.9
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Upgraded oil
dry oxygen content (wt %)
50
40
30
20
10
0
PO
Phase separation
occurred
blank
20.8Ni
16Ni2Cu
13.8Ni
6.83Cu
13.3Ni
11.8Cu
5.92Ni
16.82Cu
24.5Cu
catalyst
Deoxygenation, even without catalyst
 Not the only criterium!
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Hydrogenation activities
› Van Krevelen plot is used to calculate the hydrogenation
activities, blank experiment as the reference
0.6
1.6
PO
hydrogenation activity (g-1)
atomic O/C (dry)
0.5
0.4
0.3
13.3Ni 11.8Cu
0.2
16Ni2Cu
13.8Ni 6.83Cu
20.8Ni
0.1
blank
5.92Ni 16.82Cu
24.5Cu
0.0
0.8
0.9
1.0
1.1
1.2
1.3
atomic H/C (dry)
1.4
1.5
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
20.8Ni
16Ni2Cu
13.8Ni
6.83Cu
13.3Ni
11.8Cu
catalyst
16Ni2Cu and 13.8Ni6.83Cu are the most active
5.92Ni
16.82Cu
24.5Cu
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Upgraded oil – physical properties
50
900
45
800
40
700
35
600
Mw
30
500
25
400
20
300
15
200
10
TG residue
5
100
0
0
Py-oil
blank
20.8Ni
16.2Ni 2Cu
13.8Ni
6.83Cu
13.3Ni
11.8Cu
5.92Ni
18.2Cu
24.5Cu
catalyst
16Ni2Cu and 13.8Ni6.83Cu give products with the
best physical properties
Mw (mol/g)
TG residue (wt %)
› TGA and GPC analyses
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HRTEM
Fresh 16.8Ni6.83Cu
Spent 16.8Ni6.83Cu
Active metal particle size: 10 nm (fresh)  100 nm (spent).
ICP showed leaching of Ni, Cu, and Al
Dissolution and recrystallisation of NiCu seem to occur
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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).
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Thank you!
UIC
Boreskov Institute of Catalysis –
SB RAS
Financial support: