Catalytic de-oxygenation of
woody biomass pyrolysis vapours
over zeolite-bentonite catalysts
Atte Aho, Narendra Kumar, Kari Eränen,
Tapio Salmi, Dmitry Murzin, Mikko Hupa
Objective
ƒ Study the pyrolysis of pine wood biomass
in a fluidized bed reactor for the production
of valuable fuels and chemicals
ƒ Upgrading of the pyrolysis vapours
through catalytic de-oxygenation over
zeolite-bentonite catalysts
Pyrolysis of Biomass
Gases
Pine
Biomass
Pyrolysis
without O2
400 °C
Char
Gases
Condensation
Bio Oil
Catalytic de-oxygenation
ƒ Conventional pyrolysis oil highly
oxygenated
ƒ Quality improved by removing oxygen
from oil molecules
ƒ Upgrading over zeolites
ƒ Low temperatures, oxygen removed as water
ƒ Higher temperature, CO2 and CO
Reactor set-up
450 °C
-20 °C
400 °C
Experiments
ƒ Pine as biomass raw material (355 – 500 µm)
ƒ Quartz sand in the lower bed (100 – 150 µm)
ƒ Five different runs
ƒ
ƒ
ƒ
ƒ
ƒ
Empty upper bed (non-catalytic)
Bentonite/H-ZSM-5-23 (250 – 355 µm)
Bentonite/H-Beta-25
H-ZSM-5-23
H-Beta-25
Acidic Zeolite Catalysts
ƒ Beta
ƒ 3-D, 12 ring
ƒ 0.76 x 0.64 nm
ƒ 0.76 x 0.64 nm
ƒ 0.55 x 0.56 nm
ƒ ZSM-5
ƒ 3-D, straight 10 ring
ƒ 0.52 x 0.57 nm
ƒ Sinusoidal 0.53 x 0.56 nm
ƒ Intersection cavity ( 0.9 nm)
ƒ Surface area 450 – 500
m2/g (300 – 400)
Temperature profile
Bed
Catalyst
Furnace
500
Pyrolysis
Reactions
Temperature [°C]
400
300
N2 flow off
200
100
0
0
50
100
150
200
Time [min]
250
300
350
400
Reaction temperature
Bed
480
Catalyst
Beginning of
experiment
460
20 °C
440
420
20 °C
400
380
205
210
215
220
225
Mass balances
37.6
37.2
38.1
36.3
39.1
Gas (by
difference)
18.6
18.9
2.7
16.6
22.9
19.0
16.2
4.2
0.6
Organic
phase
21.7
24.8
16.8
15.0
2.1
Aqueous
phase
Coke on
catalyst
0.0
22.2
23.0
22.2
23.1
21.1
Hybrid ZSM-5
Hybrid Beta
ZSM-5
Beta-25
non-catalyzed
Char
(biomass
residue)
Chemical composition
Empty
1
2
3
4
5
Hybrid ZSM-5
6
7
8
9
Hybrid Beta
10
11
12
13
14
15
Products
CH3
CH3
O
OH
O
CH3
H3C
O
H3C
OH
acetic acid
OH
levoglucosan
O
O
H3C
OH
2-methoxy-4-methylphenol
H2C
O
O
CH3
O
HO
OH
2-methoxy-4-[(1E)-prop-1-en-1-yl]phenol
1-hydroxyacetone
O
HO
CH3
H3C
OH
1-(4-hydroxy-3-methoxyphenyl)ethanone
O
OH
2-methoxyphenol
OH
2-methoxy-4-vinylphenol
O
O
OH
H3C
2-hydroxycyclopent-2-en-1-one
O
O
O
OH
4-hydroxy-3-methoxybenzaldehyde
CH3
furan-2(5H)-one
Conclusions
ƒ De-oxygenation over catalysts changes
the yield of the organic phase, aqueous
phase and coke
ƒ Chemical composition of the oil changes
during upgrading
ƒ Hybrid materials more active than pure
zeolites
ƒ Beta more active than ZSM-5
Thank you
for your attention