Progress in fast pyrolysis
technology
Wolter Prins and Tony Bridgwater
Topsoe Catalysis Forum 2010
Munkerupgaard, Denmark, 19 to 20 August 2010
1
Contents
1.
2.
3.
4.
5.
6.
Fast pyrolysis principles
Bio-oil properties
Bio-oil applications
Technologies and suppliers
Opportunities for catalysis
Conclusions
2
1. Fast pyrolysis principles
3
1
Good reasons for fast pyrolysis
decoupling production and utilization
energy densification
easy handling
minerals separation
many application opportunities
4
1
Conditions for fast pyrolysis
Random chemical degradation due to rapid
heating in absence of oxygen
Process characteristics
temperature
heating rate
pressure
particle size
 vapors
 solids
500
100
1
<3
<2
> 10
oC
oC/sec
e
wood / wast
prim. electricity
gas
atm
mm
sec
sec
Products
bio-oil
permanent gas
char
70 – 80
10 - 15
10 - 15
wt.%
5
1
Fast pyrolysis times
fluidized bed pyrolysis time
of 42 mm long cylindrical
beech wood particles
versus their diameter.
6
1
Fast pyrolysis product yields
product yields for
fluidized bed pyrolysis
of cylindrical pine wood
particles as a function of
the reactor temperature;
dp = 3 mm; lp = 4.2 mm
7
1
Pyrolysis liquids elemental composition
80
derived liquid versus the reactor
70
temperature; dp= 3 mm, lp = 42 mm
a) water content of the total liquid
b) carbon content of the organic fraction
c) hydrogen content of the organic fraction
d) oxygen content of the organic fraction
organic fraction ≡ CH1.5O0.6
composition of liquid collected
in the first condenser [wt%]
composition of pine wood
a
60
b
50
40
d
30
c
5
0
200
300
400
500
600
700
o
Reactor temperature [ C]
(ethanol ≡ CH3O0.5)
8
800
2. Bio-oil properties
9
Comparison with heavy fuel oil
2
bio-oil
heavy fuel oil
vol. energy density
density
viscosity at 50 oC
acidity
water content
21
1220
13
3
20
39
963
351
7
GJ/m3
kg/m3
mm2/s
pH
0.1
ash content
0.02
52
7
40
0.1
< 0.1
0.03
86
10
0.5
0.6
2
wt.%
wt.%
wt.%
wt.%
wt.%
wt.%
wt.%
C
H
O
N
S
gas
VTT, Finland
10
2
Reported maximal(!) yields of chemicals in bio-oil
levoglucosan
30.4
hydroxyacetaldehyde
wt%
formaldehyde
2.4
15.4
phenol
2.1
acetic acid
10.1
propionic acid
waste
2.0
formic acid
9.1
acetone
2.0
acetaldehyde
8.5
methylcyclopentene-ol-one
gas
1.9
furfuryl alcohol
5.2
methyl formate
1.9
catechol
5.0
hydroquinone
1.9
methyl glyoxal
4.0
acetol
1.7
ethanol
3.6
angelica lactone
1.6
cellobiosan
3.2
syringaldehyde
1.5
1,6-anhydroglucofuranose
3.1
methanol
1.4
wood /
prim. electricity
11
Reference Pine Oil PR06-27
Water
Acids
Formic acid
Acetic acid
Propionic acid
Glycolic acid
Alcohols
Ethylene glycol
Isopropanol
Aldehydes and ketones
Nonaromatic Aldehydes
Aromatic Aldehydes
Nonaromatic Ketones
Furans
Pyrans
Sugars
Anhydro-ß-D-arabino-furanose, 1,5Anhydro-ß-D-glucopyranose(Levoglucosan)
Dianhydro-a-D-glucopyranose, 1,4:3,6LMM lignin
Catechols
Lignin derived Phenols
Guaiacols (Methoxy phenols)
HMM lignin
Extractives
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wt-%
wet
23,9
4,28
1,15
2,56
0,15
0,42
2,23
0,23
2,00
15,41
7,36
0,01
4,06
2,55
0,84
34,44
0,21
3,04
0,13
13,44
0,05
0,07
2,89
1,95
4,35
dry
0
5,6
1,5
3,4
0,2
0,6
2,9
0,3
2,6
20,3
9,72
0,01
5,36
3,37
1,10
45,3
0,27
4,01
0,17
17,7
0,06
0,09
3,82
2,6
5,7
C
H
N
O
40,0
6,7
0
53
60,0
13,3
0
27
59,9
6,5
0,1
33,5
44,1
6,6
0,1
49,2
68,0
6,7
0,1
25,2
63,5
75,4
5,9
9,0
0,3
0,2
30,3
15,4
VTT analysis of bio-oil fractions; Anja Oasmaa, 2007
12
3. Bio-oil applications
13
3
Schematic overview
Bio-oil
thermal
chemical
upgrading
gasifier
boiler
co-combustion
micro turbine
diesel engine
fractions
compounds
refinery co-feed
syngas
hydrogen
heat
steam
electricty
power
electricity
heat
liquid smoke
adhesives
fertilizer
aldehydes
phenols
levoglucosan
transportation fuels
chemicals
transportation fuels
chemicals
Dietrich Meier, 2008
14
3
Oilon boilers Finland
Opra gas turbine, Netherlands
Thermal applications
Sulzer marine diesel, Switzerland
Chemrec entrained flow gasifier, Sweden
Electrabel power station, Netherlands
Shell refinery
15
3
Chemicals
biochar
activated carbon
char
carbon black
meat browning agent
smoke flavors
water sol.
fraction
acids / road deicers
biolime
slow-release fertilizer
biomass
residues
wood preservatives
bio‐oil
boiler/engine/gasifier fuel
adhesives
hydroxyacetaldehyde
water insol.
fraction
(glycolaldehyde)
levoglucosan
phenols (from lignin)
gas
furfural (from xylose)
levulinic acid (from
glucose)
16
3
Syngas route: chemicals and biofuels
building block
chemicals
bio-oil
oil/residue
gasifier
hydrogen
methanol and MTG
mixed alcohols
syngas
bio-oil /char
slurrie
entrained
flow
slagging
gasifier
dimethyl ether
fischer tropsch
liquids
17
3
Upgrading: chemicals and biofuels
pyrol.
plant
pyrol.
plant
oil gasifier
pyrol.
plant
pyrol.
plant
H2
fast
pyrolysis
oil
pyrol.
plant
pyrol.
plant
hydro
stabilization
H2
hydrodeoxygenation
H2
traditional
refinery
H2
pyrol.
plant
gasification
in SCW
organics
in
water
chemicals
biofuels
18
4. Technology and suppliers
19
4
Technologies and suppliers
reactor type
largest unit
built
Dynamotive
Canada
fluid bed
8 ton /hr
Ensyn / UOP
Canada
circulating bed
4 ton/hr
BTG
Netherlands
rotating cone
2 ton/hr
METSO / UPM Finland
circulating bed
0.4 ton/hr
KIT
Germany
twin screw
0.5 ton/hr
Pytec
Germany
ablative
0.5 ton/hr
20
4
Dynamotive
Guelph 200 t/day
21
4
Ensyn / UOP
Renfrew 100 t/day
22
4
BTG-BTL
Malaysia 50 t/day
23
4
BTG-BTL
Demonstration plant “Empyro”
in Hengelo, The Netherlands
Premises of Akzo Nobel
120 ton/day dry wood
Supported by the EU
www.empyroproject.eu
2010: permits and design
2011: construction
2012: in operation
24
4
CFB combustor
METSO / UPM: VTT concept
connected pyrolysis system
maximum degree of integration
pilot testing in
Tampere, Finland
25
5. Opportunities for catalysis
26
5
Positions for catalysis in fast pyrolysis
hot flue gas
in-bed catalysis
natural catalysts
wet impregnation
combustor
gas cleaning
prim. electricity
gas
ex-bed catalysis
feed
hopper
gas
bio-oil gasification
bio-oil upgrading
condensor
reactor
bio-oil
bio-char
27
5
a)
natural catalysts
alkali metals such as K, Na, Ca, M
high ash contents reduces the bio-oil yield
washing of biomass leads to high concentrations of
levoglucosan in the bio-oil
pretreatment of the biomass adds significantly to the
feedstock costs
28
5
b)
in-bed and ex-bed catalysis
in-bed
immediate attack of the released volatiles
catalyst can act as the process heat carrier
char combustor in the pyrolysis process can be a
catalyst regenerator
temperature of catalysis is fixed
abrasion resistant catalyst required
ex-bed
flexibility in conditions of catalysis such as temperature,
particle size and shape, reactor type
29
5
b)
in-bed and ex-bed catalysis
ZSM‐5
Products
(iso-alkanes /) aromatics
+ coke + CO + CO2 + Hw2oOod / waste
Reactions
dehydration, decarboxylation, isomerization,
dehydrogenation, oligomerization
Catalysts
examined
FCC
H-forms of zeolites: Beta, Y, ZSM-5
alumina and silica alumina
transition metal catalysts (Fe/Cr)
metal doped MCM-41 mesoporous materials
Mordenite
Zeolite Beta
30
5
b)
in-bed and ex-bed catalysis
In-bed / ex-bed catalytic pyrolysis
CO,CO2,H2O
50 wt %
Best results with HZSM-5
Theoretically maximal
hydrocarbon yield: 55 wt%
energetic yield:
70 %
Pyrolysis oil
100 wt%
Promising is the development of modified MCM41 mesoporous materials, but hydrothermal
stability is still very poor
coke on catalyst
20 to30 wt%
Hydrocarbons
15 to 30 wt%
31
5
c)
zeolite cracking of bio-oil
separate process, or co-processing in a traditional FCC unit
FCC of bio-oil over zeolites has been tested at 350 < T <
700 oC
results similar to “in-bed” catalytic pyrolysis: predominantly
aromatics and lots of coke deposited on the catalyst
water and gases as the other by-products
32
5
d)
hydrodeoxygenation or HDO
stabilization under hydrogen pressure at 250 to 275 oC and,
after water separation, hydrotreatment at 350 to 400 oC
commercial sulphided CoMo and NiMo and new catalysts like
Ru/C and CuNi/δ-Al2O3
complete deoxygenation can be achieved, but oxygen removal is
not the ultimate goal; the oil should be made distillable and
repolymerization should be avoided
subject of the European “Biocoup” project with a.o. Shell, VTT,
CNRS, BIC, BTG, Univ. Groningen, Univ. Twente
33
5
d)
HDO with Ru/C catalysts: % oxygen removed
CH1.45O0.55
0%
CH1.3O0.10
50 %
70 %
99 % 88 %
Samples produced by Veba Oil
Venderbosch et al., J. Chem. Techn. & Biotech., 85(5), 2010
34
5
d)
HDO: elemental composition
Venderbosch et al., J. Chem. Techn. & Biotech., 85(5), 2010
35
5
d)
HDO: changing liquid properties
Ardiyanti et al., 2009 AIChE Spring National Meeting, Tampa
36
5
d)
HDO: collected literature data
Venderbosch et al., J. Chem. Techn. & Biotech., 85(5), 2010
37
no H2
no catalyst
high
molecular
weight
fragments
TT
fast
pyrolysis
oil
HSTA
with H2
and catalyst
TT(continued)
char
HDO
1 phase:
stable
fragments
soluble in
water
TT = thermal treatment
175 to 250 oC ; 200 bar; minutes
HDO
CxHy
HSTA = hydro-stabilization
175 to 250 oC ; 200 bar; minutes
2 phases:
non polar
fragments
in heavy
organic
phase
???
HCRA
CxHy
HDO = hydro-de-oxygenation
> 250 oC ; 200 bar; up to 1 hour
2 phases:
non polar
fragments
in light
organic
phase
HCRA = hydro-cracking
> 275 oC ; 350 bar; approx. 1 hour
38
5
d)
HDO: challenges
1. Limit the hydrogen consumption (200 Nm3/ton bio-oil) and
upgrade no further than required for co-feeding refinery units
2. Suppress re-polymerization and the formation of CH4, C2H6, .. .
3. Achieve high energetic yields, and valorize any by-products
(e.g. H2 or chemicals from separated water fractions)
4. Develop good catalysts and reaction systems
5. Find the optimal process conditions and route
39
5
HDO & catalytic pyrolysis: overview
complete HDO
mild HDO
in-bed catalysis
ex-bed catalysis
> 275 oC
175 to 250 oC
400 to 500 oC
flexible
pressure
200 - 350 bar
200 bar
1 bar
1 bar
hydrogen
700 Nm3/kg
200 Nm3/kg
none
none
catalysts
sulfided NiMo or
CoMo on alumina
Ru/C
Ni-Cu /δ Al2O3
FCC (zeolites )
various
products
CH1.5 , H2O
CH1.3O0.10, H2O
CH1.2 , H2O, CO2
CH1.2 , H2O, CO2
water dissolved
compounds
water dissolved
compounds
coke
coke
30 wt %
50 wt%
20 wt %
20 wt %
35 to 40 %
60 to 65 %
50 %
50 %
temperature
by-products
mass yield
energy yield
40
5
Conclusions
Biomass liquefaction by fast pyrolysis offers additional advantages in
relation to the production of 2nd generation car fuels and bio-chemicals
Main RTD items are now related to car fuels production and include
catalytic pyrolysis, bio-oil upgrading, process improvement and the
development of ASTM standards
Next-five-years world RTD budget ( public sector) for fast pyrolysis is
estimated to be approximately 100 million euro’s, to be spent mainly in
the US, Canada, Europe and China
Large scale demonstration is delayed by a lack of risk taking investors
and is waiting for industrial involvement (oil companies, food/feed
companies). This has now started!
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