from fossil to renewable feedstocks
TRANSCRIPT
Methusalem Advisory Board meeting, Ghent, 17 June 2011
1
From fossil to
renewable feedstocksKevin M. Van Geem
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Outline
• Introduction
• Fast pyrolysis of biomass
• Pyrolysis of renewable fuels: model components
• Biomass to ethylene routes
• Conclusions
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Introduction
P6: From fossil to renewable feedstocks
Multi-scale Modeling and design of chemical Reactions and Reactors
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Introduction
algae
waste bagasse
wood
corn
sugar
cane
short-rotation crops
wood wastes
etc.
Transition from fossil to renewable resources
Biomass
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Outline
• Introduction
• Fast pyrolysis of biomass
• Pyrolysis of renewable fuels: model components
• Biomass to ethylene routes
• Conclusions
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Lignocellulosic biomass
Composition strongly depends on origin biomass
plant biomass
fats, waxes, starches, terpenes
etc…
low molecular weightsubstancesmacromolecular substances
hemi-cellulose
organicmolecules
inorganicspoly-
saccharideslignin
extractivescellulose
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Biomass: cellulose
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Biomass: hemicellulose
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Biomass : lignin
Genetic engineering allows to modify the lignin structure and fraction of lignin
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Biomass: pyrolysis products
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Biomass: pyrolysis process
plant biomass
bio oilgas char
CO2, CO, CH4, H2, lower amounts of
C2’s
aldehydes, ketones, phenol
ethers, alkylphenols,
polyaromaticsetc…
pyrolysis
active carbon
15% 15%70%
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Experimental set-up
Venderbosch and Prins, 2010
AUGER reactor Fluidized bed reactor
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Auger reactor
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Bio oil: main componentsPine wood Bio-oil
Fast Pyrolysis
300 – 600 C
0.5 – 2s
Gas & Char
GC GC Aldehydes, Furans,
Ketones & Alcohols
Carboxlylic Acids
Phenols & Phenons
Guaicols, Syringols &
Catechols
Anhydrosugars
Hydroxy Acids
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GC×GC set-up
TOF-MS
GC×GC
Heated
Transfer-
line
FID
OVEN
TOF-MS
He
Rtx-1 PONA
BPX-50
BPX-50
injector
Liquid CO2
(1)
(2)
(3)
(3)
(6)
(5)
(4)
(7)
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GC×GC set-up
Initial objective
Maximal agreement
between
FID and TOF-MS
chromatograms
modulator
FID
Quantitative results
TOF-MS
Peak identification
Van Geem, Pyl, et al. J. Chrom. A. 2010
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GC×GC: Data Processing
4s 4s 4s 4s 4s 4s 4s 4s
1st dimensionseparation
Modulation 2nd dimensionseparation
Detection
Enhanced Resolution
Enhanced Signal/Noise Ratio
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GC×GC: Data Processing
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Bio oil: main components
O
OH
O
HO
OH
O
O
O
HO
levoglucosan
vanilin
eugenol
methyl-
guaiacolcycloteneO
O
furfural
OO
2-furanone
HO
HOO
O
OH
O
HO
guaiacol
190 components
GCxGC-FID & GCxGC-TOF-MS
analysis
LigninCellulose
Anhydrosugar13%
Ketone8%
Furan13%
Guaiacol20%
Phenol2%
Alcohol5%
Syringol2%
Catechol1%
Cyclo-ketone8%
Aldehyde9%
Carboxylic acid19%
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Bio oil: main components
levoglucosan
OH
HO
OCH3
vanilin
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Bio oil: untreated
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Bio oil: hydrotreated
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Outline
• Introduction
• Fast pyrolysis of biomass
• Pyrolysis of renewable fuels: model components
• Biomass to ethylene routes
• Conclusions
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Methodology
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Validation: pyrolysis in laminar flow reactor
1: butanol vessel, 2: water vessel, 3: electronic balance, 4: pump, 5: valve, 6: evaporator, 7: mixer,8: heater, 9: air, 10: pressure regulator, 11: mass flow controller, 12: nitrogen, 13: reactor, 14: nitrogen internal standard, 15: oven, 16: GC for formaldehyde and water, 17: GC×GC
18: cyclone, 19: condenser, 20: dehydrator, 21: GC for C4-, 22: data acquisition
9
MFC MFC
T1
T2
T3
T4
T5
T6
T7
T8
19
17
21
16
1
2
3
3
4
4
5
5
6
6
7
8
5
5
10 10
12
11 11
13
14
15
18 20
22
VENT
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GCxGC Tof-MS methyldecanoate
Pyl et al., 2011
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Influence COT MD pyrolysis
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Influence COT MD pyrolysis
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Influence COT: MD pyrolysis
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Influence dilution: MD pyrolysis
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Mechanism validation
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Mechanism validation
0
2
4
6
8
10
12
14
0 20 40 60 80 100
CH
4Y
ield
[w
t%]
Conv. [wt%]
Zhaoyu Luo et al.
Herbinet et al. (Red.)
Herbinet et al. (Full)
Experimental
0
5
10
15
20
25
30
0 20 40 60 80 100
C2H
4Y
ield
[w
t%]
Conv. [wt%]
Zhaoyu Luo et al.
Herbinet et al. (Red.)
Herbinet et al. (Full)
Experimental
0
1
2
3
4
5
6
7
8
9
10
0 20 40 60 80 100
CO
2Y
ield
[w
t%]
Conv. [wt%]
Zhaoyu Luo et al.
Herbinet et al. (Red.)
Herbinet et al. (Full)
Experimental
0
2
4
6
8
10
12
14
16
18
0 20 40 60 80 100
CO
Yie
ld [
wt%
]
Conv. [wt%]
Zhaoyu Luo et al.
Herbinet et al. (Red.)
Herbinet et al. (Full)
Experimental
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Reaction path analysis
0
5
10
15
20
0 20 40 60 80 100
C3
:1-2
Yie
ld [
wt%
]
Conv. [wt%]
Zhaoyu Luo et al.
Herbinet et al. (Red.)
Herbinet et al. (Full)
Experimental
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Butanol work
Oxygenated fuels
Improve octane rating
impede sooting and particulate formation
Promote formation of toxic byproducts
Examples of oxygenated fuel additives
1979 (US): MTBE (H2O decontamination)
Late 70’s (US): Ethanol (21.2 MJ/L)
2000’s (Dupont/BP): 1-Butanol (29.2 MJ/L)
2015: 2-methyl-1-propanol or 2-butanol?
Van Geem et al., 2010; Harper et al. 2011
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Acetone/butanol/ethanol pyrolysis/combustion
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 20 40 60 80 100
Yie
ld (w
t%)
Conversion [%]
BUT12
nButenes
0.0
5.0
10.0
15.0
20.0
25.0
0 20 40 60 80 100
Yie
ld (w
t%)
Conversion [%]
C2H4
C2H4
0.0
5.0
10.0
15.0
20.0
25.0
30.0
0 20 40 60 80 100
Yie
ld (w
t%)
Conversion [%]
CH4
CH4
CH4 C2H4
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0 20 40 60 80 100
Yie
ld (w
t%)
Conversion [%]
C3H6
C3H6
C3H6 nC4H8
0
5
10
15
20
25
30
35
40
45
0.50 1.00 1.50 2.00
flam
e s
pe
ed
[cm
/s]
equivalence ratio
Acetone - Burluka et al. (2010)
Acetone - Pichon et al. (2009)
Acetone
ABE
T=298K
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Outline
• Introduction
• Fast pyrolysis of biomass
• Pyrolysis of renewable fuels: model components
• Biomass to ethylene routes: from fats en greases
• Conclusions
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Biomass to hydrocarbon routes
Feedstock
Process
Diesel, Jet, Naphtha
• Biomass to hydrocarbons
– Gasification and enzyme routes not commercial
– Hydrotreated Vegetable Oil (e.g. Bio-Synfining™) commercialized
• Economics based on diesel and jet fuel
• Naphtha co-product tested as feedstock for conventional steam crackers
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Feedstock
Brown grease
Seed oils
Yellow grease
Waste animal fats
Seaweed oils
Tall oil
fatty acid
Algal oils
U.S. sources ~ 360,000 BPD (16 million tonne/y) hydrocarbon equivalent …and increasing
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Process
FEED
JET
Hydro-
deoxygenatorHydrocracker
Water
C5-C9
C10-C15
C15-C18+
C3-C18+
Recycle
Compressor
LPG
Naphtha
C3-C4
Fractionation
Hydrogen
Makeup
Simple, low capital cost process
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Chemistry
O
O
O
O
O
OHC
+ 6 H2O + C3H8
+ 15 H2
3 (1a)
(n-octadecane)
(typical triglyceride with linoleic, oleic, and stearic acids)
H2C
H2C
HO
O
+ 4 H2
+ 2 H2O (1b)
NiMo cat
(isoparaffinic
hydrocarbons)
NiMo cat
Bi-functionalcatalyst
(2)(typical)
+ + H2
Paraffinic hydrocarbons from bio oils via hydrodeoxygenation(Eqs 1a-b) and hydrocracking (Eq 2)
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Renewable kerosene vs Petroleum kerosene
GC×GC-FID analysisPetrochemical
Kerosene
n-paraffins12%
iso-paraffins86%
Naphthenes2%
C10 – C18
Aromatics free
paraffines24%
isoparaffines26%
naphthenes33%
aromatics17%
Paraffinic
Kerosene
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GC GC analysis renewable naphtha
10 40200
4
benzene
30
toluene
ethyl-
benzene
n-C13n-C12n-C11
n-C10n-C9
n-C8
n-C7
n-C6
propyl-
benzene
butyl-
benzene
Hydrodeoxygenation
Hydrocracking
Naphtha
Kerosenen-Paraffins
32.4%
iso-Paraffins59.9%
Olefins0.4%
Naphthenes6.5%
Aromatics0.8%
Pyl et al., accepted
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Follow up story
Paraffinic
Kerosene
C10 – C18 Aromatics free
Hydro-
deoxygenation
Hydrocracking
nC16
C18 olefines
nC18
nC15
nC14
nC17
nC19
nC20
nC10
nC11nC12
nC13
nC14nC15 nC16
nC17
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Simulation results
Product Yield (wt%)
COT = 820°C COT = 850°C COT = 880°C
hydrogen 0.9 1.0 1.1methane 8.2 9.7 10.9ethylene 37.3 39.9 40.4ethane 3.0 2.9 2.8propylene 14.6 14.0 12.4propane 0.3 0.3 0.3isobutene 0.2 0.3 0.32-butene 0.7 0.7 0.61-butene 3.9 1.9 0.71,3-butadiene 7.3 6.6 5.6n-butane 0.1 0.1 0.1benzene 6.7 8.6 9.5toluene 2.5 3.3 3.8Et-benzene 0.2 0.4 0.7xylene 0.1 0.1 0.1styrene 0.4 1.0 1.9indene+ vinyl toluene 0.3 0.5 0.7naphthalene 0.1 0.4 1.2
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Outline
• Introduction
• Fast pyrolysis of biomass
• Pyrolysis of renewable fuels: model components
• Biomass to ethylene routes: from talloil
• Conclusions
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Talloil: byproduct of Kraft process
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Pilot plant set-up
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Pilot plant set-up
cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7
air
oil
N2
flare
DHA
FURNACE & REACTOR TLE ANALYSIS
H2O
hyd
roca
rbo
ns
FEED
IR-GA
preheating & mixing reactor zone
P P P PP
condensate
co
ole
r
GC×GC
RGAPGA
water
oven
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Pilot plant set-up
Nitrogen is used as internal standard
Methane functions as a second internal standard
RGA (TCD)
RGA (FID)
PGA (TCD)
DHA (FID)
GC×GC (FID)
H2 CO2 C2H4 C2H6 C2H2 CH4 CON2
C2 C3 C4CH4
CO2 C2H4 C2H6 C2H2 CO CH4
C2 C3 C4CH4 C5 C6 ...
N2
...CH4
ch
eck
C16
C25
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TOFA GC
1st dimension retention time (min)
0 25
2n
d d
ime
nsi
on
re
ten
tion
tim
e (
s)
0
5 phenanthreneC1-triaro
50 75 100
nC16nC18
nC20
Norabitane
C12H14O
Norabitane-
aro
iC8
nC8
nC10nC12
nC14
nC22
nC24
nC26
C18:1
C16:1
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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DTO feedstock analysis
1st dimension retention time (min)
0 25
2n
d d
ime
nsi
on
re
ten
tion
tim
e (
s)
0
5 phenanthreneC1-triaro
50 75 100
nC16
iC8
nC18
nC20
Norabitane
C12H14O
Norabitane-
aro
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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Naphtha/DTO
1st dimension retention time (min)
0 25
2n
d d
ime
nsi
on
re
ten
tion
tim
e (
s)
0
5 phenanthreneC1-triaro
50 75 100
nC16nC18
nC20
NorabitaneC12H14O
Norabitane-
aro
benzene
toluene
xylenes
C2 arom
nC4
naphthenes
nC10
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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TOFA/DTO feedstock analysisComponent TOFA
Wt%
DTO
Wt%
C12H14O 0.053 0.802
C16:0 FAME 0.713 0.371
C18:1 FAME 2.280 0.243
C18:2 FAME 0.591 0.626
cyclo C18 0.912 0.117
decane 0.137 0.218
dodecane 0.084 0.150
eicosane 3.148 6.194
heneicosane 0.604 0.575
heptadecane 13.235 8.844
heptane 0.279 0.392
hexadecane 0.424 0.412
hexane 0.790 15.657
isoparaffin C16 0.062 0.046
isoparaffin C17 0.780 0.282
isoparaffin C18 1.594 1.062
isoparaffin C19 0.717 0.867
isoparaffin C20 0.151 0.194
nonadecane 1.164 1.829
nonane 0.113 0.145
norabietane 6.128 9.984
norabietane-1aro 1.592 3.521
octadecane 59.520 42.797
octane 0.136 0.180
olefin C18 2.247 2.016
olefin C20 0.781 0.644
paraffin C22 0.292 0.518
paraffin C23 0.250 0.235
paraffin C24 0.359 0.158
paraffin C25 0.282 0.122
paraffin C26 0.195 0.207
pentadecane 0.108 0.138
tetradecane 0.051 0.077
tridecane 0.075 0.156
undecane 0.152 0.220
Methusalem Advisory Board meeting, Ghent, 17 June 2011
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DTO/naphtha feedstock analysis
0
5
10
15
20
25
30
35
40
45
50
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29
Wei
ght f
ract
ion
%
Carbon number
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GC×GC FID chromatogram TOFA5
080
benzene
ethyl-
benzene
C4-
mono-
aromatics
toluenedi-aromaticsstyrene
cyclopentadiene
naphthalene
acenapthylene
methyl-
naphthalenes
0 1st dimension retention time (min)
2n
d d
ime
nsio
n r
ete
ntio
n tim
e (
s)
phenanthrene
unconverted
TOFA
nC18nC16
C18:1 ester
indene
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Detailed effluent with GC×GC FID
Over 100 components are identified and quantified each run
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Conslusions GC×GC analysis of bio-oils produced by fast pyrolysis of biomass allows to quantify more than 50
components qualitatively
Pyrolysis of model components for renewable fuels provides valuable information to validate the
combustion chemistry
Hydrodeoxygenation of waste fats and greases gives a highly paraffinic renewable feedstock
Excellent feedstock for conventional steam crackers
High Ethylene and Propylene yields
Low Coking tendency = long run lengths
Opportunity for petrochemical producers to transition to biorenewable feeds without modifying
process
Hydrodeoxygenated tall oil is also a valuable feed for producing light olefins, but smaller
ethylene and propylene yields are obtained compared to the DHO product of waste fats
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Glossary
Lignin: a polyaromatic structure, part of cell walls of plants and algae
Cellulose: a polysaccharide consisting of a linear chain of several
hundred to over ten thousand β(1→4) linked D-glucose units
Hemicellulose: a polysaccharide consisting of include xylose, mannose,
galactose, rhamnose, and arabinose monomers
Bio-oil: oil produced from lignocellulosic biomass via pyrolysis
Tall oil: by-product of the Kraft process of wood pulp manufacture