Distributed Bio-Oil Reforming - Energy.gov...Process Upsets Long Duration Runs Demonstrate...
Transcript of Distributed Bio-Oil Reforming - Energy.gov...Process Upsets Long Duration Runs Demonstrate...
Distributed Bio-Oil Reforming
R. Evans, S. Czernik, R. French, M. RatcliffNational Renewable Energy Laboratory
J. Marda, A. M. DeanColorado School of Mines
Bio-Derived Liquids Distributed Reforming Working Group Meeting
HFC&IT Program Baltimore, MD
October 24, 2006
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GasificationPartial oxidation
CH1.46O.67 + 0.16 O2 → CO + 0.73 H2 Biomass Syngas
Water-Gas ShiftCO + H2O CO2 + H2
CH1.46O.67 + 0.16 O2 +H2O →CO2 + 1.73 H2
Biomass Hydrogen (14.3% yield)
Practical yields 10%2
Pyrolysis
Thermal decomposition occurring in the absence of oxygen
Is always the first step in combustion and gasification processes
Known as a technology for producing charcoal and chemicals for thousands years
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Biomass
Lignin: 15%–25% Complex aromatic structure
Hemicellulose: 23%–32%
sugars
abundant sugar in the biosphere
Cellulose: 38%–50% Most abundant form of carbon
Polymer of glucose
Polymer of 5- and 6-carbon
Xylose is the second most
in biosphere
Biomass Pyrolysis ProductsLiquid Char Gas
FAST PYROLYSIS 75% 12% 13% •moderate temperature •short residence time
CARBONIZATION 30% 35% 35% •low temperature •long residence time
GASIFICATION .1 - 5% 10% 85% •high temperature •Short to long residence time
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Fast Pyrolysis
• Fast pyrolysis is a thermal process that rapidly heats biomass to a carefully controlled temperature (~500°C), then very quickly cools the volatile products (<2 sec) formed in the reactor
• Offers the unique advantage of producing a liquid that can be stored and transported
• Has been developed in many reactor configurations; at present is at early stage of development (100 t/day commercial plant)
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Bubbling Fluid Bed Pyrolysis
GAS
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BIOMASS
BIO-OIL CHAR
For reactor or export
Gas recycle
For fluidization or export
Fluid Bed
Reactor
Fast Pyrolysis
CH1.46O0.67 → 0.71CH1.98O0.76 + 0.21CH0.1O0.15 + 0.08CH0.44O1.23
Biomass Bio-oil Char Gas 75% 13% 12%
Catalytic Steam Reforming of Bio-oil
CH1.98O0.76 + 1.24 H2O ⎯→ CO2 + 2.23 H2
Bio-oil Steam Hydrogen
Biomass 13.0% yield H2 Practical yield 10%
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Fast Pyrolysis Bio-oil Bio-oil is water miscible and is comprised
of many oxygenated organic chemicals. • Dark brown mobile liquid, • Combustible, • Not miscible with hydrocarbons, • Heating value ~ 17 MJ/kg, • Density ~ 1.2 kg/l, • Acid, pH ~ 2.5, • •
time
Pungent odour, “Ages” - viscosity increases with
Approach
PYROLYSIS Bio-oilBiomass Methanol
VOLATILIZATION
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REFORMING
H2
Show that bio-oil and blends with methanol can be fed without excessive coking and develop a process to meet HFC&IT cost and performance objectives.
O2 Low Temperature Oxidative Cracking
SHIFT
CO2SEPARATION
H2O
Thermal Severity
O HO CH2 C H OH
OH
Primary TertiarySecondary
Biomass H2O CO CO2
Char
“Carbon”
Bio-Oil H2, CO, CO2, H2O, C2H4,+
Olefins… Furans, Phenols, BTX, Ketenes,
H2O H2 CH4 CO CO2 PAH
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Schematic of Pyrolysis Reactor & NREL’s MBMS Sampling System
Products and
Collisions Q1 Q2 Q3
Argon Collision
Transients Three Stage Free-Jet
{P+} +} e-
EI Source
He
He
Tpy
T1 T3 T4 T5
He
T2
Turbomolecular Pump
Turbomolecular Pump
Turbomolecular Pump
Molecular Beam Source Triple Quadrupole Mass Analyzer
{D
Detector
Molecular Gas Drag Pump
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Rel
ativ
e In
tens
ity
Lignin Pyrolysis 675 ms @ 500 oC
208 CH2 CH CH OH CH3
210180 MeO OMe OMe OHOH
m/z 210 m/z 138 138 168
124 272 302 332234 358
388 418
0 50 100 150 200 250 300 350 400 450
m/z 13
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Lignin Pyrolysis Score Plot
-3
0
3
-4 -2 0 2
500 550 600 625 650 675 700 725 750 775 800
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Lignin Resolved Component Spectra
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4
0
50 100 150 200 250 300 350 400
168
358
332 302
272 220
234
210
194
180
151
Primary
2.4
268 214
200
190 176
298 242 226
164 150
138
124
Secondary
3.2
2.4
1.6
1.6
0.8
0.8
0 0
50 100 150 200 250 300 350 400 50 100 150 200 250 300 350 400
120
66
78
94
158 170
206
264
104
128
142
184
232 248
Tertiary
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-LN
(Cp/
Cp0
)4
3
2
1
0
Lignin Empirical Kinetic Model
500 C
550 C
600 C
0 0.2 0.4 0.6 0.8
Residence time, S 16
17O0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
C
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
H
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
650 oC
550 oC
P = 1 atm
CarbonDeposition
No CarbonDeposition
12 3
4 5 6 78
910111213
14
15161718
19
2021
2223
Equilibrium Modeling Results
1 = Bio-Oil composition, which liesin the region where carbon will form at 650 C
2-8 = O2 addition points9-13 = H2O addition
14-23 = both O2 and H2O
Goal is to identify the thermodynamic and kinetic domains for deposit free operation
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oC
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 0.75 1
Dife
rent
ial S
igna
l, %
of t
otal
0
25
50
75
100
Inte
grat
ed S
igna
l,% o
f tot
al
46 mg
51 mg
54 mg
Average Residue = 6% Bio-Oil Film Volatilization – 400
0.25 0.5
Time, Min.
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Bio-Oil Film Volatilization MBMS Bio-Oil Spectrum
Toil = 300 oC Tvc = 300 oC no O2
31
272
164
137
60
43
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0
1
2
3
4
5
0 125 150 175 225 250 300
m/z
% o
f Tot
al Io
n Si
gnal
HC
O
CH2HO
CH3
OH O
O
HO
25 50 75 100 200 275
OMe
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Bio-Oil Film Volatilization Cracking 0.5 s @ 650 C
Toil = 400 oC Tvc = 650 oC no O2
124 136
110
28
31
60
43
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0
1
2
3
4
5
6
7
0 125 150 200 225 250 300
m/z
% o
f Tot
al Io
n Si
gnal
OH
OH
OH
CH3
25 50 75 100 175 275
CHO
110
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Bio-Oil Film Volatilization Oxidative Cracking 0.5 s @ 650 C
44
60
18
0
5
10
15
20
25
0 125 150 175 200 225 250 300
m/z
% o
f Tot
al Io
n Si
gnal
T = 400 oC Tvc = 650 oC 2
256240226212
198 162
144
122
110
0.00
0.10
0.20
0.30
0.40
0.50
0.60
100 150 175 225 250 275
H2O
CO
CO2
25 50 75 100 275
oil with O
125 200 300
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Ultrasonic Nozzle
• fine mist at 0.3g/min
• steady liquidfeed at low rates
Generating a
Enables
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yringe Pump
l
r
Power Supply
Gas
MBMS
Furnace
Bed
Temperature Read-Out
Gas
Dual S
Bio-Oi
Wate
MFM Ultrasonic Nozzle
Catalyst
MFM
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Ultrasonic NebulizerOxidative Cracking 0.5 s @ 650 C
0.0E+00
5.0E+07
1.0E+08
1.5E+08
2.0E+08
2.5E+08
3.0E+08
3.5E+08
0 2 4 6 8 10 12 14
Time, min
Abu
ndan
ce
18324428
0.0E+00
1.0E+08
2.0E+08
3.0E+08
4.0E+08
10 10.5 11 11.5 120.0E+00
1.0E+07
2.0E+07
3.0E+07
4.0E+07
28
44
1878
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% Residual Carbon: 7.7%
% o
f Tot
al S
igna
l
Ultrasonic NebulizerThermal Cracking 0.5 s @ 650 C
6
5
4
3
2
1
0
15013677
11094 60
43
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OH
CH3
OH
OH
OH
CH3 C
O
H
HC
O
CH2HO
31 = 13.4% 32 = 8.8%
CHO
0 20 40 60 80 100 120 140 160 180 200
m/z 25
40
Ultrasonic Nebulizer
% o
f Tot
al S
igna
l
Oxidative Cracking 0.5 s @ 650 C 28 CO
78
94 128
178
0
1
2
3
4
75 125
0.5
1.5
2.5
3.5
175
35
30
25
20 H2O
1815
10
5
0
CO2
44
MeOH OH31 78
94 128 178
0 20 40 60 80 100 120 140 160 180 200
m/z
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Carbon ConversionOxidative Cracking 0.5 s @ 650 C
Equil. CO Equil. CO2
0
20
40
60
80
Car
bon
Con
vers
ion,
%
/
/
l
CO-Bio-Oil/MeOH
CO-MeOH
CO2-Bio-Oil/MeOH
CO2-MeOH
CO-Bio-Oil MeOH/H2O
CO2-Bio-Oil/MeOH/H2O
CO-Bio-Oil/MeOH (H2O)*
*H2O not inc uded in O/C
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3
O/C Mole Ratio
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Carbon ConversionOxidative Cracking 0.5 s @ 500-650oC
0
10
20
30
40
50
60
70
80 C
O Y
ield
%
500 525 550 575 600 650
0.0 0.5 1.0 1.5 2.0
O/C
28
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Methanol
Bio-Oil
Oxidative Cracking - Methanol vs Bio-Oil
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Process Comparison0
C 44.2 H O 47.1 47.4
H/C O/C 0.8
1500 i 11.9 11.9 i
525 525 236 232
0 246 ith O2
) O/C( 0.5
/407 430
800 600
M 6 5 l 372 l 0 130
0 130 632
Fluid Bed Staged Bio-Oil Organics % 80 78
MeOH % 10 water,wt% 20 18
45 7.9 8.4
2.1 2.3 0.8
H2 production rate, kg/day 1500 H2 Y eld, wt%
Conversion eff ciency,% 70 70 Bio-Oil Feed Rate, kg/hr Feed C feed rate, kg/hr
O2 feed rate, kg/hr Ratios wH/C(H2Ofree 1.5 1.7
H2Ofree) 1.3 Starting H2O/C 0.30 0.27
H2O C after Oxcrack 0.30 0.75 Water addition, Kg/hr 1668
Catalyst load, kg 1734 Temperature, C
Reactor diameter, M 1.03 0.31 Reactor height,
Catalyst reactor vo ume, L 5029 Cracking reactor vo ume, L
Vaporizer, L Total reactor volume, L 5029
Project Timeline
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Task Name
Bio-Oil Volatilization Processing Options Modification and Characterization Injector Development Coking Studies Go / No Go on Bio-Oil performance
Oxidative Cracking Proof of Concept Reduce Catalyst Loading by 50% Partial Oxidation Database Modeling and Optimization Jon Marda Thesis
Catalytic Auto-Thermal Reforming Catalyst Development
Integrated Separation Concept Evaluation Membrane Support Integrated Laboratory System Experiment Go / No Go on Conceptual Design
Systems Engineering Oxygen, Steam and Heat Integration Engineering Design and Construction Prototype System Developed Heat and Mass Balances Process Upsets Long Duration Runs Demonstrate Distributed Hydrogen Production from Bio-Oil for $3.6/gge
Safety Analysis Review and Analysis of Pressure, O2, H2 Systems Integration
5/31
6/30
5/30
6/1
6/30
12/3
2005 2006 2007 2008 2009 2010 2011
Summary
Relevance Near Term Renewable Feedstock for Distributed Reforming
Approach Bio-Oil Processed at Low Temp Homogeneous and Catalytic Auto-Thermal Reforming
Accomplishments Progress in Volatilization and Oxidative Cracking
Collaborations •Colorado School of Mines •Chevron
Future Work •Catalysis Integration in FY07 by working with DOE funded team
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Technical Challenges
• Bio-Oil Volatilization – Management of residue
• Oxidative Homogeneous Cracking – High Reactivity but Unexpected Aromatics
• Catalyst System Design and Performance• Carbon Deposit Removal and Catalyst
Regeneration Management • Process Energy Integration • Integrated Hydrogen Separation
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Complementary Projects
• Chevron Bio-oil Feedstock Effects – Bio-oils produced from a variety of feedstocks– Performance in staged auto-thermal reforming– Determine effect of major and trace constituents
• USDA/DOE Bioenergy Initiative – ISU, Cargill, NREL, ORNL, Eprida, USDA ARS – Corn Stover Pyrolysis for H2, NH3, Bio-carbon
based soil amendments– NREL: Bio-oil characterization and reforming
• DOE Biomass Program – Bio-oil Stabilization and Derivatization
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