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Distributed Bio-Oil Reforming2006 DOE Hydrogen, Fuel Cells & Infrastructure
Technologies Program Review
R. J. Evans, S. Czernik, R. French, J. Marda
National Renewable Energy LaboratoryMay 16, 2006
This presentation does not contain any proprietary or confidential information
Project ID#PD5
Disclaimer and Government License
This work has been authored by Midwest Research Institute (MRI) under Contract No. DE-AC36-99GO10337 with the U.S. Department of Energy (the “DOE”). The United States Government (the “Government”) retains and the publisher, by accepting the work for publication, acknowledges that the Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for Government purposes.
Neither MRI, the DOE, the Government, nor any other agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe any privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not constitute or imply its endorsement, recommendation, or favoring by the Government or any agency thereof. The views and opinions of the authors and/or presenters expressed herein do not necessarily state or reflect those of MRI, the DOE, the Government, or any agency thereof.
OverviewTimeline• Project start 2005• Project end 2010• 15% completed
Production BarriersA. Fuel Processor Capital B. Fuel Processor ManufacturingC. Operation & MaintenanceD. Feedstock Issues F. Control & Safety
Target $3.60/gge
Budget• FY05 $100K• FY06 $300K
Partners• Colorado School of Mines (FY06) - Oxidative cracking• Chevron (FY06) - Feedstock Project planned for FY06
ApproachBio-oilPYROLYSIS
REFORMING
Biomass Methanol
H2
Show that bio-oil and blends with methanol can be fed without excessive cokingand develop a process to meet HFC&IT cost and performance objectives.
VOLATILIZATION
O2 Low TemperatureOxidative Cracking
SHIFT
SEPARATION
H2O
CO2
Objectives
• Overall: – Develop the necessary understanding of the
process chemistry, compositional effects, catalyst chemistry, deactivation, and regeneration strategy as a basis for process definition for automated distributed reforming
• FY06– Demonstrate partial oxidation and show that it can
reduce the required catalyst loading in the reforming step by 50%
Distributed Bio-Oil Reforming Approach
Volatilization Oxidative Cracking
Bio-Oil (+MEOH) O2
Catalytic Auto-Thermal H2
Enabling Research:
Process Integration:
H2O
Oxidative Cracking Kinetics and Mechanisms
Process Optimization
Catalyst Screening
Low Temperature Catalytic Oxidation Mechanisms
Engineering Testing
AirIndirect Heat
Heat and Mass Balance
H2O, CO, CH4,CO2
Separation
H2O + CO2
~400oC ~650oC
Q
Technical Accomplishments
• FY05: Whole oil successfully run– With 10% MeOH addition, bio-oil
processing was trouble free over short run durations (up to 16 hrs)
• FY06: Accomplishments to date– Bio-oil volatilization method developed– Oxidative cracking promising results – Progress toward July milestone on target
Thermal Severity
Primary Secondary Tertiary
Biomass H2OCOCO2
Char
“Carbon”
Bio-Oil H2OH2CH4COCO2PAH
H2, CO, CO2, H2O, C2H4,+Furans, Phenols, BTX, Ketenes, Olefins…
HC
O
CH2HO
OH
OH
Equilibrium Modeling Results
O0.0 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
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
Spray Injector Reactor System
Spray Injector Results
Run Liq. Feed
g/minAir coeff.
% Temp, C Time, s N2 O2 H2 CO CO2 CH4 C Bal, %1 0.5 163 600 2.4 79 15.96 0.00 1.19 4.19 0.00 76%2 0.5 162 599 1.1 78 17.18 0.00 0.59 4.16 0.00 68%3 1.0 99 602 1.4 79 11.61 0.00 2.78 6.26 0.00 69%4 1.0 65 601 1.5 79 5.27 0.00 4.06 11.64 0.00 65%5 1.0 66 636 1.4 80 2.28 0.00 5.96 11.74 0.08 74%6 1.0 59 650 1.4 78 0.95 0.82 6.92 13.36 0.23 71%7 1.0 53 649 1.4 75 0.48 1.45 11.05 11.27 0.40 65%8 1.0 47 650 1.4 72 0.24 3.24 14.75 9.33 0.72 56%9 1.0 34 647 1.4 29 0.19 22.11 32.11 15.38 1.63 32%
10 0.9 54 698 1.3 73 0.13 2.56 12.52 10.94 0.63 70%11 1.0 52 748 2.9 68 0.00 6.55 13.20 11.21 1.26 76%12 1.0 54 750 2.7 75 0.03 3.92 9.05 11.23 0.74 72%
Gas Composition, vol. %
Spray injection resulted in low carbon conversionto CO and formation of aromatics and carbon
Schematic of Pyrolysis Reactor & NREL’s MBMS Sampling System
MolecularDragPump
CollisionsQ1 Q2 Q3
ArgonCollision
Gas
TurbomolecularPump
TurbomolecularPump
TurbomolecularPump
ProductsandTransients Three Stage Free-Jet
Molecular Beam SourceTriple QuadrupoleMass Analyzer
{P+} {D+}
Detector
e-
EISource
He
He
Tpy
T1 T3 T4 T5
He
T2
Bio-Oil Film Volatilization – 400 oC
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 0.25 0.5 0.75 1
Time, Min.
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 MBMS Bio-Oil Spectrum
Toil = 300 oC Tvc = 300 oC no O2
31
272
164
137
60
43
18
0
1
2
3
4
5
0 25 50 75 100 125 150 175 200 225 250 275 300
m/z
% o
f Tot
al Io
n Si
gnal
HC
O
CH2HO
CH3
OH
OMeO
O
HO
Bio-Oil Film Volatilization Cracking 0.5 s @ 650 C
Toil = 400 oC Tvc = 650 oC no O2
124136
110
28
31
60
43
18
0
1
2
3
4
5
6
7
0 25 50 75 100 125 150 175 200 225 250 275 300
m/z
% o
f Tot
al Io
n Si
gnal
OH
OH
OH
CHO
CH3
Bio-Oil Film VolatilizationOxidative Cracking 0.5 s @ 650 C
44
11060
18
0
5
10
15
20
25
0 25 50 75 100 125 150 175 200 225 250 275 300
m/z
% o
f Tot
al Io
n Si
gnal
Toil = 400 oC Tvc = 650 oC with O2
256240226212
198162
144
122
110
0.00
0.10
0.20
0.30
0.40
0.50
0.60
100 125 150 175 200 225 250 275 300
H2O
CO
CO2
Ultrasonic Nozzle
• Generating a fine mist at 0.3g/min
• Enables steady liquid feed at low rates
Dual Syringe Pump
Bio-Oil
Water
Power Supply
Gas MFM
MBMS
Ultrasonic Nozzle
Furnace
Catalyst Bed
Temperature Read-Out
Gas MFM
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
32
% Residual Carbon: 7.7%
Ultrasonic NebulizerThermal Cracking 0.5 s @ 650 C
15013677
1109460
43
18
0
1
2
3
4
5
6
0 20 40 60 80 100 120 140 160 180 200
m/z
% o
f Tot
al S
igna
l
31 = 13.4%32 = 8.8%
OHCHO
CH3
OH
OH
OH
CH3 C
O
H
HC
O
CH2HO
Ultrasonic NebulizerOxidative Cracking 0.5 s @ 650 C
31
18
28
44
7894 128 178
0
5
10
15
20
25
30
35
40
0 20 40 60 80 100 120 140 160 180 200
m/z
% o
f Tot
al S
igna
l
OH
CO2
CO
H2O
78
94 128
178
00.5
11.5
22.5
33.5
4
75 125 175
MeOH
Carbon ConversionOxidative Cracking 0.5 s @ 650 C
Equil. COEquil. CO2
0
20
40
60
80
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3
O/C Mole Ratio
Car
bon
Con
vers
ion,
%
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 included in O/C
Project Timeline
Task 2: Distributed Reforming of Renewable Liquid Feedstocks
Distributed Reforming
FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012
P2 P5F2 C12
5P6Sf3 C5 A1 A2 Sf5V9
C3
P3 4
Milestones
4 Verify feasibility of achieving $3.60/gge for renewable liquids distributed reforming.5 Down-select research for distributed production from bio-derived renewable liquids.
Outputs
P2 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.P3 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P5 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P6 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.
Inputs
C3 Input from Codes and Standards: Preliminary Assessment of Safety, Codes and Standards requirements for the hydrogen delivery infrastructure.
Sf3 Input from Safety: Safety requirements and protocols for refueling.C5 Input from Codes and Standards: Completed hydrogen fuel quality standard as ISO Technical Specification.A1 Input from Systems Analysis: Complete technoeconomic analysis on production and delivery technologies currently
being researched to meet overall Program hydrogen fuel objective.F2 Input from Fuel Cells: Research results of advanced reformer development.V9 Input from Technology Validation: Final report on safety and O&M of three refueling stations.A2 Input from Systems Analysis: Initial recommended hydrogen quality at each point in the system.C12 Input from Codes and Standards: Final hydrogen fuel quality standard as ISO Standard.Sf5 Input from Safety: Safety requirements and protocols for refueling.
Task 2: Distributed Reforming of Renewable Liquid FeedstocksTask 2: Distributed Reforming of Renewable Liquid Feedstocks
Distributed Reforming
FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012
P2 P5F2 C12
5P6Sf3 C5 A1 A2 Sf5V9
C3
P3 4
Milestones
4 Verify feasibility of achieving $3.60/gge for renewable liquids distributed reforming.5 Down-select research for distributed production from bio-derived renewable liquids.
Outputs
P2 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.P3 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P5 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P6 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.
Inputs
C3 Input from Codes and Standards: Preliminary Assessment of Safety, Codes and Standards requirements for the hydrogen delivery infrastructure.
Sf3 Input from Safety: Safety requirements and protocols for refueling.C5 Input from Codes and Standards: Completed hydrogen fuel quality standard as ISO Technical Specification.A1 Input from Systems Analysis: Complete technoeconomic analysis on production and delivery technologies currently
being researched to meet overall Program hydrogen fuel objective.F2 Input from Fuel Cells: Research results of advanced reformer development.V9 Input from Technology Validation: Final report on safety and O&M of three refueling stations.A2 Input from Systems Analysis: Initial recommended hydrogen quality at each point in the system.C12 Input from Codes and Standards: Final hydrogen fuel quality standard as ISO Standard.Sf5 Input from Safety: Safety requirements and protocols for refueling.
Distributed Reforming
FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012
P2 P5F2 C12
5P6Sf3 C5 A1 A2 Sf5V9
C3
P3 4
Milestones
4 Verify feasibility of achieving $3.60/gge for renewable liquids distributed reforming.5 Down-select research for distributed production from bio-derived renewable liquids.
Outputs
P2 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.P3 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P5 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P6 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.
Inputs
C3 Input from Codes and Standards: Preliminary Assessment of Safety, Codes and Standards requirements for the hydrogen delivery infrastructure.
Sf3 Input from Safety: Safety requirements and protocols for refueling.C5 Input from Codes and Standards: Completed hydrogen fuel quality standard as ISO Technical Specification.A1 Input from Systems Analysis: Complete technoeconomic analysis on production and delivery technologies currently
being researched to meet overall Program hydrogen fuel objective.F2 Input from Fuel Cells: Research results of advanced reformer development.V9 Input from Technology Validation: Final report on safety and O&M of three refueling stations.A2 Input from Systems Analysis: Initial recommended hydrogen quality at each point in the system.C12 Input from Codes and Standards: Final hydrogen fuel quality standard as ISO Standard.Sf5 Input from Safety: Safety requirements and protocols for refueling.
Project TimelineTask Name
Bio-Oil VolatilizationProcessing OptionsModification and CharacterizationInjector DevelopmentCoking StudiesGo / No Go on Bio-Oil performance
Oxidative CrackingProof of ConceptReduce Catalyst Loading by 50%Partial Oxidation DatabaseModeling and OptimizationJon Marda Thesis
Catalytic Auto-Thermal ReformingCatalyst Development
Integrated SeparationConcept EvaluationMembrane SupportIntegrated Laboratory System ExperimentGo / No Go on Conceptual Design
Systems Engineering Oxygen, Steam and Heat IntegrationEngineering Design and ConstructionPrototype System DevelopedHeat and Mass BalancesProcess UpsetsLong Duration RunsDemonstrate Distributed Hydrogen Production fromBio-Oil for $3.6/gge
Safety AnalysisReview and Analysis of Pressure, O2, H2Systems Integration
5/31
6/30
5/30
6/1
6/30
12/3
2005 2006 2007 2008 2009 2010 2011
Future Work• FY06
– July milestone: Oxidative cracking proof of concept• FY07
– Catalyst testing and collaborative development for this new approach with emphasis on deactivation and poisoning
– “Go/no go” on bio-oil performance– Kinetic modeling and process optimization– Reaction engineering
• FY08– Bench scale bio-oil reforming tests for long-term testing– Prototype design– “Go/no go” on conceptual design
• FY09– Scale up system development
• FY10– Long duration runs
SummaryRelevance Near Term Renewable Feedstock
for Distributed ReformingApproach 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 •Low Temperature Oxidative Cracking Proof of Concept in FY06•Catalysis in FY07
Response to Reviewers Comments• Project would benefit from commercial and
university collaborations – Work to date has been proof of concept – Collaboration began in FY06 with School of Mines
on modeling and Chevron on feedstock effects– Discussions with UMN on catalysis and GE on
prototype development in progress• More detailed collaborative research plan needed
– Elements are in the plan, pending budget• Bio-feed variation effects• Oxidative cracking kinetics• Catalytic oxidation mechanisms • Factor interactions• Catalyst development
Publications and PresentationsCzernik, S. and French, R., Production of Hydrogen from
Plastics by Pyrolysis and Catalytic Steam Reforming, Energy & Fuels, 2006, 20, 754-758
Czernik, S., Evans, R., and French, R., Hydrogen from Biomass; Distributed Production by Steam Reforming of Biomass Pyrolysis Oil, 1st International Symposium on Hydrogen from Renewable Resources, 231 ACS National Meeting, Atlanta, GA, March 26-30, 2006
Critical Assumptions and Issues
• Bio-Oil Volatilization• Oxidative Homogeneous Cracking
Performance & Benefits• Catalyst Design and Performance• Carbon Deposit Removal and Catalyst
Regeneration Management• Process Energy• Hydrogen Separation