Integrated Short Contact Time Hydrogen Generator (SCPO)
2007 DOE H2 Program Annual Review Meeting
Ke Liu, Rick Watson, Gregg Deluga, Court MoorefieldWei Wei, Joel Haynes , Zhe Cui & Greg GilletteGE Global Research Center
Project ID # PDP9
This presentation does not contain any proprietary or confidential information
Theodore KrauseArgonne National Lab
Lanny Schmidt & Anders LarsenUniv. of Minnesota
2
Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Overview
Project start date: 05/30/2005Project end date: 05/30/2008Percent complete: 38%
• Technical Barriers Addressed:-
A. Cost of Fuel Processor-
C. Operation and Maintenance (O&M)-
D. Feedstock Issues-
E. Catalyst sulfur tolerance & durability• Technical Targets (2010):
-
Total Energy Efficiency (%LHV) > 75%- Total H2
Cost < $3.00/gge H2
Total project funding>
DOE share: $2.6M>
Contractor share: $1.4MFunding received in FY05: $490KFunding received in FY06: $400KFunding received in FY07: $890K
Timeline
Budget
Barriers
• University of Minnesota• Argonne National Lab
Partners
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
SCPO Program Highlights & Accomplishments in 2006
Designed, built, shakedown high-P CPO unitTested CPO catalysts use both NG & DieselDesign & build the integrated SMR&WGS
reactorSystem analysis and designEconomic analysisDevelop new bio-liquids reforming programCoordinate R&D activities GE, ANL & UoM, and report to DOE the progress quarterly.
Project Objective
DemoLarge ScaleLaboratory
3 00 μm3 00 μm
Technical Approach•Develop S-tolerate Short Contact Time CPO & SMR Catalysts
•Design Compact Reformer System (SCPO )•Demonstrate Critical Components
S-tolerate CPO catalyst discoveryS-tolerate CPO catalyst developmentCPO catalyst characterization: XRD, XPS
SMR catalyst discoveryVendor CPO & SMR catalyst screening
CPO & SMR catalyst durability test w/wo sulfur dope
SMR & CPO catalyst characterization
Project Overview
To Develop a Compact Hydrogen Generator that can Deliver H2
at a Cost of <$3.0/kg
4
Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
SCPO Tasks, Schedule & Budget
2007 Budget:Materials (k$): 360Labor (k$): 1030Total Funding (k$): 1390
Note: The material budget includes $80K to UoMn
1 2 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 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52
Tasks Subtasks
Task 1: Premix CPO + Sulfur Tolerate CPO Catalyst
1). Pre-mix + CPO Catalyst tests at GE Niska; 2). Low P tests at UoM; 3). High P tests at GE Irvine; 4). Durability tests & APS analysis at
Task 2: Compact SMR Reactor
1). Low P tests at ANL; 2). High P tests at GE; 3). Durability Tests at ANL
Task 3: Cooled WGS Reactor
1). Design, build C-WGS unit; 2). Test C-WGS; 3). Evaluate the benefit of C-WGS for SCPO & IGCC
Task 4: Sorption Kinetics Study with TGA
1). Multi-pollutants detection; 2). Adsorption kinetics; 3). Regeneration kinetics
Task 5: System & Economic Analysis
1). Aspen system model based on new test results; 2). Economic model ( H2A) based on new test results and updated system design.
Task 6: Project Management & Reporting
1). Coordinate the R&D activities of GE-ANL-UoM. Manage the overall SCPO project.
2007 Tasks & Schedule for SCPO & Warm Gas Clean-up
Mar AprQ4/07
Sep Oct Nov DecQ1/07 Q2/07
Jan FebQ3/07
May Jun Jul Aug
YTD Labor: $322KYTD Material: $87KYTD Total:
$409K
TTD Labor: $1,304KTTD Material: $630KTTD Total:
$1,935K
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
B- BurnerBV- Ball ValveCV- Check ValveFM- Flow MeterGV- Globe ValveHV- Hand ValveNG- Natural GasNLV- Not in LabviewOFM- Orifice Flow MeterPDC- Pressure Differential CellPG- Pressure GaugePT- Pressure TransducerRD- Rupture DiskS- Start Up Burner TC- Thermocouple
Test Stand Cart
Water
GE Confidential & Properitery
DOE SCPO System
Process and Instrumentation DiagramSCPO Test Unit
Bay I Hood 3 Chief Tech: D Ladd
SCPO Laboratory Test UnitPage 1
Revision #1
Drawn By: GAD
GEGRC FCL
Date Created: 03/04/05
Date Updated: 03/04/05
Isco !00D Syringe Pump
Shut off ValveVaporizorSuperheater3-way valve for steam ventCheck Valve
Gas Cylinders
Mass Flow Controllers
Check Valves
4 Port Hot Manifold
Hot Box for preheat control
8 Port Manifold for gas mixing
TC preheat Control
3 way valves for fuel lines
TC Precatalyst
TC Post Catalyst
Reactor
TC1TC2
Gas Analysis Valve Burner & Vent
Reactor is 1" OD, 20 mm ID
System is 250 PSIG
All lines SS, ¼ “
Aalborg MFC
Hot Box furnace is custom
Manifolds welded SS
Gas analysis via GC
Back Pressure Valve
Fuel Feed System Prehe
atSteam Generator
Gas Analysis
Task 1: Premix CPO with Sulfur Tolerate CPO CatalystSystem Designed System ConstructedControl & Data
Acquisition Added
Status• Completed the shake-down and started the high-P CPO tests•
Two catalysts tested at diff conditions, high quality data obtained.
Plans:•Heavy usage in Q1 of 2007•Integration with Mixer•Integration with SMR & WGS
Test in 2007
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
High-P CPO Data Obtained in FCL
Time (milliseconds)
Tem
p
CH4
O2mol
%
~350 oC
~1150 oC
~800 oC
10
FLOW
CO, H2
Pressure Drop versus PPI
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Results: Catalyst Testing-Baseline Performance
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Future Work: Ongoing Catalyst Testing• Have Begun Catalyst Testing
–
Atmospheric and high pressure screening–
Evaluating process conditions•
GHSV, Temp., Pressure Drop, S/C, and O2
/C
9
Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Future Work: Ongoing Catalyst Testing
•
System construction completed and commissioned
HAZOP and FMEA Safety Review and System modificationsSystem Calibration and Shakedown with CatalystCurrently testing optimized catalystsUp to 1,000,000 GHSV and 400 psig
Operator Interface
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Task 2 & 3 SMR & Shift Experiments
Bottle RegulatorPressure Switch
Ball valve
Check Valve
Screw-down valve
Legend:
T
F
Pressure Transducer
Temp Controller
Mass Flow Controller
Solenoid valve
setpoint controller
3-Way Valve
w/SolenoidP
Pressure Gauge
Relief Valve
Audible Alarm
Light, Red/Green
Flashing Light, Shutdown
Thermocouple
Data Thermocouple
Cooled-Shift Test StandMar 15, 2007
110 V plug
Digital Display
Inline Filter
E-Stop
Boiler 1
Dra
in
Water
Nitrogen
F
T
Preheater
T
Ven
t
Pump
P
P
PS-105 SV-105 BV-110
F-105 FM-105
CV-105
PT-105PG-105
BV-115
BV-305
B-305 (boiler)PT-305
PG-305
P
PG-510
PT-510
P
PG-705PT-705
PG-710PT-710
TC-705
TC-710
PPT-725
PG-725
SL-710
SL-720
SL-715
PR-705
SL-705
SL-720
SL-715
SL-710 CondensorChiller
GC
SV-720
SV-715
SV-710
SV-705
PH-405
TC-405
P PT-405
PG-405
CT-705
CT-715
HX-710
CV-305
CV-405
PR-305
CO-705CH-705
SL-705
Back PressureRegulator
FPR--705
BPR-705
***S-705 (reactor stand)
3/8" Tube
3/8" Tube
1/2" Tube
Notes: a) All electric valves. b)Flare TBD c) location of vents TBD
FFM305
F
P
PS-605 SV-605 BV-605
F-605 FM-605 CV-605
PT-605PG-605
WGS Mixture
L-105
L-605
C-605
HL-305
P
TC-310
PG-310PT-310
T
TC-315
Di Water
DI-300
T
SL-515SV-515
SulfurAnalyzer
S-700
PR 105
PR 605
FV-305
TC-700
TC-510
TC-725
74C Max
Drain
TC-703
OS-500Hot Oil Skid
Bed-bBed-aChiller
Ven
t
Drain
Drain Drain
Flare
TC-510
P
PG-510
Original: G DelugaRevised: CM Jan 23 ’07
Revised: Wei W Mar 15' 07
Gas Cabinate
LEL Sensor
LEL Sensor LEL Sensor
LEL SensorLEL Sensor
1 USensor UPS
Personal Sensor/Alarm
TTC-a TC-b
PPT-a
PG-a
T
Contamination Skid
Ven
t
PR-705
P
Sulfur TrapOption 1: Double Walled Bubble Column: NaOH
Option 2: Double Walled ZnO/FeO Fixed Bed
P PT-b
PG-b
T
T
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Task 2 &3: SCPO SMR/WGS Test Rig and Control System
•
Labview: Schematic/Blueprint of all controls complete
•Programming in progress: Includes flow control, data monitoring and acquisition, and alarm warnings. • 60Kg/ day Test Rig installation in progress
• Hood & Safety System installed (gas detection, E-stops)
• Burner installation and plumbing 90% complete• Control system design complete: Labview coding
in process• Shakedown May 31. Full test status July 1.• Footprint of the 1500 kg/day SCPO unit including
PSA: 15ft x 10ft (Preliminary estimates, size depends on the compactness of packaging)
Zone 1
Zone 2
Zone 3
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
ANL –
FY07 Workscope and StatusSteam reforming catalyst evaluation and development>
Precious metal catalysts (3 catalysts from vendor A; 2 catalysts
from vendor B; and 3 catalysts from Argonne)
–
Activity (Status: completed)•
Low temperature SMR conditions•
High temperature SMR conditions–
Durability (Status: completed)•
Low temperature SMR conditions–
Sulfur-tolerance (Status: completed)•
Low temperature SMR conditions at 5 and 20 ppm H2
S>
Base metal catalysts (4 catalysts from two commercial vendors)–
Activity (Status: in progress)–
Durability (Status: in progress)Water-gas shift catalyst evaluation>
Precious and base metals (1 PM and 1 base metal catalyst, two different vendors)
–
Activity (Status: in progress)–
Durability (Status: in progress) FY07 funding: $125K
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
SMR Catalysts Were Evaluated for Activity and Durability
•Activity was evaluated by cycling catalyst between low and high T SMR conditions over a period of 48 hours.•Durability was evaluated for low T SMR conditions by cycling between temperatures.•Identified the catalyst that exhibits the best combination of activity and durability.
80
85
90
95
100
600 700 800 900Temperature, oC
CH
4 con
vers
ion,
%
A_1 Cycle_1 A_1 Cycle_2
A_2 Cycle_1 A_2 Cycle_2
B_1 Cycle_1 B_1 Cycle_ 2
B_2 Cycle_1 B_2 Cycle_220
40
60
80
100
500 600 700 800Temperature, oC
CH
4 con
vers
ion,
%
A_1 Cycle_1 A_1 Cycle_2
A_2 Cycle_1 A_2 Cycle_2
B_1 Cycle_1 B_1 Cycle_ 2
B_2 Cycle_1
0
20
40
60
80
100
0 24 48 72 96 120 144 168 192Time, h
CH
4 con
vers
ion,
%
A_1B_1
Temp_1
Temp_2
Activity -
Low Temp SMR Conditions Activity -
High Temp SMR Conditions
Durability –
Low Temp SMR Conditions
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
All Precious Metal SMR Catalysts Have Poor Sulfur Tolerance 5 ppm H2
S0 ppm H2
S
0
20
40
60
80
100
600 650 700 750 800 850Inlet Temperature, oC
CH
4 con
vers
ion,
%
A_1A_2A-3B_1B_2ANL_1ANL_2ANL_3
0
4
8
12
16
20
600 650 700 750 800 850Inlet Temperature, oC
CH
4 con
vers
ion,
%
A_1A_2A_3B_1B_2ANL_1ANL_2ANL_3
• Sulfur poisoning was generally reversible, even at 20 ppm H2
S. Most of the activity could be recovered over 1-2 h by raising the temperature or lowering H2
S concentration.• No evidence of carbon buildup on catalysts.• Increasing the metal loading led to high rates in the absence of H2S but had no
effect on improving the sulfur tolerance (Argonne catalysts).
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
UoMn Accomplishments
•
Completed screening of catalyst systems.10 systems were investigated and Rh-Ce was shown to have the best performance
•Investigated the effect of steam addition in the system at high space velocities
•
Characterized the catalyst using surface analysis (XRD, XPS). This showed that the catalyst is reduced under reaction conditions to oxidation state 0.
•
Developed an experimental technique that allows to sample inside the reactor while running experiments
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Effect of Steam Addition
Tfeed°C
Fm
mo
l/s
Tb
ack
°C
150 200 250 300 350 400 450 500 5500
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
600
650
700
750
800
850
900
950
1000
CO2
H2O
CH4
Tfeed°CF
mm
ol/s
Tb
ack
°C
150 200 250 300 350 400 450 500 5500
0.5
1
1.5
2
2.5
3
3.5
600
650
700
750
800
850
900
950
1000
CO
H2
• Open symbols are with steam replaced by N2
.• The water flow is FH20
in-FH2Oout
• No effect from SR but WGS does play a role• O2
/C=0.68, S/C=1, GHSV 750,000h-1
Spatial Profiles Inside the Foam Catalyst
•Developed a system that allows to in situ
sampling in a system with very high temperature and species gradients
•
Unprecedented spatial resolution (~300μm) on the order of the characteristic length of the support
•
Sampling method introduces minimal disturbance in flow. Sample rate 10ml/min, total flow 5000ml/min
•
Analysis is done by mass spectroscopy which is continuously calibrated by gas chromatography
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
−10 −8 −6 −4 −2 0 2 4 6 8 10 12 14 16 180
0.5
1
1.5
2
2.5
3
3.5
4
Position [mm]
Flo
w [
mm
ol/s]
Rh 0.5%−2%Ce 80ppi GHSV 275,000 h−1 O2/C=0.5
−10 −8 −6 −4 −2 0 2 4 6 8 10 12 14 16 180
100
200
300
400
500
600
700
800
900
Te
mp
era
ture
oCCH
4
O2
CO
H2
CO2
H2O
Tsurf
Tgas
Results From Spatial Profiles
•
0mm is the front face of the catalysts
• 2 zones can be identified:
•
First a short ~2mm oxidation zone, where all O2
is consumed. Second a longer endothermic steam reforming zone
•
Very high temperature gradients in the front of the catalyst
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Sulfur Adsorption Tests via TGA•Absorption Tests / Optimization
—Temperature (P is determined by gasification condition)—H2
S Level—Particle Size (2 levels: study effect of pore-diffusion)—Absorption Kinetics —Optimized Absorption Conditions
( ) nmSHSH xKpTpxf
dtdxr )1(,, 22 −=== ⎟
⎠⎞
⎜⎝⎛−⋅=RTEkK exp
•Regeneration Tests / Optimization—Temperature—O2
Concentration (Air/N2
ratio)—Optimized Regeneration Conditions
•Sorbents Lifetime (Absorption / Regeneration)—Fixed Bed or Fluidized Bed Reactor is Suggested
time, min
weigh
t, m
g
Absorption Regeneration
0
100
time, min
conc
entrat
ion,
%
Empty BedWith Sorbent
•
Break-through point for the sorbent
•
Absorption/regeneration kinetics
•
Optimized operating condition•
Solid residence time in reactor (absorber/regenerator)
•
Fluidized bed reactor/regenerator design
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
TGA
N2
Syngas
He
N2
Air
Water
BPRMFC1
MFC2
MFM
MGC
GC
HP Pump
Vent
Vent
Moisture Knockout Cell
FG
RG1
PG
MFC –
Mass Flow ControllerMFM –
Mass Flow MeterMGC –
Micro GCCEMS –
Continuous Emission Monitoring SystemBPR –
Back Pressure Regulator
FTIR
P&ID –
TGA System
RG2
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Summary & Highlights• High-P CPO data obtained from our high-P CPO unit. Conducting tests daily now.
Preparing more CPO catalysts. • Prepared the catalyst & shipped to Niskayuna; Completed the pre-mixer design, the
mixer is being fabricated. Modified the test rig. Pre-mixer CPO tests is being conducted • SMR & Cooled shift test rig are being built, and the hood is installed, and major
equipments are in place.• Completed the shift kinetics modeling based on literature kinetics found recently.
Completed the preliminary economics analysis. • Completed the IP & literature analysis on WGS catalysts.• ANL & UoMn continuity generate good test data for GE• System analysis/design completed; System pressure trade off analysis completed• Base case catalysts identified, Reactor sizing / design completed.• HEX technology tradeoff completed, HEX technology selected, design completed• Control strategy, start-up & shut-down procedure developed • Completed cost analysis using GE’s process model & DOE’s H2A model
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Ke Liu et al. GE Global Research, EPT-FCL, Irvine, CA PDP9_Liu
Conclusions & Recommendations
SCPO will be a leading technology for H2 production from NG. It is a cost-effective distributed H2 production technology based on the economic analysis of different H2 production technologies. With minor catalyst and process condition modification, we can extendthe feed to gasoline, diesel, ethanol & methanol.
The technologies developed in this program has good synergies with application in fuel blending, NGCC with CO2 capture, SOFC &syngas production for GTL….
Design and built high-P CPO unit and tests are being conducted. Designed and building the SMR & WGS reactors test rig, and conduct testing in 2nd
half of
2007.
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