integrated short contact time hydrogen generator (scpo)ke liu et al. ge global research, ept-fcl,...

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

http://www.anl.gov/index.html

3


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


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

5


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

6


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

7


Results: Catalyst Testing-Baseline Performance

8


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


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

10


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

11


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

12


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

13


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


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,

%



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

14


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).

15


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

16


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

18


−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

19


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

20


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

21


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

22


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.

integrated short contact time hydrogen generator (scpo)ke liu et al. ge global research, ept-fcl,...

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