IGCC and COIGCC and CO 22 Capture Research at the PSDFCapture Research at the PSDF

University of Mississippi Chemical Engineering Clim ate Change CoUniversity of Mississippi Chemical Engineering Clim ate Change Co urseurseApril 15April 15 --16, 200916, 2009

Bob Dahlin, Carl Landham, Robert Strange, Pannalal Vimalchand, WBob Dahlin, Carl Landham, Robert Strange, Pannalal Vimalchand, W anWang Peng, Alex anWang Peng, Alex BonsuBonsu , , XiaofengXiaofeng GuanGuan

–– 250+ years of 250+ years of coal reservescoal reserves

–– Limited natural Limited natural gas availabilitygas availability

–– Need to utilize Need to utilize coal reserves coal reserves more efficientlymore efficiently

U.S. has a wellU.S. has a well--known, readily available supply of coalknown, readily available supply of coal

Courtesy of Robert Wayland, PhD, EPA OAR

Coal: America’s Most Abundant Fuel and Strategical ly Important

Taken from: “Critical Technology Needs for IGCC” pr esented by Ron Schoff at the CURC-EPRI Annual Meetin g, April 10, 2008.

Syngas Diluent (N2)

Extraction

Air

Coal

OxygenGasification

(including High Temp.

Heat Recovery)

Water Gas

Shift

Slag

Air

Separation

Acid Gas / CO2Removal

Unit

Fuel Gas

Sulfur

Recovery

Unit

Sulfur

CO2 Comp.

CO2To Pipeline

CO2

Steam

Syngas

Prep

Clean

Fuel Gas

Air

Air

Acid

Gas

Tail Gas Recycle

HRSG

Gas Turbine

Syngas

Cooling &

Hg Removal

Steam

Turbine

IGCC Simplified Flowsheet

From: “Tampa Electric’s IGCC Plant” presented by B. T. Burrows at the 11 th Annual FDEP Central District Power Generation Confe rence, July 26, 2007

IGCC and Gasification Background

• Coal gasification first used for streetlights in 1792.

• Late 1800’s widely used for lighting and industrial applications in Europe and US.

• By the 1920’s there were over 1200 gas plantsoperating in the US. Post WW II discoveries ofnatural gas led to demise of these plants.

• Widespread use in South Africa during apartheidfor liquid fuel production.

• Renewed interest and development in the 70’s due tooil embargo and concerns over natural gas reserves.

• Today’s high natural gas prices and stringentenvironmental regulations focused interest on IGCC.

• 117 operating plants, 385 gasifiers

• Feedstocks: Coal 49%Oil 37%Nat Gas, PetCoke, Biomass, waste 14%

• Products: Chemicals 37%Liquid fuels 36%Power 19%Gas fuels 8%

• Over 20 Combustion turbines firing syngas

• Solids IGCC’s Nuon Power, Netherlands, 253 MW 1993Wabash River, Indiana, 262 MW 1995Polk, Mulberry FL 250 MW 1996Puertollano, Spain 330 MW 1997

From: “Tampa Electric’s IGCC Plant” presented by B. T. Burrows at the 11 th Annual FDEP Central District Power Generation Confe rence, July 26, 2007

Gasification Worldwide

Gasification Cooling SyngasClean-up

Air Separation

System

Combined Cycle

SystemElectricity

Sulfur

Air

Coal

Clean FuelSlag

Air/N 2

Heat

CO2

Oxygen

The Five Basic Steps of IGCC

From: “Tampa Electric’s IGCC Plant” presented by B. T. Burrows at the 11 th Annual FDEP Central District Power Generation Confe rence, July 26, 2007

Taken from: “IGCC Cleaner Coal – Ready for Carbon C apture” presented by GE Energy at the UBS 2007 Clima te Change Conference, May 14, 2007.

Comparison of IGCC to Conventional Power Plant

CO2

Energy Efficiency

Useful Byproducts

Very Low Emissions

Courtesy: DOE/NETL

PolyGen: IGCC with Chemicals Production

IGCC Generates More Electricity per Ton of Coal

Two Options for IGCC: Oxygen vs Air-Blown

Economics of Oxygen vs Air-Blown IGCC

Emissions Comparison: Oxygen vs Air-Blown

IGCC Demo Plant – Kemper County, Mississippi

IGCC Research at thePower Systems Development FacilityWilsonville, Alabama

Hot-Gas Filter for Particulate Control

Analysis and solution of HGF performance problems (high ∆P, bridging, tar deposition, filter element damage, etc)

Development and validation of HGF design procedures

AllowableBaseline

∆∆∆∆P

∆∆∆∆P fromVesselLosses

Change in

Candle ∆∆∆∆P

Changein

Failsafe∆∆∆∆P

AllowableResidualDustcake

∆∆∆∆P= - - -

AllowableResidualDustcake

∆∆∆∆P

NormalizedResidualDustcake

Drag

ResidualDustcake

ArealLoading

AllowableFace

Velocity=

·Dustcake

DragDetermined

fromRAPTOR

Temp(Viscosity)Correction

DustcakePorosity

Determinedfrom

RAPTOR

AssumedDustcakeThickness

TrueParticleDensity

Particulate Removal by Hot-Gas Filtration

Sampling probe inserted through gland seal

Close-up view of isolation valveswith nitrogen purge and vent lines

Sampling nozzle, filter holder and alkali getter

HTHP In-Situ Particulate Sampling System

RAPTOR system for measuringdust flow resistance

Validation of RAPTOR with HGF performance data

Mass-Median Diameter, µµµµm

0 2 4 6 8 10 12 14 16

Nor

mal

ized

Dra

g, in

wc/

(ft/m

in)/

(lb/ft

2 )

0

50

100

150

200

Data obtained using variouscyclone configurations withRAPTOR device -- All dataon GCT2 charBest curve fit to RAPTOR dataGCT2 residual dustcake

Allowable Baseline ∆∆∆∆P, inwc

60 70 80 90 100 110 120 130 140

Min

imum

Req

uire

d Fi

lter

Are

a, ft

2 /100

0 ac

fm

0

200

400

600

800

1000

Combustion Ash Similar to TC05, Drag = 20Gasifier Char Similar to GCT2, Drag = 80Gasifier Char Similar to TRDU, Drag = 160 Use of

RAPTOR results in design of new HGF systems

Development of HGF Drag Correlations for System Des ign

Tar Cracking and Gas Cleanup Testing Area

Medium-Temperature Reactors(Used for low-temp tar cracking, desulfurization)

MiniMini --Reactor Operating Parameters for G117RR and GReactor Operating Parameters for G117RR and G --3131

Gasifier operation Air Blown Air BlownCoal type PRB PRB

Reactor RX301 RX301Reactor size 1.5”ID x4’ Ht 1.5”ID x4’ HtReactor material 310SS 310SS

Sorbent manufacturer Sud-Chemie Sud-ChemieSorbent G-117RR G-31Sorbent mass, lb 0.3 0.3-0.5Sorbent bed height, in 5 5

Syngas flow, scfh 10-12 15-20Pressure, psig, 2-10 2-10 Temperature, oF 1650 1650-1750Space velocity, hr -1 2155 1950-3430Ammonia inlet, ppm 2040 2250Ammonia outlet, ppm 86 6Benzene inlet, ppm 860 825Benzene outlet, ppm 210 20

Operating time, hr 290 13 / 300

Desulfurization Sorbents Developed by DOE andTested at PSDF

Gasifier Operation Air / O2 Blown O2 BlownCoal Type Powder River Basin Powder River BasinReactor RX700A RX700BReactor Size 5.187”ID x5’ Ht 5.187”ID x5’ Ht

Catalyst RVS-1 RVSLT-1Catalyst Mass, lb 2 2Bed Height, in 2.3 2.3

Syngas flow, lb/hr 45 - 3 12Pressure, psig, 210 - 130 135Temperature, oF 550 - 700 650Space Velocity, hr -1 24,000 - 1,700 6700Inlet H2S, ppm 160 - 620 580

Source: Environmental Footprints and Costs of Coal-Based Integrated Gasification Combine Cycle and Pulverized Coal Technologies, U.S. Environmental Protection Agency, EPA-430/R-06/006, July 2006

CO2 Capture with IGCC and Conventional PC Plants

7347Capital cost increase (%)

4016.5Efficiency Decrease (%)

2914Unit output derating (%)

9091CO2 capture (%)

PC Plant *IGCC Plant

7347Capital cost increase (%)

4016.5Efficiency Decrease (%)

2914Unit output derating (%)

9091CO2 capture (%)

PC Plant *IGCC Plant

High-Pressure CO 2 Capture Reactor

ApproachApproach

Data Acquisition

CO2 Analyzer

CO2 N2SpanGas

FrittedSolventBubblerFor CO2Absorption

Open-TubeH2SO4BubblerFor NH3Absorption

Flowmeters

Regulatorsand flowmetering valves

Thermocouple

ConstantTemperatureBath withCirculator

Data Acquisition

CO2 Analyzer

CO2 N2SpanGas

FrittedSolventBubblerFor CO2Absorption

Open-TubeH2SO4BubblerFor NH3Absorption

Flowmeters

Regulatorsand flowmetering valves

Thermocouple

ConstantTemperatureBath withCirculator

• Begin screeningtests with simple labsystem.

• Identify most promisingsystems.

―Abs rate & capacity.

―Energy requirements.

―Corrosion.

―Solvent stability.

• Maintain steady dialogwith other researchersto identify new materialsthat should be addressed.

Photograph of Initial Absorber SetupPhotograph of Initial Absorber Setup

Circulator/heaterfor constanttemperature bath

Inlet gas(CO2 in N2)

Fritted bubblerfor CO 2

absorption

Exit gasto analyzer

Thermocoupleoutput to datalogger

Gas flow = 1.5 L/min

Liquid volume = 200 mL

Gas residencetime ~1 sec

Open-tubebubblerfor absorptionof residual NH 3

Some Candidate Solvents and AdditivesSome Candidate Solvents and Additives

Initially, all of the primary solvents are being compared at a concentration of 1 M, but tests will also be done at other concentrations, including those used commercially. A tentative list of the solvents and additives to be tested is given below. Various combinations of solvents and additives are being tested as appropriate. The lists of solvents and additives are continually updated based in input from other researchers and developers.

Solvents Solvents (continued) Additives Additives (continued) Monoethanolamine N-acetylmorpholine Piperazine Methyl Diethanolamine Diethanolamine Sodium Glycinate Guanadine Hydrochloride Triethanolamine Methyl-Diethanolamine Potassium Glycinate Monoethanolamine Diaza-Bicyclo-Undecene Triethanolamine Potassium Taurate Ammonium Chloride Other Sterically-Hindered Amines Diglycolamine Potassium Sarcosinate Sodium Chlorides Sodium Glycinate Diisopropanolamine Diaza-Bicyclo-Undecene Other Chloride Salts Potassium Glycinate Methyl-Monoethanolamine Other Sterically-Hindered Amines Chloroform Potassium Taurate Morpholine Other Amino Acid Salts Carbon Tetrachloride Potassium Sarcosinate Ammonium Hydroxide Other Nitrogen-Containing Solvents Dimethyl Sulfoxide Other Amino Acid Salts Dimethyl Ether Polyethylene Glycol Other Nitrogen-Free Solvents Isopropanol Other Chlorinated Hydrocarbons Sodium Hydroxide Diaza-Bicyclo-Undecene-1-Hexanol Acetone N-formylmorpholine Piperazine Other Amidine-Alcohol Systems Ammonium Sulfate N-acetylmorpholine Potassium Carbonate Guanadine-Alcohol Systems Ammonium Bisulfate Hexanol N-formylmorpholine Perfluoro-Perhydro-Benzyltetralin Diethanolamine Other Alcohols

Derived from literature and discussions with other researchers and process developers.

Primary purpose of additives to enhance reaction rate.

Some additives selected to simulate effects of dual capture of CO2 and SO2.

List is being updated continually based on input from many sources.

Note: These initial results were obtained with low-concentration (1-M) solvents for comparison of

absorption rate and capacity with gas residence time of ~1 sec. These measurements were

made before the constant-temperature bath was available, so an ice-bath was used as a

convenient means of providing a constant temperature (0°C). Future tests will be done at various

temperatures representative of scrubber operation. Note that over time interval studied

absorption curves show asymptotic approach to saturation for all solvents except NH4OH.

Example 1 Example 1 -- COCO22 Removal Results Obtained with Removal Results Obtained with ““ StandardStandard ”” MaterialsMaterials

Cumulative CO2 Absorption vs Time with Various Primary Solvents

Time, sec

0 100 200 300 400 500 600 700 800 900 1000

Mol

es C

O2

Abs

orbe

d pe

r M

ole

Sol

vent

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7 MEADEATEAMDEAPZ NH4OH

NaOHNaGlyDEPG

Solvent Conc = 1 M Temperature = 0 °C

CO2 Removal vs Time with Various Primary Solvents

Time, sec

0 100 200 300 400 500 600 700 800 900 1000

CO

2 R

emov

al, %

0

10

20

30

40

50

60

70

80MEADEATEAMDEAPZ NH4OH

NaOHNaGlyDEPG

Solvent Conc = 1 M Temperature = 0 °C