Testing of Pre-Combustion CO2 Capture

Technologies at the National Carbon

Capture Center

John Wheeldon, Electric Power Research Institute

Tony Wu, Southern Company Services

2012 Gasification Technologies Conference

Washington, October 28 to 31, 2012

• 80% funded by US Department of Energy with 20% cost share

from major power and coal companies.

- High financial leverage for participants

DOE-Funded CO2 Capture Test Facilities in

Wilsonville, Alabama

Power Systems Development Facility (PSDF)

started combustion testing June 1996 and

gasification Sept. 1999.

In May 2009 PSDF transitioned to the

National Carbon Capture Center (NCCC).

Existing facilities used to support development

of pre-combustion CO2 capture.

Additional facility, the Post-Combustion

Carbon Capture Center (PC4) built and

started testing March 2011.

Located at adjacent power plant, Alabama

Power’s Plant Gaston near Birmingham.

Role of NCCC in CO2 Capture Technology Development

• Supports transition from laboratory to

commercial environment.

• All necessary infrastructure to support

testing of developer’s technology.

• Experienced operators and maintenance

staff.

• Comprehensive data collection and

analysis capability.

• Access to advanced analytical

techniques at SRI/UAB Birmingham.

• Flexible facilities allow for scale-up from

bench- to engineering-scale.

Provides first-class facilities to test developer’s technologies for extended periods under commercially representative conditions with coal-derived flue gas and syngas. Simultaneous testing at a range of sizes helps accelerate development of cost-effective carbon capture technologies.

Testing support to advance developer’s

technologies is top priority

Oxygen-Blown, Entrained-Flow IGCC from DOE’s

Advanced Technologies Portfolio

Selection of technologies for testing supported by screening process

Pre-Combustion CO2 Capture R&D at NCCC

Able to provide raw and sweet syngas up to 200 psia and 450°F for up to 1000

hours. Also able to augment syngas with hydrogen and CO2.

Syngas Cleanup Test Loop

Expansion to +5000 lb/hr of syngas possible if required

Membrane Technologies Tested

Preparing to test Eltron’s membrane system using 4.5 kg/hr (10 lb/hr)

of sweet syngas

A. Syngas inlet B. Permeate exit C. Residual exit

Spiral-wound design using polymer

materials

• Over 3000 hours testing. Various

membranes exposed to raw shifted and

unshifted syngas.

Membrane Technology & Research (MTR)

CO2 Membrane

One micron

Protective Coating Layer

Selective Layer (1,000 Å thick)

Gutter Layer

Support Membrane

One micron

• Two 10-cm OD x 115-cm long membranes (4-inches x 45-inches) can be

installed and tested using up to 23 kg/hr (50 lb/hr) of syngas at 40 C (100 F).

Scale-Up Support for MTR Syngas Membranes

Membrane stamp,

0.5 kg/hr (1 lb/hr) Pilot module, 230

kg/hr (500 lb/hr)

Lab-scale module, 4.5 kg/hr

(10 lb/hr)

Hydrogen membranes CO2 membranes

Small pilot

module, 23 kg/hr

(50 lb/hr)

Includes 20-cm OD (8-inch)

membrane modules

Scale Up of MTR’s Membrane Technology

• Two-stage polymeric CO2 separation membrane

processing 225 kg/hr (500 lb/hr) sweet syngas.

– First stage at 40 C and 14 bar (100 F and 200 psi)

– Permeate compressed to 30 bar (435 psi) before

passing to second membrane stage.

• 15 kg/hr (35 lb/hr) of +98% pure liquefied CO2

produced at 30 bar and -30 C ( 435 psi and -22 F).

MTR’s skids being installed

H2S removal vessels

• Test program will start in

December, achieving +500 hours

of operation.

• Second run planned for early in

2013.

Sources: WPI

• Worcester Polytechnic Institute (WPI) awarded $1.5

million by DOE to test palladium membranes.

• Hydrogen dissociates to atoms at palladium surface

and diffuse across the membrane.

• 2.5-cm (1-inch) OD by 25-cm (10-inch) long by

membrane tube housed in oven to maintain

temperature close to 450°C (840°F). Designs tested:

• Palladium-only

• Palladium with gold layer for sulfidation protection.

• 4.5 kg/hr (10 lb/hr) of sulfur-free syngas augmented

to 30 vol% hydrogen provided by NCCC.

• Stable H2 flux with +99.9% purity achieved.

Membrane housed within tube

and located in oven

WPI Palladium-Based Hydrogen Membrane

• WPI has submitted a proposal to DOE to

scale up the membrane module from 4.5 to

23 kg/hr (10 to 50 lb/hr) syngas using

multiple membrane tubes to achieve 85 %

hydrogen recovery.

Exposing Membrane Materials to Syngas

• On behalf of DOE, exposed multiple formulations of

hydrogen membrane materials to determine how they react

to “sour” syngas.

• Over 1000 hours exposure at 390°C and 16 bar (740°F and

230 psia).

• Post-run analysis by X-ray photoelectron spectroscopy,

X-ray diffraction, scanning electron microscopy, energy

dispersive microscopy, inductively-coupled plasma optical

emission spectrometry, inductively coupled plasma mass

spectrometry, and weight loss.

• Results indicate palladium can resist sulfidation when

amalgamated with appropriate elements in correct

proportions.

• Testing accelerated understanding and opened up new

opportunities.

Ready to test other developer’s materials in similar manner

Media Processing Technology (MPT)

Membrane Development & Scale-Up

• Carbon molecular sieve (CMS) membrane deposited on

alumina tubes 5.7 mm OD x 76 cm long (30 inches long)

• Operates 250 to 300 C (480 to 570 F), tolerant to sulfur so can

use raw syngas augmented to 40% hydrogen

• Full-scale bundle (84 tubes) processes 23 kg/hr (50 lb/hr)

syngas: permeate 90+% hydrogen with yields around 30%.

• Added single-tube palladium membrane to purify CMS

permeate to achieve 99+% purity

– CMS permeate has some H2S so sulfur guard bed required.

TDA High-Temperature CO2 Sorbent

• Carbon sorbent that removes CO2 via strong physical adsorption

– CO2-surface interaction is strong enough to allow operation at elevated temperatures

– No covalent bond so regeneration energy low.

• Heat of adsorption of CO2 4.9 kcal/mole at 250 C and 20 bar (480 F and 290 psia)

– Selexol ~4 kcal/mol but at 20 C at 5 bar (70 F and 70 psia)

– Ability to regenerate at higher temperature and releasing CO2 at higher pressure

improves cycle efficiency up to 4%

• Completed over 200 cycles with sweet syngas at NCCC achieving 98+% CO2 removal from syngas at temperatures above 200 C (390 F)

• Preparing to test sorbents with WGS functionality

that allow simultaneous shift reaction and CO2

adsorption

– Allows for higher CO2 production for same

steam-to-CO ratio.

– Potential to improve cycle efficiency up to 6%.

Expansion of SCU Testing Capability

• Covered area includes solvent, high-

temperature mercury sorbent, and

water gas shift catalyst test units.

• New area will supply 225 kg/hr (500 lb/hr) syngas

to MTR’s CO2 separation membrane (late 2012)

and 360 kg/hr (800 lb/hr) to developer in

negotiation (mid 2013).

• Ohio State’s 360 kg/hr (800 lb/hr) Chemical

Looping Module to be located to left of photograph

(mid 2013).

• Contract discussions in progress with other

technology suppliers and further test campaigns

are expected.

Space and enthusiasm to support

other developers

NCCC Pre-Combustion Capture Progress

Closing Comments

• The NCCC is able to test multiple pre-combustion technologies

simultaneously over a range of syngas flow rates

– This flexibility accelerates technology development.

• Testing developer’s technologies is NCCC’s top priority

– Support provided at design stage and during operation (with

operators and mechanical, electrical, and I&C services) to ensure

reliable accurate data are collected, efficiently and safely, and allow

the next stage of development to be planned successfully.

• Testing capabilities are being expanded to accommodate more

developers and test additional technologies at larger scales.

• Similar program in progress testing post-combustion capture

technologies.

Abbreviations Used

CMS carbon molecular sieve

DOE US Department of Energy

I&C instrumentation and control

MPT Media Process Technology

MTR Membrane Technology Research

NCCC National Carbon Capture Center

NETL National Energy Technology Laboratory

OD outer diameter

OSU Ohio State University

PC4 Post-Combustion Carbon Capture Center

PSDF Power Systems Development Facility

SRI Southern Research Institute

UAB University of Alabama, Birmingham

WGCU warm gas cleanup

WGS water gas shift

WPI Worcester Polytechnic Institute