Shaojun Zhou - Gas Technology Institute

Hybrid Membrane/Absorption Process
for Post-Combustion CO2 Capture

(Membrane Contactor)
Jim Zhou, Howard Meyer, and Ben Bikson

Sept. 15, 2010 DE-FE0004787
Outline
 Introduction of GTI and PoroGen

 Project Overview
 Fundamentals of Membrane Contactor
Technology
 Project Objectives and Approach
 Plan and Summary
Review Meeting 09/15/2010 2

Facilities & Staff
> Main Facility:

18-Acre Campus
Near Chicago
─ Over 200,000 ft2 of
laboratory space
─ 28 specialized
laboratories
and facilities
Flex-Fuel
> Staff of 250 Offices
Test
Facility
& Labs
─ 70% are scientists
and engineers
─ 45% with advanced
degrees
Energy & Environmental Technology Center
Specific GTI Programs Related to CCS
 R&D on membrane contactor (Carbo-Lock™) Technology for pre-.
and post-combustion CCS
 Morphysorb® for pre-combustion CO2 capture, natural gas CO2

removal
 U-Gas ® fluidized-bed coal or biomass gasification
 Wood gasification (to liquid transportation fuels) and gas cleanup
 Selective removal/recovery of H2S from syngas (UCSRP)
 CO2 to Biomethane (Algae)
 Regional Partnership for Carbon Capture (SW and Midwest

Partnerships)
 Reservoir monitoring and site selection

PoroGen Technology
>Material technology company
>Building products manufactured from specialty
high performance plastic PEEK
>Core of PoroGen’s patented technology is
porous PEEK materials
>Diverse line of products ranging from
membrane fluid separation filters to heat
transfer devices
>Module area up to 1000 ft2 and module
diameter from 2 to 12 inches

Project Overview

Overall Budget
 Total Budget: $3,736 K
• Federal $2,986 K
• Cost Share $750 K
 ICCI $375K
 Midwest Generations $225K
 PoroGen $150K
 Performance Date
• Oct. 1, 2010 – Sept. 30, 2013

Performing Organization and Key
Staff
 Gas Technology Institute
• Jim Zhou as PI, Howard Meyer as PM
• Working on process development and testing
 PoroGen
• Ben Bikson and Yong Ding
• Working on membrane and membrane module development
 Aker Process Systems
• Pal Nokleby
• Working on membrane process modeling and economic
analysis
 Midwest Generations EME, LLC
• Kent Wanninger
• Pilot test site

Fundamentals of Membrane
Contactor Technology

Basic Principles
Membrane mass transfer principle
 Porous, hollow fiber membrane
 Unique membrane material, PEEK
 Membrane matrix filled with gas
 Mass transfer by diffusion reaction
 Driving force: difference in partial pressures of component to
be removed/absorbed (PCO2(g)>PCO2(l))
 Liquid on one side, gas on the other side of the membrane
 Pressure difference between shell and tube side almost zero
 (Pl≥Pg), i.e. the mass transfer is not pressure driven

Process Description
Afft FGD 40 to 80 C
16 to 20 psia

General Approach
Hybrid membrane/solvent absorption process

─ Nano-porous, superhydrophobic PEEK hollow fiber membrane
─ Increases interfacial gas/liquid contact area 10x over conventional packed or

tray columns — increases overall mass transfer coefficient
─ Selectivity controlled by solvent chemical affinity
─ Low steam regeneration energy
─ CO2 can be generated at pressure
─ Planned slipstream test at Midwest Generation’s Joliet Power
Station (Size: 25 kWe)

Process Features
 The gas/liquid contactor is a hybrid between membrane

and the conventional absorption processes.
Process features:
 Higher CO2 loading differential between rich and lean solvent is
possible
 Increased mass transfer reduces system size
 High specific surface area available for mass transfer
 Independent gas and liquid flow
 Linear scale up
 Concentrated solvents or specialty absorbents can be used
 Conventional and developmental solvents

Benefits of Membrane Contactor
Process
Membrane Advantages:
• Capital Cost (CapEx) 35%
• Operating Costs (OpEx) 40%
• Dry Equipment Weight 35%
• Operating Equipment Weight 37%
• Total Operating Weight 47%
• Footprint Requirement 40%
Conventional Amine Carbo-Lock™ • Height Requirement 60%
Scrubber Column Membrane Contactor
*Data by Aker Kvaerner

Previous Work – ePTFE
 GTI worked closely with Kvaerner (now Aker) on ePTFE
based membrane contactor process development
 This project was successful technologically
 ePTFE system was found to have high mass transfer rate
 Resulted in up to 75% reduction in volume and 65% reduction in weight
 GTI worked with Kvaerner, Duke Energy, and Chevron on
membrane contactor field tests for dehydration
 Successfully demonstrated the technology
 Wetting of pores observed resulting in solvent loss and
loss of productivity
 Process economics was high due to
 High cost of ePTFE membrane module per attainable performance
 High cost of pressure control system

Membrane Material Properties of
PEEK
 Very high heat resistance
 High rigidity
 High dimensional stability
 Good strength
 Excellent sliding friction behavior
 Excellent chemical resistance
 Excellent hydrolytic stability
 Average pore size 1 to 50 nm
 Average porosity 40 to 70%
 800 psi water breakthrough pressure
PEEK can operate continuously in contact with aggressive solvents.

Technology Challenges
 Long-term membrane wetting in contact with solvent
• By membrane surface treatment
• By making composite membrane with non-porous coating
 Membrane contactor mass transfer coefficient
• By optimizing of membrane physical properties
• By optimizing membrane module physical properties
 Process cost
• By reducing membrane cost itself through gradual maturity of the
technology and large scale production
• By reducing energy cost of solvent regeneration through novel
regeneration methods and deployment of new solvents

Performance Characteristics
• Tests were performed with a variety of absorbents including carbonate

solution and amine solvents.
Example: Potassium Carbonate Solution and amines

Inlet P =6 psig
Gas T = 25 C
Liquid T = 50 C
N2, KGa,
kmol/m2/hr kmol/(m3.hr.kPa) GPU Equivalent Solvent
35.27 0.21 3200 K2CO3 20 wt%
34.42 0.56 3512 Amine Solvent
48.02 0.94 4910 Amine Solvent

Process Economics Analysis
CCS economics for pulverized coal power plants
Pulverized Coal Boiler

Basis DOE PC Subcritical PC Subcritical
with Membrane
Case 9 c Case 10 c
Contactor and
(MEA ) KS-1 solvent
CO2 Capture No Yes Yes
Gross Power Output 583,315 679,923 625,000
(kWe)
Auxiliary Power 32,870 130,310 75,000
Requirement
(kWe)
Net Power Output 550,445 549,613 550,000
(kWe)
LCOE (mills/kWh) a 64.0 118.8 91.0 b
a Based on an 85% capacity factor
b Valueis based on membrane cost of $100/m2
c Case 9 and 10 are from ―Cost and Performance Baseline for Fossil Energy Plants,‖ DOE/NETL-2007/1281

Sensitivity Analysis of LCOE
LCOE Vs. Membrane Cost
$93
KGa = 0.7
$92
KGa = 0.96 3kmol
m ·hr·kPa
$91 KGa = 1.4
$90
LCOE $/MW
$89
$88
35% Increase of
$87 LCOE from base
case
$86
$85
$84
$0.0 $20.0 $40.0 $60.0 $80.0 $100.0 $120.0 $140.0
Membrane Cost $/m2

Project Objectives and General
Approaches

Objectives
>Overall objective: To develop cost effective
separation technology for CO2 capture from flue
gases based on a hollow fiber membrane
contactor technology
1. A highly chemically inert and temperature stable
PEEK hollow fiber membrane for contactors
2. Integrated membrane absorber and desorber, and,
3. An energy efficient process for CO2 recovery from
the flue gas

Lab Membrane Test Unit P&ID

Test Rig to Be Built
 Design Approach
Complete solvent cycle with absorption and
regeneration
 Process monitoring, control and automation
 Data gathering and analysis

Tasks and Activities

Plans for Further Testing
 Pilot-scale Field Testing of Membrane Contactor

• Objective: Process validation and performance
testing with realistic feed
 Engineering and Economics
• Objective: Engineering components, integration into
power plant, economic impact of technology on COE
 Demonstration-scale Field Testing of Membrane
Contactor
• Objective: Scale-up testing to obtain engineering
parameters for design of full-scale units

Steps After Current Technology
Development Project
 Membrane module scale up
 Bench scale testing at pilot scale
 Determine operational challenges and membrane
life
 Technology scale up and demonstration
 Detailed process and economic modeling using
plant data

Summary
 We have a well laid out plan for successful
development of the membrane contactor
technology
 Preliminary economics promising
 Membrane contactor technology has many
advantages over other competing technologies
for carbon capture

Acknowledgement
• DOE-NETL, Program Manger: Andrew O’Palko

• ICCI for financial support
• Midwest Generation EME, LLC for test site and
financial support

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Hybrid Membrane/Absorption Process

for Post-Combustion CO2 Capture

Jim Zhou, Howard Meyer, and Ben Bikson

 Introduction of GTI and PoroGen

Review Meeting 09/15/2010 2

> Main Facility:

 Morphysorb® for pre-combustion CO2 capture, natural gas CO2

 U-Gas ® fluidized-bed coal or biomass gasification

 Wood gasification (to liquid transportation fuels) and gas cleanup

 Selective removal/recovery of H2S from syngas (UCSRP)

 CO2 to Biomethane (Algae)

 Regional Partnership for Carbon Capture (SW and Midwest

 Reservoir monitoring and site selection

Review Meeting 09/15/2010 5

Review Meeting 09/15/2010 6

Review Meeting 09/15/2010 7

Review Meeting 09/15/2010 8

Review Meeting 09/15/2010 9

Review Meeting 09/15/2010 10

Review Meeting 09/15/2010 11

Hybrid membrane/solvent absorption process

─ Increases interfacial gas/liquid contact area 10x over conventional packed or

Review Meeting 09/15/2010 12

 The gas/liquid contactor is a hybrid between membrane

Review Meeting 09/15/2010 13

*Data by Aker Kvaerner

Review Meeting 09/15/2010 14

Review Meeting 09/15/2010 15

PEEK can operate continuously in contact with aggressive solvents.

Review Meeting 09/15/2010 16

Review Meeting 09/15/2010 17

• Tests were performed with a variety of absorbents including carbonate

Example: Potassium Carbonate Solution and amines

34.42 0.56 3512 Amine Solvent

48.02 0.94 4910 Amine Solvent

Review Meeting 09/15/2010 18

Pulverized Coal Boiler

Review Meeting 09/15/2010 19

Review Meeting 09/15/2010 20

Review Meeting 09/15/2010 21

Review Meeting 09/15/2010 22

Review Meeting 09/15/2010 23

Review Meeting 09/15/2010 24

Review Meeting 09/15/2010 25

 Pilot-scale Field Testing of Membrane Contactor

Review Meeting 09/15/2010 26

Review Meeting 09/15/2010 27

Review Meeting 09/15/2010 28

• DOE-NETL, Program Manger: Andrew O’Palko

Review Meeting 09/15/2010 29

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