RTI International

RTI International is a trade name of Research Triangle Institute. www.rti.org

RTIs Carbon Capture Experience
Luke Coleman, PhD
Program Manager Carbon Capture
Energy Technology Division
RTI International

June 2, 2014
Copyright 2014 RTI. All rights reserved
RTI International
One of the worlds leading research organizations
RTI is an independent, nonprofit institute that
provides research, development and technical
services to government and commercial clients
worldwide

Our mission is to improve the human condition by
turning knowledge into practice

Located in Research Triangle Park, NC
RTI International
Turning Knowledge Into Practice
RTI International
Technology Development with RTI
RTI develops advanced process technologies in
partnership with leaders in energy
Span the gap between University R&D and
Industry Deployment
Full alignment with industry objectives
Defined commercialization pathways
Flexible intellectual property arrangements
Potential leveraging of industrial R&D
funding with government provided funding
Biomass
and
Biofuels
Syngas
Natural
Gas
Carbon
Capture
Industrial
Water
RTI International
Post-Combustion Capture Areas
Non-Aqueous Solvents
Advanced Solid Sorbents
Membrane Processes
Hybrid Processes
Pre-Combustion Capture Areas
Sorbents for warm CO
2
removal from syngas
Integration of advanced CO
2
capture processes
with RTIs Warm Desulfurization Process
Carbon Capture R&D Activities at RTI
Water
NAS
Almost 15 years of continuous involvement in
developing CO
2
capture technologies
Broad technology portfolio with significant
activity in all major areas
Building key capabilities in materials and
process development
Growing IP portfolio
4
RTI International
RTIs Carbon Capture (CC) Technologies
5
Non-Aqueous Solvents*
(Post-CC)

Polymeric Membranes
(Pre- & Post-CC)
Advanced Solid Sorbents*
(Post-CC)
Warm CO
2
Removal from Syngas*
(Pre-CC)


* Highlighted in this presentation
Water
NAS
Warm desulfurization enabling
advanced CC process*
Advanced sorbents for warm
CO
2
removal from syngas
RTI International
Post-Combustion (PC) CC Technologies
Coal +Air CO
2
+H
2
O +N
2
+Contam. +Heat

CC process is end of pipe (retrofit)
No/minimal changes to power plant
Key Challenges:
Low CO
2
concentration
2-3 Million acfm of flue gas (550 MWe)
Contaminants
Integration with steam cycle
~12-15%CO
2
~1%CO
2
6
RTI International
PC Capture State of the Art
7
Mitsubishi Heavy Industries
(MHI) &Southern Company
MHIs KM CDR Process
150,000 tpy CO
2
~25 MWe
Technology Centre Mongstad (CO
2
TCM)
Aker Clean Carbon Amine Plant
Alstom Chilled Ammonia Plant
100,000 tpy CO
2

~20 Mwe - total

Commercially-available PCC Technologies
1
All solvent-based process; Not demonstrated at scale
Fluor - Econamine FG+Process
Mitsubishi - KM-CDR Process
Aker Clean Carbon J ust Catch Process
Cansolv Cansolv CO
2
Capture Process
Hitachi - H3 CO
2
Capture Process
Toshiba Toshiba CO
2
Capture Process
Alstom/Dow Advanced Amine Process
Alstom - Chilled Ammonia Process
1
http://www.iea-coal.org.uk/documents/83086/8635/Coal-fired-CCS-
demonstration-plants,-2012,-CCC/207
High thermal and electrical energy requirements
Large quantity of high quality steam required for solvent
regeneration derates low-pressure steam turbine
Large compression energy requirement due to low CO
2
partial
pressure generated during solvent regeneration derates
electrical generation
Parasitic power load ranges from 1,200 to 1,500 kJe / kg CO
2
High capital and operating costs
Expensive materials of construction due to corrosivity of solvents
Extremely large process equipment
High degradation rates due to O
2
and
SO
2
in flue gas
Evaporative losses and wastewater
treatment requirements
Large plant footprint
Rochelle, G. T. Amine Scrubbing for CO
2

Capture. Science 2009, 325, 1652-1654.
Result:
Increase in Cost of Electricity (ICOE) > 65%
Cost of CO
2
Avoided > $60 / tonne

Current USDOE Targets:
ICOE <35%
Cost of CO
2
Captured <$40/tonne
RTI International
CO
2
Capture Cost - R&D Focus
Breakdown of the Thermal Regeneration Energy Load
Sensible Heat Heat of Vaporization Heat of Absorption
Thermal
Energy Penalty
Solvent
C
p
[J/g K]
h
abs
[kJ/mol]
h
vap
[kJ/mol]
X
solv
[mol solv./
mol soln]

[mol CO
2
/
mol solv.]
Reboiler Duty
[GJ/tonne
CO
2
]
MEA (30%) 3.8 85 40 0.11 0.34 3.22
Lower Energy
CC Process
Process capable of achieving these criteria will have a lower energy
penalty than SOTA processes
8
RTI International
Absorb
er CO
2
-lean
solvent
Treated Flue
Gas
CO
2
Product
Desirable Characteristics
Favorable thermodynamics
High working capacity
Low heat of absorption
Low regeneration temperature
Low specific heat capacity
Low vaporization of solvent
Low water solubility
Low viscosity and high surface tension
Low foaming tendency
Non-Aqueous Solvent CO
2
Capture Process
Post-Combustion Capture
Challenges
Undesirable reactions with water
Accumulation of water from flue gas in solvent
Solids formation in rich solvent
Viscosity, foaming tendency
Solvent cost and availability
Emissions in process water and treated flue gas
Aq. Amine Solvent NAS
9
Precipitation during
absorption (Undesirable)
Formation of a second
liquid phase
RTI International
Non-Aqueous Solvent CO
2
Capture Process
CO2-lean Flue Gas
Flue Gas
from WFGD
Flue Gas
Wash
C
O
2

A
b
s
o
r
b
e
r
R
e
g
e
n
e
r
a
t
o
r
Condenser
CO2 Product
To
Compression Train
Trim
Cooler
Cooling
Water
Low Pressure
Steam
Crossover
Heat Exchanger
CO2-lean
Solvent
CO2-rich
Solvent
C
O
2

A
b
s
o
r
b
e
r
Waste Water
Condensate
Make-up Water
CO
2
Steam

Technology in development at RTI since 2009

Strong partnerships with government and
industrial partners







Comprehensive patent portfolio
3 formulation related applications filed
3 process related applications filed


RTI is developing a NAS CO
2
capture process for post-combustion applications that has the potential to
reduce the regeneration energy penalty to < 2.0 GJ
t
/ tonne CO
2
(~40% < state-of-the-art solvents).
Treated FG

FG

10
RTI International
Previous
Work
DOE ARPA-E Project DOE NETL Project (Current) Future Development
Yr 2009-10 2010-13 2014-15 2016-20 2020+
TRL 1 2 3 4 5 6 7 8 & 9
Proof of
Concept/Feasibility
Pre-Commercial
Demonstration
NAS CO
2
Capture Process: Technology Roadmap
Pilot-scale prototypical systemdemonstrated in a relevant environment (Future)
Large pilot system, ~ 1 MWe (20 tonnes/day), using real flue gas and a complete process unit
Collect critical process information to support detailed T&E assessments and scale-up efforts
Lab Scale Development (Previous)
Solvent screening to identify promising solvent formulations
Lab-scale evaluation of NAS Process
Preliminary technical and economic assessments
Small Pilot System/ Relevant Environment Testing (Current)
Bench-scale testing with in a process unit with major process components
Demonstrate 2 .0 GJ/tonne CO
2
using bench-scale system
Address process, environmental, and economic challenges
Detailed solvent degradation and emissions studies
Detailed Techno-Economic & EH&S Assessments
11
RTI International
NASs achieve larger dynamic capacities () with
smaller Ts
CO
2
pressure of > 2bar can be achieved around 90C
CO
2
Isotherms
Heat of absorption ranging from 55 to 75 kJ/mol CO
2
Specific heat capacity of 1.2 to 1.5 kJ/kg K
Heat of Absorption
Why are RTIs NASs so promising?
Superior Thermodynamic Properties
12
RTI International
30 wt% MEA / Water
NAS-2
CO
2
-Lean CO
2
-Rich
NAS Physical Properties
30 wt% MEA-water Solvent
Foaming issues observed
Failed test by expanding > 3x to overflow cylinder
NASs
No foaming issues observed
Very little retention of gas in solvent
13
Viscosity measured for CO
2
-lean and CO
2
-rich solvents at
absorption (40C) and regeneration (80C) temp.
30 wt% MEA is reported to be 1.7 cP (lean) and 2.7 cP (rich)
at 40C
1
Non-aqueous solvents have very reasonable viscosities and
can utilize conventional gas absorption equipment
Measured Viscosity
Sample Name Viscosity [cP] Temp [C]
NAS-1, CO
2
-Lean
4.5 40
1.6 80
NAS-1, CO
2
-Rich 20.7 40
NAS-2, CO
2
-Lean
7.2 40
2.5 80
NAS-2, CO
2
-Rich 27.1 40
RTI International
Demonstrated stability of non-aq. solvents in a representative process arrangement
Evaluated/demonstrated key process concepts specific to non-aqueous solvent process
Water balancing; effectiveness of numerous regenerator types
Compared performance of the NAS process and 30 wt% MEA-H
2
O
Prelim. data verifies 30-40% reduction in thermal regeneration energy
Evaluated the effect of long-term (>500 h) exposure to common flue gas contaminants
Supported design of small pilot unit for engineering-level evaluation of NASs
14
Small Bench-scale Testing
60
70
80
90
100
110
120
130
140
150
160
0
5
10
15
20
25
30
35
40
45
50
0 10 20 30 40 50 60 70 80 90 100
C
O
2

C
a
p
t
u
r
e

E
f
f
i
c
i
e
n
c
y

&

C
O
2

B
a
l
a
n
c
e

[
%
]
C
O
2

C
o
n
c
e
n
t
r
a
t
i
o
n

[
v
o
l
%
]
Time-on-Stream[h]
CO2 Concentration
CaptureEfficiency
CO2 Balance
SampleCollection
RTI International
Regeneration Energy & Technical Assessment

15
Several candidates identified that have potential to
achieve regeneration energies < 2.0 GJ
t
/ tonne CO
2
Note: Density of NASs is ~ 1.35-1.45 kg/L
RTIs NASs
CO
2
Capture
Process
Net Power
[kWe]
Net
Efficiency
[%]
Efficiency
Point Loss
No Capture* 784,700 39.3 -
Fluor
Econamine FG+*
549,970 28.4 10.9
RTIs NAS
Process
652,079 32.7 6.6
NAS CO
2
capture process has potential to reduce
parasitic power load by ~ 40% compared to MEA-
based process
NAS Process requires lower quantity and quality of
steam for solvent regeneration
40%less steam; upto 30
o
C cooler steam
Potential for significant reduction in increase in cost
of electricity --- much more work needs to be done
Process modeling to estimate parasitic power load Thermal Regeneration Energy
* Cost and Performance Baseline for Fossil Energy Power Plants, Volume 1: Bituminous Coal and Natural Gas to Electricity
(Nov 2010)
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
5,000
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
R
e
g
e
n
e
r
a
t
i
o
n

E
n
e
r
g
y

[
k
J
t
/
k
g

C
O
2
]
L/G [kg/kg]
30 wt% MEA
NAS 1
NAS 2
NAS 3
NAS 4
2,500kJ
t
/kgCO
2
2,000kJ
t
/kgCO
2
3,680kJ
t
/kgCO
2
1,700 kJ
t
/kg CO
2
Range of most
advanced
processes
RTI International
Project Objective: Continue the advancement of the NAS CO
2
Capture Process
address specific challenges facing technical and economic potential
bench-scale demonstration of the potential to reduce the energy penalty to <2,000 kJt/kg of CO
2

understand potential for scale-up and demonstration at NCCC
Current Efforts:
Bench-scale testing to demonstrate
2 .0 GJ/tonneCO
2

Address process, environmental,
and economic challenges
Detailed solvent degradation and
emissions studies
Collect key performance data for all
major process units to estimate the
size and cost of full-scale process
components
Detailed Techno-Economic & EH&S
Assessments
Next Development Steps
Inventor of non-aqueous CO
2

solvent chemistry
Lead bench-scale testing
campaign to optimize process
performance
Global leader in gas separations
& purifications solutions
Expertise in the design,
engineering, and operation of gas
treatment processes
Techno-economic and EH&S
assessments of novel processes
Extensive experience in amine
degradation & amine plant
emissions
RTI International
Advanced Sorbent CO
2
Capture Process
Post-Combustion Capture
17
Advantages
Potential for reduced energy consumption compared to
SOTA solvent processes
High CO
2
working capacity compared to solvents
Reduced sensible heat load due to lower heat capacities
Steam stripping can be minimized / eliminated
Avoids evaporative emissions
Potential for reduced capital costs through simplified process
designs and inexpensive materials of construction
Challenges
Low-cost sorbent with high and stable working capacity
suitable for fluidized-bed processes
Effective heat management in absorber & regenerator
Pressure drop across sorbent bed
Sorbent make-up and particulate matter emissions
TCWS
TCWR
TCWS
TCWR
TCWS
TCWR
Flue Gas from Deep
Desulfurization Wash
G [kg/h]
CO
2
Absorber CO2-lean
Sorbent Feed
CO2-rich
Sorbent Exit
S [kg/h]
Treated Flue Gas
RTI International
Technology in development at RTI and PSU
since ~2000

Strong partnerships with government and industrial
entities





Current development efforts:
transition a promising sorbent chemistry to a low-cost
sorbent suitable for use in circulating fluidized-bed
process
bench-scale demonstration of complete circulating
fluidized-bed process
Advanced Sorbent CO
2
Capture Process
RTI is developing a sorbent-based CO
2
capture process that uses a supported, polymeric amine
sorbent and a fluidized-bed process arrangement for post-combustion applications (power and
industrial installations).
18
H--CH
2
-CH
2
-NH--H
n
( )
Nano-porous Material
CO
2
/H
2
S-philic Polymer
(Polyethylenimine)
Molecular Basket Sorbent (MBS)
+
CO2-philic Polymer
(e.g. Pol yethylenimine)
Immobilize PEI into Nano-Pore
Polyethylenimine (PEI)
Promising sorbent
chemistry
RTI International
Sorbent Improvement
Reduce sorbent cost
Many supported sorbents being developed are experimental
materials with cost in the $1,000s / kg
Numerous low-cost, commercially-available support materials
have been identified
To-date 1,000x reduction in cost compared to mesoporous
silicas
Certain low-cost materials exhibit superior performance
Cost Target <$5/kg
0
2
4
6
8
10
12
14
65 75 85 95
C
O
2
L
o
a
d
i
n
g

[
w
t
%

C
O
2
]
Absorption Temperature [C]
MCM-41
Trisyl p100
FS
Absorption: 65C, 15%CO2, 5.6%H2O, 2.6%O2
Regeneration110C, 5.7%H2O, N2
Aging: 120C, 90%CO2, 10%H2O for 10 hours
Sorbent performance improvement
Sorbent must be stable under realistic process conditions
Eliminate leaching of polymeric amine from porous supports
under process conditions
Mitigate / control oxidative degradation
Measure degradation rates with flue gas contaminants (SO
2
,
NO
x
, dust, HCl, etc.) and determine acceptable limits
19
RTI International
Conversion to a Fluidizable Platform
20
Converted powder sorbents to low-cost,
fluidizable, attrition-resistant particles suitable
for use in a fluidized-bed process
Spray Drying
Suitable particle size and density
Physically strong and resistant to attrition
Non-cohesive
Evaluation of fluidizability under process conditions
Lab-scale, visual fluidized bed constructed to evaluate prepared
sorbents at specific process conditions to allow for visual
observation / characterization of the sorbent bed
Pilot-Scale NIRO Mobile Minor spray dryer
RTI International
Staged, Circulating Fluidized-bed with
Integrated Heat Management
evaluate effectiveness of staged reactor
design with integrated heat management
system for CO
2
removal from flue gas
evaluate fluidizable, attrition-resistant,
supported polymeric amine sorbent

Specifications
Flue gas throughput: 300 and 900 SLPM
Solids circulation rate: 75 to 450 kg/h
Sorbent inventory: ~100 kg of sorbent
Mechanically completed
Field verification of instrumentation and
daq./control system (1
st
wk of 6/14)
Cold and hot flow verification (2
nd
wk of 6/14)
System operation with CO
2
Sorbent starting 3
rd

week of June 2014
Bench-scale Contactor Evaluation Unit
21
RTI International
22
Next Development Steps
Process Demonstration at an Industrial Source
Demonstrate RTIs advanced sorbent CO
2
capture
process in an operating cement plant
Norcems Brevik Cement Plant
(Source: Norcem)
Project Team
Timeframe: 2 years [May 13 Sept 15]
Project Scope
Phase I Current
Feasibility study of RTIs technology applied to a
commercial cement plant through detailed economic
evaluations

Perform sorbent exposure testing real cement plant
flue gas to demonstrate sorbent stability
Phase II
Optimize the sorbent preparation and reactor
designs for cement plant application
Detailed engineering, permitting, construction of pilot
system
Pilot field testing of technology at Norcems Brevik
cement plant
22
RTI International
On-stream Testing at NORCEM
23
Evaluate sorbent performance under realistic process conditions using real cement plant kiln gas
Measure sorbent stability in presence of untreated kiln gas and treated kiln gas
Acceptable contaminant levels for SO
2
and NO
x
to be determined at RTI prior to testing at Norcem
Multi-cycle stability in excess of 200 cycles (this is arbitrary need to find a better definition)
Determine efficacy of pretreatment processes for removal of SO
2
and NO
x
using real kiln gas
>80 abs-des cycles on-stream so far
Currently awaiting cement plant restart
RTI International
Pre-Combustion CO
2
Capture IGCC
Syngas produced via gasification of coal with purified O
2
Mixture of H
2
, CO, CO
2
, and H
2
O
Water-gas shift and CO
2
removal to produce a H
2
-rich fuel gas
CO + H
2
O H
2
+ CO
2

H
2
is combusted to produce power
Integrated Gasification Combined Cycle (IGCC)
Advantages
High chemical potential (T, P
CO2
)
Low Volume Syngas Stream
Commercially-available CO
2
capture options
e.g. Selexol
30+ years of operation (55 worldwide
plants)
Highly selective for H
2
S and CO
2

CO
2
is produced at pressure
Challenges
Complex, integrated & expensive power
process
Additional process (WGS) to achieve high
capture efficiency
Current technology (Selexol) requires cooling
and reheating
Opportunities
Sorption Enhanced Water-Gas Shift (SEWGS)
Improved IGCC efficiency through CO
2
capture
at elevated temperatures no gas cooling
24
Coal +O
2
+H
2
O H
2
/H
2
O +CO/CO
2
+Contam.
RTI International
A unique process technology based on transport reactor
design (related to Commercial FCC Reactor Designs]
based on the development of a highly
active, attrition resistant sorbent.

RTI proprietary desulfurization sorbent
R&D 100 Award in 2004
Developed through long-term
cooperation with Clariant
Part of comprehensive high temperature contaminant
removal platform.
RTIs Warm Desulfurization Process
Enabling Pre-Combustion CC Technologies
25
RTIs Warm Desulfurization Process (WDP) has been developed to remove sulfur compounds (H
2
S,
COS, CS
2
, mercaptans) from syngas to ~ 1ppm-levels at > 350
o
C.
RTI International
>20 year development timeline with numerous stages & partners
RTIs Warm Desulfurization Process
Enabling Pre-Combustion CC Technologies
26
Demonstration (2010-2015): Syngas cleanup / carbon capture
Tampa Electric IGCC Plant, Florida
$168.8MM DOE funding to design, construct, operate
50 MW
e
equivalent scale
Invention (2001)
Proprietary desulfurization sorbent
R&D 100 Award (2004)
Pilot testing (2006-2008)
Eastman Chemical Co.
3000hr, coal-derived syngas
Lab/bench testing (2001-2003)
RTI
Concept proven & modeled
Technology Team
RTI BASF
Tampa Electric Clariant
Shaw Group, AMEC DOE/NETL
CH2M Hill Eastman Chemical
Large teams/partnerships are necessary to
complete projects at this scale &beyond
RTI International
Source: BASF
CO
2
Capture: BASF aMDEA

Process
Activated MDEA (aMDEA

)
aMDEA

has the lowest specific energy consumption
of any standard amine solvent for CO
2
removal.
aMDEA

has higher absorption kinetics and capacity
reducing equipment size resulting in lower capex and
opex.
Extensively used in hydrogen production, ammonia
manufacture, cryogenic gas processing, and LNG
production
Exploiting aMDEA

for CCS in IGCC requires
selective sulfur removal technology
RTIs Warm Desulfurization Process (WDP) enables use of advanced CC technology previously not
used for this application.
Feed Gas
CO
2
, H
2
S
aMDEA
27
RTI International
Integration of Syngas Cleaning and Carbon Capture Systems at Tampa Site
Clean
Fuel Gas
Process
Water
20% slipstream test (~50 MW
e
) enables direct commercial scale-up from this demonstration scale
Air
Air
Separation
GE Gasifier
(400 psig)
Syngas
Cooling
Scrubbers
COS
Hydrolysis
Oxygen
Coal/Petcoke
Char
Syngas
Cooling
MDEA
Sulfuric
Acid Plant Sulfuric
Acid
Process Condensate
Reheat/
Humidify
Clean Fuel Gas
Slag
Acid Gas
Syngas Diluent (N
2
)
128 Mwe
(122 Mwe)
8% H
2
O
Extraction Air
~
~
Water Gas
Shift Reactor
WDP
Syngas
Cooling
aMDEA
CO
2

Recovery
Regenerator Gas
Project Scope
Raw Syngas
Currently vented, but
could be sequestered or
recycled
WDP enables advanced CC
technology previously not used
for this application
28
RTI International
RTIs 50 MW Demo Project
Demonstrate RTIs technology to reduce capital costs, improve efficiency, and lower the carbon
footprint of advanced gasification
Mitigate design and scale-up risks for the first commercial plant
Obtain 5,000 to 8,000 hours of operations
Determine performance metrics
Verify capital and operating costs
Validate start-up and shut-down procedures
Capture >90% of CO
2
in syngas
~1,000 tonnes CO
2
/ day
50 MW Installation at TECO [Nov. 2013]
29
RTI International
Completed Construction &
Currently on Syngas
March 19, 2014
RTI International
Our experience with CCS at Tampa Electric
Designed and built a carbon capture system
equivalent to a 50 MWe plant
Characterized the geology for on-site storage
Determined that Polk Power Station (TECO) is
located above a suitable aquifer
Modelling indicated rapid mineralization of CO
2
and found synergies with waste water injection

EPA originally granted a Class V well permit
but later insisted on Class VI permit
Class V: Inject non-hazardous fluids underground
Class VI: Injection of CO
2
into underground
subsurface rock formations for long-term storage,
or geologic sequestration.
50 year MVA requirement
Clarified and expanded financial responsibilities
Project team decided to not sequester CO
2

since responsibility & liability would exceed
project lifetime
31

RTI International

Banholzer, 2008
CO
2
Utilization
32
CO
2
Properties
Fully oxidized form of carbon
Extremely chemically stable
Conversion to useful products requires abundance of
reducing agents and energy

Challenge
Low-cost, abundantly available reducing agents that
have a small CO
2
footprint
Large enough market to mitigate CO
2
emissions
Cost-effective (competitive) pathways to valuable
products


Potential pathways that RTI is developing
CO
2
to CO using pet-coke and waste chars
CO
2
+ C 2CO [Reverse-Boudouard Reaction]

Ethylene epoxidation

RTI International
Acknowledgements
33
Strategic Partners
U.S. Department of Energy
Office of Fossil Energy - National Energy
Technology Laboratory (NETL)
Advanced Research Project Agency Energy
(ARPA-E)

U.S. EPA

Gassnova The Norwegian state enterprise for
carbon capture and storage.

Commercial Partners
BASF
Linde
Masdar
Norcem
SINTEF

University Collaborators
Pennsylvania Sate University
Masdar Institute
Key RTI Staff Contributing to CO
2
Program
Dr. Marty Lail
Mr. Thomas Nelson
Dr. Atish Kataria
Dr. Markus Lesemann
Dr. Jak Tanthana
Dr. Paul Mobley
Dr. JP Shen
Dr. Sree Pavani
Dr. Brian Turk
Dr. Raghubir Gupta
RTIs Energy Technology Division