Capture of Carbon Dioxide from

Flue Gas Using a Cyclic Alkali

Carbonate-Based Process
Research Triangle Park, North Carolina
Second Annual Conference on Carbon Sequestration
Alexandria, Virginia
May 2003
Research Triangle Institute
Poster Presentations Participants Plenary Sessions Technical Sessions Main Menu
2
Project Team
RTI
David A. Green
Raghubir P. Gupta
Santosh K. Gangwal
LSU
Douglas P. Harrison
Church & Dwight
Robert Berube
Steve Lajoie
DOE/NETL
Michael K. Knaggs
Brian S. Turk
William J. McMichael
Jeffrey W. Portzer
3
Objectives
To develop a carbon dioxide separation technology that is
Regenerable sorbent-based
Applicable to both coal and natural gas-based power plants
Applicable as a retrofit to existing plants, as well as to new
power plants
Compatible with the operating conditions in current power
plant configurations
Relatively simple to operate
Less expensive than currently available technologies
4
Integration of the Dry Carbonate
Process in a Combustion Facility
5
Concept Evaluation
(Sodium Bicarbonate Sorbent Baking Soda)
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Time (min)
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(

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)
Temperature
Mass
Calcination/
Regeneration:
130 C in He
Carbonation:
11% CO
2
7% H
2
O
74%N
2
7% O
2
Inexpensive CO
2
getler identified
Getler is readily
regenerated
Low temperature
process
Convenient for
flue gas treatment
6
Materials Screened
Sodium bicarbonate (SBC) NaHCO
3
Grade 1
Grade 2
Grade 3
Grade 5
Spherical
Trona--Na
2
CO
3
NaHCO
3
2H
2
O
Grade T-50
Grade T-200
Potassium Carbonate K
2
CO
3
Analytical Grade
Commercial Grade
Jet-milled
Supported Sorbents
40% K
2
CO
3
/60% support
10% K
2
CO
3
/90% support
20% Na
2
CO
3
/80% support
40% Na
2
CO
3
/60% support
7
Sorbent Characterization and Testing
Physical
Particle Size Distribution (RTI)
Surface Area (RTI & C&D)
Attrition Resistance (RTI)
Pore Size Distribution (RTI)
Bulk Density (RTI)
X-ray Diffraction (C&D)
Scanning Electron Microscopy (C&D)
Fluidization Characteristics (RTI)
Chemical
Thermogravimetry (RTI & LSU)
Fixed Bed Testing (LSU)
Fluidized Bed Testing (RTI)
8
Sodium Carbonate Chemistry
30.8 2NaHCO
3
X Na
2
CO
3
+CO
2
+H
2
O
32.1
5 NaHCO
3
X Na
2
CO
3
3NaHCO
3
+CO
2
+H
2
O
32.8
2/3 Na
2
CO
3
3NaHCO
3
X 5/3 Na
2
CO
3
+CO
2
+H
2
O
H
Kcal/gmol CO
2
Reaction
CO
2
removal is exothermic
Sorbent regeneration is endothermic
9
Fundamental Kinetic and
Thermodynamic Studies
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60C
70C
80C
8%CO
2
16%H
2
O
76%He
Na
2
CO
3
3NaHCO
3
SBC Grade #3 Sorbent
First order reaction kinetics
CO
2
H
2
O
Temperature sensitive
kinetics
NaHCO
3
product at 60 C
Intermediate product
(WS) at 70 C
Higher temperatures
decrease CO
2
removal
Potential temperature control
strategies
Cold diluents solids
Liquid H
2
O addition
( H
VAP
= 10 Kcal/gmol)
10
Sorbent Operating Temperature Ranges
Sodium Carbonate
Carbonation: 60 80 C
Regeneration (decarbonation; calcination): > 120 C
Potassium Carbonate
Carbonation: up to 120 C
Regeneration (decarbonation; calcination): > 140 C
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TGA Cyclic Reactivity Testing
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Time (minutes)
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Sorbent: 40% supported potassium
carbonate
Temperature: 70 C (Isothermal)
Gas: Carbonation 7.5% CO
2
, 5.7%
H
2
O, He
Regeneration 100% He
12
Fixed-Bed Reactor System at LSU
N
2
O
2
CO
2
Syringe Pump
(H
2
O)
Vent
BPR : Back
Pressure
Regulator
COND: Condenser
CV : Check valve
D : Dryer
F : Filter
MFC : Mass Flow
Controller
PI : Pressure
Indicator
PRV : Pressure
Relief valve
Furnace
BPR
To GC
COND
PRV
MFC
CV
F
D
MFC
CV F
D
D
MFC
CV F
PI
PI
13
Fixed-Bed Testing of SBC
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100
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Time (minutes)
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(
%
)Cycle 1
Cycle 2
Cycle 3
Cycle 4
Cycle 5
Sorbent: SBC Grade #3
Regeneration
Temp: 120 C
Gas: He
Carbonation
Temp: 60 C
Gas: 8% CO
2
, 16%
H
2
O in He
14
SBC Sorbent Interaction with HCl and SO
2
Hydrogen Chloride
1-inch Fluidized-bed testing
100 ppm HCl in simulated flue gas
>98% removal with 1.2 sec superficial residence time
Sulfur Dioxide
TGA tests and 1-inch fluidized-bed testing
1000 ppm SO
2
in simulated flue gas
>95% removal
Irreversible at temperatures 200 C
15
RTIs Bench-Scale Fluid-Bed Test Unit
16
Fluid-Bed Testing of 40% Supported
Sodium Carbonate
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Time (minutes)
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)
Cycle 1
Cycle 2
Cycle 3
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Time (minutes)
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Cycle 1
Cycle 2
Cycle 3
Carbonation in 7% Carbon Dioxide, 6% Water Vapor
17
Conceptual Transport Reactor System
18
Transport Reactor Approach
Advantages
Low pressure drop (<1 psi [< 30 in. W.C.])
Reliable and effective solid sorbent movement
Superior temperature control
Sorbent design challenges
High sorbent reactivity required
Short residence times (2-6 seconds)
Highly attrition-resistant sorbent required
High sorbent flux rate
19
Engineering Design Challenges
Heat integration
Capturing low-grade, low-value heat in the steam cycle for
sorbent regeneration
Minimizing parasitic power consumption
Heat transfer:
Removal of carbonation heat of reaction
Addition of regeneration energy
Low pressure drop of flue gas stream
Minimizing additional power requirements of the I.D. fan
Sorbent Transfer
Efficiently move sorbent between carbonation reactor and
regenerator
20
Heat Integration Analysis
Goal: Minimize process energy requirements
Target: Regeneration
Largest energy requirement
Low-level heat (120-140 C)
Solutions
Steam usage
Low-level heat sources
Recover flue gas heat
Extract heat from cooling water
Alternative air preheating schemes
21
Comparison of Coal Fired Power Plants
With and Without CO
2
Removal
Heat Require- Auxiliary Plant
ment for CO
2
Sor- Gross Plant Power Net Plant Efficiency
bent Regeneration, Power Requirement Power (HHV)
Case Btu/lbmol CO
2
kWe kWe kWe %
EPRI Base
Case 7C
Coal Fired Steam Not Applicable 491,108 29,050 462,058 40.5
Plant; no CO
2
Removal
EPRI Case 7A
MEA CO
2
71,140
E
402,254 72,730 329,524 28.9
Removal
EPRI Case 7A
Re-calcd 103,400
A
362,178 72,730 289,448 25.4
Comparison Case
Na
2
CO
3
-based 60,000 416,144 72,730 343,414 30.1
Dry CO
2
Removal
90% CO
2
Removal for Applicable Cases
For all cases: Heat input = 1,140,155 kW
heat
(HHV)
E
EPRI, Evaluation of Innovative Fossil Fuel Power Plants with CO
2
Removal, 2000
A
Alstom Power, Engineering Feasibility and Economics of CO
2
Capture on an Existing Coal-Fired Power Plant, 2001
22
Summary of Research Findings
The sodium and potassium carbonate sorbents react readily
to remove CO
2
The materials can be cycled repeatedly without appreciable
loss of activity
The carbonate/carbon dioxide reaction may be limited by
considerations of heat removal from the sorbent particle
The high initial rates of reaction may be suitable for short
residence time transport reactor systems
Regeneration of sorbent can be carried out in an essentially
pure carbon dioxide stream
Supported materials provide suitable activity and attrition
resistance
23
Technology Development Plan
Evaluate concept
Kinetic studies
Material screening
Sorbent development
Process modeling
Preliminary economics
Scale-up of sorbent production
Sorbent evaluation
Reactivity
Capacity
Attrition
Stability
Energy analysis
Heat requirements
Temperature constraints
Economic evaluation
Thermodynamic Analysis
& Lab Testing
Bench-scale
Testing
Pilot-Plant
Testing
Slip Stream
Testing
Demonstration
Testing
COMMERCIAL
IMPLEMENTATION
24
Acknowledgements
U.S. DOE/NETL Cooperative Agreement No.
DE-FC26-00NT40923
Project Manager: Michael K. Knaggs
Sequestration Project Manager: Scott M. Klara