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Evaluation of Dry Sorbent Technology for Pre-Combustion
CO2 Capture (FE-0000465)
Carl Richardson URS Group
2013 DOE/NETL CO2 Capture Technology Meeting
Pittsburgh, PA • July 10, 2013
Joe Hirsch Elaine Everitt Bill Steen Carl Richardson
M. Rostam-Abadi Hong Lu
Yongqi Lu
2
Project Funding & Performance Dates
BP1: $ 633,669
BP2: $1,134,602
BP3: $ 916,123
Total: $2,684,394
Funding Distribution by Budget Period
0
250
500
750
1000
FY2010 FY2011 FY2012
Year
Dol
lars
, $1,
000
ICCI ISGS DOE
• Cost Share is 25%
• POP is September 2009 through September 2013
3
Project Objectives and Scope of Work
Objective
• Identify, develop, and optimize engineered sorbents for a process that combines CO2 capture with the water gas-shift (WGS) reaction
Scope of Work
• Thermodynamic, molecular and process simulation modeling to identify/predict optimal sorbent properties and process operating conditions
• Synthesis and characterization of sorbents
• Experimental evaluation of sorbents for CO2 adsorption and regeneration
• Techno-economic analysis
4
Research Tasks
2.1Thermodynamic analysis (materials with known thermo-
properties)
2.3 Molecular simulation
(new materials)
3.1/2 synthesize/ characterize sorbents with
desired properties
2.4 Acquire/screen sorbents with desired
properties
4.1 Parametric tests for CO2 adsorption using P-TGA and HTPR
5. Engineering feasibility analysis using optimal sorbent and parameters
4.2/4/5 Parametric tests for optimal regeneration
conditions
4.3/4/5 Parametric tests for effects of impurities
2.2 Process simulation to analyze energy performance
of SEWGS
1. Project management and planning
Computational modeling to
identify sorbents
Sorbents screening and
synthesis
Sorbents Evaluation
Engineering analysis
5
Research Tasks
2.1Thermodynamic analysis (materials with known thermo-
properties)
2.3 Molecular simulation
(new materials)
3.1/2 synthesize/ characterize sorbents with
desired properties
2.4 Acquire/screen sorbents with desired
properties
4.1 Parametric tests for CO2 adsorption using P-TGA and HTPR
5. Engineering feasibility analysis using optimal sorbent and parameters
4.2/4/5 Parametric tests for optimal regeneration
conditions
4.3/4/5 Parametric tests for effects of impurities
2.2 Process simulation to analyze energy performance
of SEWGS
1. Project management and planning
Computational modeling to
identify sorbents
Sorbents screening and
synthesis
Sorbents Evaluation
Engineering analysis
Final Year of Project
7
IGCC + SEWGS vs. Conventional IGCC
Conventional CO2 capture
SEWGS
400-180C
CO + H2O = CO2 + H2
Exothermic reaction Kinetically limited at low temperatures, multiple stages / temperatures required SEWGS can achieve high CO conversion at high temperature
9
Current Status Overview • Computational Modeling
• Thermodynamic Modeling, Process and Molecular Simulations
• Helped down-selected from ‘optimal’ sorbents
• Sorbent Preparation • Goal is to synthesize sorbents per computational modeling and with high
capacity, WGS reactivity, long cycle life, etc.
• Ultrasonic Spray Pyrolysis, Flame Spray Pyrolysis, and Molecular Alloying
• Sorbent Evaluation • Analytical Characterization and TGA for screening
• High Temperature, High Pressure Reactor Studies: laboratory simulated, closest to real world conditions short of pilot studies
• Techno-Economic Study • Evaluated different approaches to process
• Identified keys to economic viability
10
High Temperature, High Pressure Reactor
• Syngas, CO2/N2, steam introduced as water
• Corrosive / toxic environment (e.g., NH3, H2S, HCl)
water pump Preheater
Control panel (T, P. F)
CO/CO2 analyzers
Reactor
Data logger
Gas supply
• Up to 1000oC, 40 bar
• PLC Controlled
• CO/CO2 monitoring
11 11
• Adsorption in CO2/N2 and desorption in N2
0 2 4 6 8 10 120
10
20
30
40
wt. c
hang
e (g
-CO2
/g-s
orbe
nt) (
%)
Cycle
FSP Ca/Al
0 2 4 6 8 10 120
10
20
30
40
wt. c
hang
e (g
-CO2
/g-s
orbe
nt) (
%)
Cycle
MA Ca/Mg
Sorbent FSP32 Sorbent MA63
Temperature, °C
Time, min
PCO2, bar
Ptotal, bar
Adsorption 650 12* 4 12 Regeneration 650 ~ 830 ~90 0 12 *30 min CO2 adsorption in Cycle 12.
CO2 Adsorption / Desorption Tests
• Capacity of the sorbents: 0.3 – 0.4 gCO2/gsorbent (70-80% of theoretical)
• Comparison between cycle 12 and cycles 1-11 indicated CO2 adsorption completed in ≤12 min
12 12
0 2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Regeneration: up to 830 °C, 12 bar N2
Sor
bent
cap
acity
(g-C
O2/g
-sor
bent
)
SEWGS-Regeneration cycles
Sorbent: FSP Ca/Al
0 2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Regeneration:up to 830 °C, 12 bar N2 (Black sqaure), or up to 830 °C, 10 bar N2 and 2 bar H2O (Green circle)
Sor
bent
cap
acity
(g-C
O2/g
-sor
bent
)
SEWGS-Regeneration cycles
Sorbent: MA Ca/Mg
Sorbent FSP32 Sorbent MA63
• CO2 adsorption/WGS (SEWGS) in syngas and desorption in N2 or N2/H2O
Temperature,
°C Time, min
PCO, bar
PH2O, bar
PN2, bar
Ptotal, bar
SEWGS 650 20 4 8 0 12 Regeneration 650-830 ~90 0 0 12 12 Regeneration* 650-830 ~90 0 2 10 12
*Regeneration conditions used for Sorbent MA63 in Cycles 7-9.
An example of CO and CO2 concentration profiles (Sorbent MA63)
SEWGS Performance Tests
• CO conversion increased from 47% to ~100% with sorbent (equilibrium CO conversion 77% at tested conditions without sorbent)
• Improved sorbent performance in syngas (w/ water vapor)
13
Test Results: Working Capacity and Impact of H2S
13
FSP25 44:56 wt% CaZrO3:CaO (FSP)
USP199 25:75 wt% Meyenite:CaO (USP)
FSP32 1:4 Al:Ca at% (FSP)
MA63 23:77 wt% MgO:CaO (MA)
• Sorbents perform better in syngas
• USP199 seems to perform better
• Low impact of H2S
A1: CO2/N2 & A2: Syngas B3:Syngas plus H2S
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Gra
ms
CO2
/ G
ram
s Ca
lcin
ed S
orbe
nt
FSP25, Test A1.1 FSP25, Text A2.1
USP199, Test A1.2 USP199, Text A2.2
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Gra
ms
CO2
/ G
ram
s Ca
lcin
ed S
orbe
nt
FSP25, Test B3.1USP199, Test B3.2FSP32, Test B3.3MA63, Test B3.4
14
HTPR Results: Impact of Steam:CO Ratio on FSP25
• Steam:CO ratio difficult to control (parametric conditions not always achieved)
• Apparent trend with decreasing ratio of CO conversion
• Conversion lower than observed by ISGS
• Hybrid sorbents may be necessary; could include WGS catalyst usage
1.4
1.6
1.8
2
2.2
2.4
0%
5%
10%
15%
20%
25%
30%
0 2 4 6 8 10 12
Stea
m:C
O R
atio
CO to
CO
2Co
nver
sion
Cycle Number
Sorbent #2 FSP25
CO to CO2 Conversion
Steam:CO Ratio
15
Technoeconomic Assessment, Initial Approach
28 ft
42 ft
4,315 ACFM6 min residence time
• Sorbent • 0.2gCO2/gsorbent
• Heat Exchange• 2” diameter• 81 tubes/row, 27
rows• 22,866 ft2
• Water/steam• Fluidized bed
• Gas distribution plate
• 644 kg/m3
(effective density)
90% CO2-free syn-gas
• Cyclone 16 ft tall, ‘lose’ 5.3 ft of reactor volume
• Reactors switching between adsorption and regeneration
• Heat of adsorption removed by water
• Steam generated superheated to regenerate
• Resulted in long cycle times, many reactors, many heat exchange tubes
• Failed to take advantage of benefits of SEWGS
16
0
20
40
60
80
100
120
140
160
COE,
mill
s/kW
h or
$/M
Wh
Sorbent Variables
SEWGS Base Case
12 reactors, ↓$ sorbent, 1 sorbent change/yearNo Claus unit, ↑P regen, ↑ sorbent capacity
SEWGS Base Case
8 reactors, ↓$ sorbent, 1 sorbent change/yearNo Claus unit, ↑P regen, ↑ sorbent capacity
12 Reactors 8 Reactors
CO2 Capture Scenario TOC ($M) COE (mills/kWh or $/MWh)
Case 6 (DOE Report) 1,940 119.4 SEWGS – Base Case 2,208 145.1 SEWGS – Fewer reactors (1/2) 2,031 136.4 SEWGS – Fewer reactors (1/3) 1,933 131.9
Techno-economic Assessment, Initial Approach
Base case for SEWGS not
competitive, so assumed fewer reactors, still not competitive….
Even with all optimistic
assumptions using initial approach, SEWGS can’t
compete with Case 6
17
• Dedicated adsorbers and regenerators
• Result: Reduced the number and size of reactors (24 to 12)
• Combust H2 with O2 to generate the heat for regeneration
• Result: Need another ASU and parasitic losses increase, but more efficiently generate pure CO2
• Design process such that the water used to remove the heat of the adsorption can feed a steam turbine
• Result: Need another steam turbine, but gain MWe capacity
Techno-economic Assessment, Alternative Approach
18
Case ASU
Penalty, MW
CO2 Comp Penalty,
MW
Regen Penalty,
MW
Energy Gen. from H2, MW
Energy Gen. from Adsorption,
MW
Net MW
COE, $/MWh
Case 6 -60 -30 -19 464 -0- 497 119 SEWGS, Regen @ 1165°C
-107 -6 -213 251 419 594 128
SEWGS, Regen @
950°C -81 -30 -93 371 419 774 98
Techno-economic Assessment, Alternative Approach
SEWGS becomes viable, but technological hurdles remain
19
Summary • Four nano-engineered sorbents chosen for HTPR testing
• Capacities approaching 0.4 gCO2/gsorbent
• Performance improved in syngas / water vapor
• No significant impacts of H2S observed (other impurity studies ongoing)
• Steam:CO ratio still under investigation
• Techno-economics – Traditional process approach not competitive – More technically challenging approach
• Creating turbine quality steam from heat of adsorption • Moving sorbent from dedicated sorption reactor to regenerator • Combusting H2 slip with O2 from ASU • Economically competitive, but technical challenges remain
20
Plans for Future Work • Complete parametric tests with all impurities
– (H2S, NH3, HCl, COS)
• Long-term tests on select sorbents (USP199)
• Revise Techno-economic Assessment
• Final Report
Next Phase
• Determine WGS viability / CO to CO2 conversion of different sorbents
• Evaluate sorbents in more accurate regeneration environment
• Engineering challenges: reactor design, moving sorbent at operating conditions
21
Acknowledgments
• U.S. Department of Energy/ National Energy Technology Laboratory (DOE/NETL), through Cooperative Agreement No. DE-FE-0000465
• Illinois Department of Commerce and Economic Opportunity (IDCEO), through the Office of Coal Development (OCD) and the Illinois Clean Coal Institute (ICCI) under Contract No. 10/US-2
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