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

6

Technology Fundamentals/Background

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

8

Progress and Current Status

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