Non-Aqueous Solvents for Post-Combustion CO 2 Capture...RTI’s Non -Aqueous Solvent have potential...

Center for Energy Technology

Non-Aqueous Solvents for Post-Combustion CO2 Capture

RTI InternationalLuke Coleman, Marty Lail, Steven Reynolds, Markus Lesemann, Raghubir Gupta

BASFChristian Riemann, Kumar Sugavanam, Sean Rigby, Georg Sieder, Todd Spengeman, Torsten Katz

1st Post-Combustion Capture Conference (PCCC1)Abu Dhabi

May 18, 2011

RTI International

RTI International

RTI International Research budget >$750MM 13% average annual growth over

the last 10 years. One of the worlds leading research

organizations: >4,200 professionals in more

than 40 countries High-quality scientific staff with

tremendous breadth Over 130 different academic

disciplines

Mission: To improve the human condition by turning knowledge into practice


RTI Center for Energy TechnologyProgram Areas Advanced Gasification Syngas Conversion and Clean Fuels CO2 Capture and Conversion Biomass Conversion and Biofuels


Core CompetenciesCatalyst, sorbent and solvent developmentReaction engineeringProcess design and optimizationBench-scale and prototype testing

Technical Maturity

Basic Science Developmental Commercial

Bench

Production

Pilot

Scale

University

Industry

Engineering and Technology Unit

Access to Mission-Oriented Federal Programs

Objective: Development of new energy technologies fromlaboratory bench to full-scale commercialization

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BASF – The Chemical Company

The world’s leading chemical company

Sales 2010: €63,873 million

Income from operations (EBIT) 2010: €7,761 million

Employees at year-end 2010: 109,140

BASF Gas Treatment Leading provider of

gas treatment solutions

Customer focused solution provider

+300 industry references

Innovation driven business unit

Gas treating excellence


Novel Non-Aqueous CO2 Solvent-based Capture ProcessProject Team:U.S. Department of Energy

Objective: Develop novel non-aqueous CO2 scrubbing solvents and

capture process that could substantially reduce the parasitic energy load and corresponding increase in Cost of Electricity (COE) for post-combustion CO2 capture

Funding: $2.75 M ($2.2M ARPA-E) Performance Period: July 2010 → June 2013

Inventor of novel, non-aqueous CO2solvent chemistry

Novel solvent synthesis and formulation, solvent screening and evaluation, and process design and simulation efforts

Global leader in gas treatment solutions Extensive experience in the design,

engineering, and servicing of acid-gas removal systems

Guide solvent evaluation and process design to focus efforts on solving technical challenges to commercialization

ARPA-E IMPACCT ProgramCO2


Process Performance TargetsPower Performance• Reboiler Duty < 2.0 GJth/tonne CO2• Plant Efficiency Point Loss < 7 points

Economic Indicators• Increase in COE < 50%• Cost of CO2 Avoided < $45/tonne CO2

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Overview of the State-of-the-Art Amine SolventsState-of-the-Art Current state-of-the-art technologies are

estimated to be ~85% in ICOE Current DOE post-combustion research target

for increase in COE (ICOE) is 30-35% R&D Focus:

Largest contributor to ICOE is Power Consumption → Reboiler Duty

Basis: 450 MWe Coal-fired Power Plant

SolventParasitic Energy Cost [$/ton CO2 removed] Cost of CO2

Removed[%] Power Capital Operating [$/ton CO2]†

30 % MEA1 27 29 15 8 52

KS-12 22 23 14.4 8.4 46†Assumed $80/MWh1. Rochelle, G. T. (2009). "Amine Scrubbing for CO2 Capture." Science 2009, 325, 1652-16542. http://www.co2management.org/proceedings/Masaki_Iijima.pdf3. Abu-Zahra, M. R. M.; Niederer, J. P. M.; Feron, P. H. M.; Versteeg, G. F. International Journal

of Greenhouse Gas Control I 2007, 135.

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PowerCapital

OperatingICOE Breakdown


http://www.co2management.org/proceedings/Masaki_Iijima.pdf�


Sensible Heat Heat of Vaporization Heat of Absorption

𝐪𝐪𝐑𝐑 = �𝐂𝐂𝐏𝐏(𝐓𝐓𝐑𝐑 − 𝐓𝐓𝐅𝐅)

∆𝛂𝛂 ∙𝐌𝐌𝐬𝐬𝐬𝐬𝐬𝐬

𝐌𝐌𝐂𝐂𝐎𝐎𝟐𝟐∙𝟏𝟏𝐱𝐱𝐬𝐬𝐬𝐬𝐬𝐬

� + �∆𝐇𝐇𝐕𝐕,𝐇𝐇𝟐𝟐𝐎𝐎 ∙𝐩𝐩𝐇𝐇𝟐𝟐𝐎𝐎𝐩𝐩𝐂𝐂𝐎𝐎𝟐𝟐

∙𝟏𝟏

𝐌𝐌𝐂𝐂𝐎𝐎𝟐𝟐� + �

∆𝐇𝐇𝐚𝐚𝐚𝐚𝐬𝐬,𝐂𝐂𝐎𝐎𝟐𝟐𝐌𝐌𝐂𝐂𝐎𝐎𝟐𝟐

�

SolventCp

[J/g K]∆habs

[kJ/mol]∆hvap

[kJ/mol]

Xsolv[mol solvent/ mol solution]

∆α[mol CO2/ mol

solvent]

Reboiler Heat Duty [GJ/tonne CO2]

MEA (30%) 3.8 85 40 0.11 0.34 3.22

Lower Energy Solvent System

Reboiler Heat Duty – R&D Opportunity

All aqueous systems have similar properties such as high heat capacities, heats of absorption and vaporization, and high dilutions

Reboiler heat duties are similar and can only be improved by lower heats of absorption or increase in concentration of amine.

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RTI’s Approach: Non-aqueous, organic-based solvent systems More suitable physical and chemical properties Alternative reaction pathways to conventional carbamate and bicarbonate chemistry


RTI’s Approach to Non-aqueous Solvents


Potential Reaction Pathways

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CO2

Non-aqueous reactions offer lower energy reaction pathways

Reactions are reversible at low temperatures

Achieve high dynamic CO2 loadings

Non-aqueous solvents have low specific heat capacities and low solvent dilutions

Diverse group of nitrogenous bases


Challenges facing Non-Aqueous CO2 Solvents


Water accumulation and involvement in the CO2capture mechanism Non-aqueous reaction pathway must be essentially exclusive

in the presence of water (no selectivity for rxns involving H2O) Solvent systems with low water solubility form separate liquid

phase

Solvent viscosity Solvent viscosity affects rate of CO2 capture and column

dimensions

Solids formation in rich solvent Solids can accumulate in packing or other undesirable areas in

the process

Foaming Many aqueous and non-aqueous solvents foam when purged

with gasesRTI’s Non-Aqueous Solvents Easily Separate from Aqueous Phase

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Automated, Multi-cycle Solvent Evaluation SystemMulti-Cycle Testing With High-Fidelity Flue Gas

Automated batch recycling of solvent Continuous cycling between absorption and

regeneration conditions ~ 150 mL solvent volume Temperature controlled, atmospheric pressure

reactor Simulated flue gas including CO2, H2O, O2, and SO2

(balance N2) Automated data analysis

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Reactor

Saturator

CO2 Analyzer

Chiller

Condenser

Gas Metering and Switching


Automated CO2 VLE and Reaction Calorimeter

Capabilities CO2 Partial Pressure – CO2 Loading Relationship (Vapor-liquid Equilibrium) Heat of CO2 Absorption (Reaction Calorimetry) Specific Heat Capacity Vapor Pressure12


Heat-balance reaction vessel

Automated Gas Switching

Automation, Control, and Acquisition

Batch Charge Vessel

Calorimeter / Equilibrium Cell


Screening Results of RTI’s Novel Non-aqueous CO2 Solvents

Screened a broad array of non-aqueous solvent families

Summary of Results: Low regeneration temperatures

40 to 110 C High CO2 loading capacities

60 to 163 g CO2 / L solvent

Identified promising candidate solvents systems that have higher loadings and lower regeneration temperatures than conventional aqueous-amine solvents

0

20

40

60

80

100

120

140

160

180

A B C D E F G H I J K L Aq. MEA

CO2 Lo

ading

[gCO 2/L

solven

t] Pe

ak Re

genera

tion Te

mpera

ture [°C

]

Non-Aqueous Solvent System

LoadingTemperature

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Multi-cycle Testing with High-fidelity Flue Gas

Absorption:Temperature: 30 CFlue Gas Composition:

14%CO2, ~3 % H2O, 4% O2, 50 ppm SO2, Balance N2

Regeneration:Temperature: Ramp to 80 CGas Composition: N2 Purge

Summary of Results: Stable CO2 loading and regeneration

temperature in presence of water Not degraded by water

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10

20

30

40

50

60

70

80

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

CO2A

bsorbe

d [gram

s]

Cycle Number

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Representative Non-aqueous Solvent


Water Accumulation is a Major Hurdle for Non-aqueous SystemsRTI’s Non-Aqueous Solvents: Are selective for non-aqueous reaction pathways in the

presence of water

Have low water solubility and therefore form a separate liquid phase in the presence of water

Have low regeneration temperatures allowing use of lower quality steam

Phase Separation15



Lowering Power Load and ICOE

Beneficial Characteristics Lower specific heat capacity (CP) Lower heat of absorption (∆habs) Lower solvent dilution (Increasing xsolv) Increased CO2 working capacities (∆α)

Challenges Lower absorption T for optimal capture Water accumulation due to condensation or desiccation of

water from flue gas Evaporative losses in absorber Degradation by flue gas contaminants (O2, SO2) Cost of solvents

SolventCp

[J/g K]

∆habs

[kJ/mol]

∆hvap

[kJ/mol]

xsolv[mol solvent / mol solution]

∆α[mol CO2 /

mol solvent]

Reboiler Heat Duty

[GJ/tonne CO2]

MEA (30%) 3.8 85 40 0.11 0.34 3.22

Lower Energy Solvent System 1.45* 30* 38 0.3* 0.6* 1.97

*Experimentally measured data

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Technology Development Plan – Current Project EffortsPrevious Work Current Project Future Development

Yr 2009-10 2010-13 2014-15 2016-18 2019+TRL 1 2 3 4 5 6 7 8 9

Proof of Concept/Feasibility

Laboratory Validation• Comprehensive solvent screening

• Identify promising solvent systems• Determine thermodynamic and physio-chemical properties for novel

systems• CO2 capture process modeling

• Develop comprehensive process model• Evaluate novel process configurations and integration schemes• Compare performance with conventional solvent systems

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Technology Development Plan – Next Stage of ProjectPrevious Work Current Project Future Development

Yr 2009-10 2010-13 2014-15 2016-18 2019+TRL 1 2 3 4 5 6 7 8 9

Relevant Environment Validation • Bench-scale testing to assess solvent performance

• Continuous flow, 10 kg/day CO2 capture unit operated using simulated flue gas• Long term (1,000 hours) performance stability testing with

high-fidelity flue gas• Collect process and scale-up data to support simulation and

pilot-scale unit design efforts• CO2 capture process modeling

• Update process models• Techno-economic analysis

• Preliminary engineering design package for a pilot unit

Prototype Testing at Power Plant

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Summary

RTI’s CO2 Capture and Conversion Program Team

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RTI’s Non-Aqueous Solvent have potential to significantly lower ICOE Significantly lower energy penalty Potential for lowering operating costs

Project Status Nearing completion of Year 1 of the project Identified several promising non-aqueous solvents

exhibiting Reboiler heat duties ranging from 2.0 to 2.5 GJth /tonne CO2

Evaluating process configurations, solving process challenges

Designing continuous bench-scale unit

Non-Aqueous Solvents for Post-Combustion CO 2 Capture...RTI’s Non -Aqueous Solvent have potential...

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