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Passive CO 2 Separation Membranes for Hot Flue Gases Improving CO 2 capture energy efficiency by integrating passive separation membranes into heat recovery steam generators (HRSG) and boilers Matthew Merrill, PhD Luna Innovations www.lunainc.com 434-220-2512 [email protected] Separation Membranes and Features Acknowledgments This material is based upon work supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Numbers DE-SC0015123 and DE-SC0017124. The dual phase membrane enables passive CO 2 separation from incipient flue gas in the temperature range of 200 – 700 °C and 1 – 20 ATM. The Need: An economically practical technology is needed to retrofit existing infrastructure for capturing CO 2 from fossil fuel power plants and other, large scale sources of flue gas. The Problem: Conventional CO 2 technologies capture cold (< 150 °C) CO 2 and divert power from electricity generation to thermally regenerate the CO 2 sorbent. Further development of CO 2 sorbents can only offer incremental improvements to the severe energy costs of the additional heat cycle required for thermally regenerating CO 2 sorbents. The Solution: To achieve substantial improvements in overall energy efficiency, this new technology must avoid the Carnot energy inefficiency caused by the additional heat cycles. The solution is to apply passively separation membrane to the flue gas while the CO 2 is still hot and at high pressure. A process that can passively separate CO 2 from the flue gas while it is still hot is more energy efficient with a theoretical minimum separation energy 10-15 times smaller (0.2 GJ/ton CO 2 at 300 °C) than the conventional amine solvents. The Technology: Luna is developing a robust, inorganic membrane capable of separating CO 2 and other acid gases from flue gases in the operational conditions of 200 – 700 °C and 0.1 – 20 ATM. Luna is partnering with Nooter/Eriksen to integrate the modular membrane technology into heat recovery steam generation systems (HRSG). Luna’s membrane is distinct from conventional dual phase membranes in that all mass transport is conducted through the liquid phase. In contrast, conventional ceramic-carbonate dual phase membranes are slow and require >700 °C because of dependence on solid oxide ion conduction. 1 10 100 10 100 1,000 Capillary Pressure, ATM Maximum pore diameter, nm Overcoming the Conventional Energy Efficiency Limitations of CO 2 Capture Application Highlights Both low (200 – 500 °C) and high temperature (500 – 700 °C) membranes under development for modular insertion into HRSG temperature zones. Separation of acid gases (CO 2 , NO 2 , SO X ) from non-acid gases (N 2 ,O 2 ) may eliminate need for selective catalytic reduction (SCR) systems. Adaptation of separation chemistry to efficiently separate O 2 from air at 200 – 300 °C for oxy-fuel combustion and gasification. Dual Phase Membrane: The non-volatile liquid phase is retained in the nanoporous solid phase with capillary pressures up to 100 ATM. The Liquid Phase: The liquid phase is a molten electrolyte that selectively and reversibly sorbs gases as ions. All mass transport is conducted within the liquid phase for rapid permeation through the fastest ion conductors in the temperature range. The Solid Phase: The solid phase is an inert, high strength ceramic forming thin membranes capable of withstanding high pressures. The Performance: The combination of selectivity and permeability exceed those of competitive technologies and meet performance requirements expected for post-combustion capture of CO 2 with membranes (Ramasubramanian, J. Membrane Science 2012). Operational Conditions: The inorganic, oxidation resistant membranes enable separation in previously unattainable conditions that include 200 – 700 C and 0.1 – 20 ATM. The nanoporous, ceramic solid phase retains the liquid separation phase with capillary action capable of withstanding 10’s of ATM pressure gradients. The dual phase membrane is similar to membranes used in molten fuel cells and is not limited by the physics governing Robeson’s Upper Bound. Ohio State University, 2017 NETL Continuation Application Status Meeting Membrane Technology and Research (MTR), NETL Advanced CO 2 Capture R&D Program Technology Update May 2013 Research Triangle Institute, 2013 NETL Advanced CO 2 Capture R&D Program Technology Update General Electric (GE), 2013 NETL Advanced CO 2 Capture R&D Program Technology Update Gas Technology Institute (GTI), 2017 NETL BP1 Review Meeting Lu, B. and Lin, Y.S., Journal of Membrane Science 444 (2013) 402–411 Performance Highlights Molten phase sorption reactions and mass transport produce unrivaled combination of selectivity and permeability. Stable inorganic materials enable operation in previously unattainable temperatures, pressures, and environments. The separation chemistry is being adapted to O 2 , NH 3 , HCl, Cl 2 , and NO 2 for widespread industrial applications. The post-combustion CO 2 capture membranes are being developed with computer assisted design (CAD) and finite element modeling (FEM). The determination of membrane dimensions are based upon factors including safety, separation performance, material properties, and operational stresses. In partnership with Nooter/Eriksen, the next steps include designing modular units with computational fluid dynamics (CFD) and system level analysis modeling for integration into N/E HRSG systems.

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Page 1: Passive CO2 Separation Membranes for Hot Flue Gases...thermally regenerating CO 2 sorbents. The Solution: To achieve substantial improvements in overall energy efficiency, this new

Passive CO2 Separation Membranes for Hot Flue Gases

Improving CO2 capture energy efficiency by integrating passive separation membranes into heat recovery steam generators (HRSG) and boilers

Matthew Merrill, PhDLuna Innovations [email protected]

Separation Membranes and Features

AcknowledgmentsThis material is based upon work supported by the Department ofEnergy, Office of Science, Office of Basic Energy Sciences underAward Numbers DE-SC0015123 and DE-SC0017124.

The dual phase membrane enables passive CO2 separation from incipient flue gas in the temperaturerange of 200 – 700 °C and 1 – 20 ATM.

The Need: An economically practical technology is needed to retrofit existing infrastructure for capturingCO2 from fossil fuel power plants and other, large scale sources of flue gas.

The Problem: Conventional CO2 technologies capture cold (< 150 °C) CO2 and divert power from electricitygeneration to thermally regenerate the CO2 sorbent. Further development of CO2 sorbents can onlyoffer incremental improvements to the severe energy costs of the additional heat cycle required forthermally regenerating CO2 sorbents.

The Solution: To achieve substantial improvements in overall energy efficiency, this new technology mustavoid the Carnot energy inefficiency caused by the additional heat cycles. The solution is to applypassively separation membrane to the flue gas while the CO2 is still hot and at high pressure. Aprocess that can passively separate CO2 from the flue gas while it is still hot is more energy efficientwith a theoretical minimum separation energy 10-15 times smaller (0.2 GJ/ton CO2 at 300 °C) than theconventional amine solvents.

The Technology: Luna is developing a robust, inorganic membrane capable of separating CO2 and other acidgases from flue gases in the operational conditions of 200 – 700 °C and 0.1 – 20 ATM. Luna is partneringwith Nooter/Eriksen to integrate the modular membrane technology into heat recovery steamgeneration systems (HRSG).

Luna’s membrane is distinct from conventional dualphase membranes in that all mass transport isconducted through the liquid phase. In contrast,conventional ceramic-carbonate dual phasemembranes are slow and require >700 °C because ofdependence on solid oxide ion conduction.

1

10

100

10 100 1,000

Cap

illar

y P

ress

ure

, ATM

Maximum pore diameter, nm

Overcoming the Conventional Energy Efficiency Limitations of CO2 Capture

Application Highlights

• Both low (200 – 500 °C) and high temperature (500 – 700 °C) membranes under development formodular insertion into HRSG temperature zones.

• Separation of acid gases (CO2, NO2, SOX) from non-acid gases (N2, O2) may eliminate need forselective catalytic reduction (SCR) systems.

• Adaptation of separation chemistry to efficiently separate O2 from air at 200 – 300 °C for oxy-fuelcombustion and gasification.

Dual Phase Membrane: The non-volatile liquid phase is retained in the nanoporous solid phase with capillary pressures up to 100 ATM.

The Liquid Phase: The liquid phase is a molten electrolyte that selectively and reversibly sorbs gases as ions. All mass transport is conductedwithin the liquid phase for rapid permeation through the fastest ion conductors in the temperature range.

The Solid Phase: The solid phase is an inert, high strength ceramic forming thin membranes capable of withstanding high pressures.

The Performance: The combination of selectivity and permeability exceed those of competitive technologies and meet performancerequirements expected for post-combustion capture of CO2 with membranes (Ramasubramanian, J. Membrane Science 2012).

Operational Conditions: The inorganic, oxidation resistant membranes enable separation in previously unattainable conditions that include200 – 700 C and 0.1 – 20 ATM.

The nanoporous, ceramic solidphase retains the liquid separationphase with capillary action capableof withstanding 10’s of ATMpressure gradients.

The dual phase membrane is similar to membranesused in molten fuel cells and is not limited by thephysics governing Robeson’s Upper Bound.• Ohio State University, 2017 NETL Continuation Application Status Meeting

• Membrane Technology and Research (MTR), NETL Advanced CO2 Capture R&D Program

Technology Update May 2013

• Research Triangle Institute, 2013 NETL Advanced CO2 Capture R&D Program Technology Update

• General Electric (GE), 2013 NETL Advanced CO2 Capture R&D Program Technology Update

• Gas Technology Institute (GTI), 2017 NETL BP1 Review Meeting

• Lu, B. and Lin, Y.S., Journal of Membrane Science 444 (2013) 402–411

Performance Highlights• Molten phase sorption reactions and mass transport produce

unrivaled combination of selectivity and permeability.

• Stable inorganic materials enable operation in previouslyunattainable temperatures, pressures, and environments.

• The separation chemistry is being adapted to O2, NH3, HCl, Cl2,and NO2 for widespread industrial applications.

The post-combustion CO2 capturemembranes are being developedwith computer assisted design (CAD)and finite element modeling (FEM).The determination of membranedimensions are based upon factorsincluding safety, separationperformance, material properties,and operational stresses.

In partnership with Nooter/Eriksen,the next steps include designingmodular units with computationalfluid dynamics (CFD) and systemlevel analysis modeling forintegration into N/E HRSG systems.