Rapid Temperature Swing Adsorption using

Polymer/Supported Amine Composite

Hollow Fibers

Christopher W. Jones, Ryan Lively, Yoshiaki

Kawajiri, William J. Koros, Matthew Realff, David S. Sholl

Georgia Institute of Technology

Katherine Searcy

Trimeric Inc.

Ryan Lively

Algenol Biofuels

Post-Combustion Sorbent-Based Capture

2014 NETL CO2 Capture Technology Meeting

Sheraton Station Square, Pittsburgh, PA

Tuesday, July 29, 2014

DOE Award #: DE-FE0007804

Budget:

DOE contribution:

Year 1: $ 691,955

Year 2: $ 847,672

Year 3: $ 847,006

Total: $2,386,633 (79%)

Cost Share Partners:

GE Energy: $ 420,000

Algenol Biofuels: $ 183,900

Southern Company: $ 33,147

Total: $ 637,047 (21%)

Total Budget: $3,023,680

Project Performance Dates – October 2011 to September 2014

Key Idea:

Combine:

(i) state-of-the-art supported amine

adsorbents, with

(ii) a new contactor tuned to

address specific weaknesses of

amine materials,

to yield a novel process strategy

Ideal temperature swing adsorption

1000 µm

RP Lively et al., Ind. Eng. Chem. Res., 2009, 48, 7314-7324

Bundle of 40 fibers in a

1.5’ module at GT

Hollow Fiber Contactor:

4

RTSA Qualitative Cycle:

Flue gas

CO2/N2

N2

Cooling

water

Cooling water +

sorption enthalpy

Hot water:

140°C

Hot water

N2 sweep

Concentrated CO2

Hot

water:140°C

N2

N2

Cooling

water

Hot water 140°C 55°C

32 s

60 s

10 s

35 s Concentrated CO2

Hollow Fiber Contactor:

Key Experimental Tasks:

1) Spinning of high solid content (50-66 volume%), flexible hollow fibers, using low

cost commercial polymers (e.g. cellulose acetate, Torlon®).

2) Incorporating amines into composite polymer/silica hollow fibers.

3) Building and demonstrating RTSA systems for CO2 capture from simulated flue

gas.

4) Assessing the impact of operating conditions on deactivation via (i) oxidation, (ii)

SOx exposure, (iii) NOx exposure.

5) Constructing a barrier lumen layer in the fiber bore, allowing the fibers to act as a

shell-in-tube heat exchanger.

6) Demonstrating steady-state cycling of multi-fiber module with heating/cooling.

Post-Spinning Infusion:

Spinneret

Dope

Water Quench Bath

Dope

Bore

Fluid

Bore

Fluid Take-Up Drum

Air Gap

Fiber module with

lumen layer and PEI

on silica & fiber pore

walls

MeOH+ PEI infuse

Module

makeup,

add lumen

layer

Post-spinning

processing

1) Spinning of high solid content (50-66 volume%), flexible hollow fibers

2) Incorporating amines into composite polymer/silica hollow fibers.

Y. Labreche et al., Chemical Engineering Journal, 2013, 221, 166-175.

F. Rezaei et al., ACS Applied Materials & Interfaces, 2013, 5, 3921-3931.

Y. Fan et al., International Journal of Greenhouse Gas Control, 2014, 21, 61-72.

4) Assessing the impact of operating

conditions on deactivation via (i)

oxidation, (ii) SOx exposure, (iii) NOx

exposure.

-- conditions whereby oxidation via

residual oxygen in flue gas can be

avoided identified

-- equilibrium and dynamic sorption

measurements of NO, NO2, SO2

completed

-- single component and

multicomponent sorption studies

SOx/NOx Experiments:

F. Rezaei et al., Industrial &

Engineering Chemistry Research,

2013, 52, 12192-12201.

F. Rezaei et al., Industrial &

Engineering Chemistry Research,

2014, in press.

SOx/NOx studies facilitated by support of Southern Company.

4) Assessing the impact of operating

conditions on deactivation via (i)

oxidation, (ii) SOx exposure, (iii) NOx

exposure.

-- NO2, SO2 adsorb strongly, but have

modest impact at low concentration

-- saturation capacity loss observed

-- high concentration of gases (200

ppm) cause significant capacity loss

-- deactivated fibers can be stripped of

amine and recharged in the field for full

capacity regeneration

SOx/NOx Experiments:

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

1.2

no

rma

lize

d q

b

Number of Cycles

36 ppm NO

2 ppm SO2

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

1.2

no

rmalized

qb

Number of Cycles

200 ppm NO

200 ppm SO2

recharged fiber

Hollow Fiber Contactor as Heat Exchanger:

5) Constructing a barrier lumen layer in the fiber bore, allowing the fibers to act as a

shell-in-tube heat exchanger.

Two approaches:

(i) Post-treatment: Flow of a polymeric, Neoprene ® latex and cross-linker through

fibers

Sample He permeance (GPU)

CA/Silica 72,200 (25 psi)

CA/Silica/Neoprene®/TSR-633 3.4

-- Large decrease in mass flux from bore to shell

with lumen layer = good barrier layer

Y. Labreche et al., ACS Applied Materials & Interfaces, 2014, submitted.

Hollow Fiber Contactor as Heat Exchanger:

5) Constructing a barrier lumen layer in the fiber bore, allowing the fibers to act as a

shell-in-tube heat exchanger.

Two approaches:

(i) Post-treatment: Flow of a polymeric, Neoprene ® latex and cross-linker through

fibers

- Disadvantage – fibers can become clogged by latex, requires careful

handling of latex

(ii) Dual layer fiber spinning – spin the lumen layer when initial fiber formed

- Advantage – highly scalable synthesis when poly(amide-imide)

like Torlon® employed

- Main fiber: porous Torlon® containing 50-60 wt% silica;

Lumen layer: dense Torlon®; post-treatment with PDMS gives excellent

barrier properties

Hollow Fiber Contactor as Heat Exchanger:

Lab scale heat capture efficiency during

adsorption: ~72% • Torlon®, commercially available

• Improved thermal & chemical

stability

• Excellent barrier properties for

both water and gases

• No need for problematic latex

post-treatment

Y. Fan et al.,

AIChE Journal, 2014, submitted.

Y. Labreche et al.,

Polymer, 2014, in preparation.

Fiber Cycling – Model and Realistic Conditions:

6) Demonstrating steady-state cycling of multi-fiber module with heating/cooling.

Flue gas composition: 35 oC, 1 atm

~ 13% CO2, ~13% He (Inert tracer),

6% H2O, balance gas N2

36 inch

Fiber module

0 10 20 30 40 500.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

qb (

mm

ol/g

)

Cycles

0 200 400 600

0

2

4

6

8

10

T

(oC

)

Time (s)

z/z0=0.3

z/z0=0.5

z/z0=0.7

0 200 400 600

0

4

8

12

16

Co

nc

en

tra

tio

n (

mo

l%)

Time (s)

He

CO2

He

CO2 breakthrough curves

Thermal wave moved

along Z direction

* Estimated

thermal

excursion is

~ 63 oC in full

size module

qb 1.10 mmol/g

qb remains ~ 1.1 mmol/g over 50 cycles

tb

*

CO2 Sorption in Uncooled Generation 2 Fibers:

Generation 3 Fibers:

Dynamic process modeling and system technoeconomic analysis suggest

there are several factors to lowering costs:

(i) Improved sorption capacities [pseudo-equilibrium (qpe),

breakthrough (qb), swing capacities (qs)]

(ii) Improved process configuration allowing for enhanced heat

management without integrating with power plant

Generation 3 Fibers:

Dynamic process modeling and system technoeconomic analysis suggest

there are several factors to lowering costs:

(i) Improved sorption capacities [pseudo-equilibrium (qpe),

breakthrough (qb), swing capacities (qs)]

(ii) Improved process configuration allowing for enhanced heat

management without integrating with power plant

(mol/kg fiber) qpe qb qs

Generation 1 fibers: 1.1 0.5 0.30

Generation 2 fibers: 1.5 1.1 0.65

Generation 3 fibers: 2.0 1.3 0.75

(260% increase in qb in 2 years)

Adsorption = 32 s

Self Sweeping/Heating = 60 s

N2 sweeping = 10 s

Cooling = 35 s

Cycle Time = 137 s

Parameter Estimation

& Model Validation

from Experiments

Process Analysis &

Parametric Studies

Model Development

Input to Design of

Experiments

Model Development (Single Gen 2 Fiber Modeling):

Cyclic steady state simulation

F. Rezaei et al., Chemical Engineering Science, 2014, 113, 62-76.

Model predicts increase in breakthrough capacity due to decrease of mass transfer resistance

Smaller silica particles to be employed experimentally.

Overall mass transfer resistance vs. sorbent size

Process Improvement from Modeling : Effect of Sorbent Size:

Hollow fiber schematic with different mass transfer resistance components

Overall approach:

32 seconds

60

se

co

nd

s

10 seconds

35

se

co

nd

s

Coo

ling

Adsorption

Gas Sweeping

Se

lf-s

we

ep

ing

Cycle Design on Single

Fiber (GT)

Flue Gas

Feed Flue Gas

From FGD

Stack

CO2 to

Injection

CO2 Compression

and Dehydration

Treated Flue

Gas to Stack

KEY TO FLOW LINE COLORS:

RED = Tempered Water System

BLACK = Flue Gas

BROWN = Plant CTW, Plant IP Steam,

and other utility systems

S-101

Trim SO2 Removal

E-101

Trim SO2 Cooler

CWS

CWR

Process

Water

SO2 Removal

Reagent

To Wastewater

Treatment

Fiber Modules in

Adsorption Mode

F-112

Draft Fan 2

Fiber Modules in

Self-sweeping Step

Fiber Modules in

N2-sweeping Step

Fiber Modules in

Cooling Mode

P-102

Trim SO2 Recirculation

Pumps

Notes:

1.Items not shown include:

- Water filtration of closed loop and cooling water

- Details of compression train and CO2

dehydration

- Details of reagent delivery for trim SO2 removal

2. Configuration of inlet gas cooler and

condensate removal is TBD.

Compressor

Stages

Compressor

Scrubbers

After-CoolersE-314

Main

Heater

Co

nd

en

sa

te

EXP-351

Power Recovery

TurbineS-351

Desuperheater

P-351

Condensate

Pump

Condensate

Return to

Hot Well

F-101

Draft Fan 1

E-102

Gas Trim

Cooler

CWR

V-102

Condensate KO

P-506

CO2 Pump

T-303

Hot Water

Tank

P-302

Cool Water

Recirc Pump

Warm Frac

Hot Frac

26.7 C

CWS

E-315

Main

Cooler

CWS

CWR

CWR

130 C

120 C

32 C137 C to

150 C

Cool Frac

35 C15.6 C

26.7 C

Cool Frac

Treated

Flue

Gas

Condensate

LP Steam

Low

Pressure

Steam

T-181

Caustic Tank P-181

Caustic Pump

Condensate

Wastewater

Condensate

To Wastewater

TreatmentP-511

Condensate Pump

Note 4

C-501

C-502

C-503

C-504

C-505

V-501

V-502

V-503

V-504

V-505

E-501

E-502

E-503

E-504

E-505

Dehy

Unit

Warm Frac

P-303

Hot Water

Recirc Pump

T-302

Cool

Water

Tank

CWS

Pre-cooler

15.6 C

32 C

E-500

Fiber Modules in

Cooling Mode

Fiber Modules in

Adsorbing Mode

Fiber Modules in

Self Sweeping Mode

Fiber Modules in

N2 Sweep ModeSweep Gas

Draft Fan

CWS

CWR

Flue Gas

Conditioning

(Cooling, Trim

SO2 Removal)

Flue Gas

From FGD

Cool

Tempered

Water

Steam

Condensate

Warm

Tempered

Water

Inlet Gas

Blower

To CO2

Compression &

Dehydration

To

Stack

Cycle Model Validation

and Scale Up to Module

Level (GT and Trimeric)

Integration with Plant

Design and Escalation for

TEA (Trimeric)

Water Looping for Heat Integration

DOE Metric Calculation. Feedback to

single fiber design and optimization

Process Flow Diagram - Cycle Steps:

Fiber Modules in

Cooling Mode

Fiber Modules in

Adsorbing Mode

Fiber Modules in

Self Sweeping Mode

Fiber Modules in

N2 Sweep ModeSweep Gas

Draft Fan

CWS

CWR

Flue Gas

Conditioning

(Cooling, Trim

SO2 Removal)

Flue Gas

From FGD

Cool

Tempered

Water

Steam

Condensate

Warm

Tempered

Water

Inlet Gas

Blower

To CO2

Compression &

Dehydration

To

Stack

CO2 Balance:

CO2 purity of 95% and recovery of 90% per pass

Year 2

Year 3

7%

20%

73%

The current technoeconomic evaluation employs a similar methodology to the first and second year:

• Outputs from cyclic steady state fiber model (e.g., tempered water flow rates and temperatures) were abstracted and used as inputs to steady-state process model

• Heat and material balances were used to size and select equipment

• Capital costs, operating costs, and technoeconomic metrics were calculated according to DOE methodology

Equipment pricing was improved over year 1:

• Equipment cost curves were developed to accommodate more rapid evaluation of process options by overall modeling team.

• Aspen In-plant Cost Estimator replaced PDQ$ as the equipment cost estimating software.

Year 2, CO2 recovery target (93%) was met, but CO2 purity was not (82%).

Year 3, CO2 recovery (90%) and purity targets met, (95%).

Technoeconomic Evaluation Methodology:

DOE Design Basis:

• Specified in solicitation, similar but not identical to DOE baseline reports

• 550 MWe net, 90% CO2 capture• Supercritical steam cycle• Inlet flue gas conditions and composition• Outlet CO2 at 95% purity and 15272 kPa (2215 psia)• Cooling water supply, return, and approach temperatures• Steam delivery conditions:

– IP/LP crossover– 395 C (743 F) and 1156 kPa (168 psia)– Thermal energy penalty of 0.0911 kWh/lb

Energy and Escalation Results Year 3:

Description Units Value

Escalation Factor - 1.532

Energy

Sorption enthalpy MWth 183.2

Sensible heat MWth 1006

Total enthalpy per sorption or desorption step MWth 1190

Main heater duty MWth 550

Main cooler duty MWth -563

Intraprocess heat recovery %

Steam usage kg/h 819000

Derate

Direct Electrical Derate MWe 110.8

Steam Derate MWe 252.6

Steam Turbine Energy Recovery MWe -71.0

Total Derate for CO2 Capture MWe 292

Escalated Capital Costs:

Description Units Year 3 Comments

Total purchased equipment

costs (PEC) MM$ 221.6

1850 modules

Fibers MM$ 135.9 450,000 fibers/module

CO2 capture MM$ 57.6

CO2 compression MM$ 28.1

Process Plant Cost (PPC) MM$ 641.5 PPC = PEC + Direct Costs

Total Plant Cost (TPC)

MM$ 1078.5

TPC = PPC + Engineering +

Process Contingency + Project

Contingency (30%)

Total Plant Investment (TPI) MM$ 1142.6 TPI = TPC + Interest and Inflation

Total Capital Requirement

(TCR) MM$ 1175.3

TCR = TPI + Startup + Initial Fill +

Working Capital + Land + Others

Annual Capital Charge MM$/year 205.7

Technoeconomic Metrics Escalated Case:

Description Units Year 3 Q3

Levelized Costs of Electricity and Steam

Levelized cost of electricity mills/kWh 154

Levelized cost of steam $/1,000 lb 14.0

Cost of CO2 Capture

Total Annual Cost of CO2 Capture MM$/year 303

Impact of CO2 Capture on Plant Efficiency

Net Plant Efficiency without CO2 Capture (HHV) % 39.3

Net Plant Efficiency with CO2 Capture (HHV) % 25.6

Change in Net Plant Efficiency % -11.2

Metrics were calculated using simplified equations specified in the solicitation.

Summary & Future Work:

• Rapid Temperature Swing Adsorption (RTSA) enabled by a new contactor

combined with solid amine sorbents.

• Cycle allows quasi-isothermal adsorption with significant sensible heat

recovery due to nanoscopic shell-tube heat exchanger design.

• Refined Technoeconomic analysis suggests targets for improvement.

-- Current parasitic load, Gen 2 fibers (1.53 escalation factor)

• Refinement Approaches:

-- Gen 3 fibers = 1.43 escalation factor

-- Gen 3 fibers (VTSA, 0.33 bar desorption pressure)

Lower bound steam savings = 30% less heat used

-- Gen 3 fibers (VTSA, 0.33 bar desorption pressure)

Upper bound steam savings = 50% less heat used

-- Multi-bed adsorption

Acknowledgements:

DOE Award #: DE-FE0007804

Algenol Biofuels

GE

Southern Company

Funding

Dr. Ron Chance – Algenol Biofuels

Dr. Ying Labreche – hollow fiber spinning

Dr. Yanfang Fan – experimental system design and testing

Dr. Fateme Rezaei – sorbent synthesis and fiber modeling

Dr. Swernath Subramanian – fiber modeling

Ms. Jayashree Kalyanaraman – fiber modeling

Ms. Grace Chen – sorbent synthesis & characterization / fuel gas upgrading

Mr. Morgan French – Southern Company

Mr. Jerrad Thomas - Southern Company

People

Program officer Bruce Lani – NETL, DOE

Contact Christopher W. Jones

Georgia Institute of Technology

cjones@chbe.gatech.edu