Development and Bench-Scale Testing of a Novel Biphasic ... · Completion of 40 kWe bench unit design (Design heat duty ≤ ~2,100 GJ/tonne of CO 2 and stripping P ~4 bar) BP2 Identify

1

Development and Bench-Scale Testing of a Novel

Biphasic Solvent-Enabled Absorption Process for

Post-Combustion Carbon Capture (DE-FE0031600)

Presenter: Yongqi Lu

Illinois State Geological Survey

University of Illinois at Urbana-Champaign

2019 Carbon Capture, Utilization, Storage, and Oil &

Gas Technologies Integrated Review Meeting

Pittsburgh PA • August 26, 2019

2

Project Overview

Technology Background

Scope of Work/Technical Approaches

Progress and Current Status

Plan for Future R&D and Scale-Up

Objectives

❑ Advance the development of biphasic solvents and

absorption process from lab- to bench-scale

❑ Design, fabricate and test an integrated 40 kWe bench-

scale capture unit with simulated and real coal flue gases

❑ Demonstrate the technology progressing toward achieving

DOE’s Transformational Capture goals

3

Participants and Major Roles:

❑ Illinois State Geological Survey: Solvent & process development; Oversight of equipment fabrication & assembly; Bench tests

❑ Illinois Sustainable Technology Center: Chemical analysis for tests; EH&S study

❑ Trimeric Corporation: Equipment specs and design; TEA study

Project Duration and Budget

Project duration: 36 mon (4/6/18–4/5/21)

❑ BP1: 9 mon (4/6/18-1/5/19)

❑ BP2: 12 mon (1/6/19-1/5/20)

❑ BP3: 15 mon (1/6/20-4/5/21)

Funding Profile:

❑ DOE funding of

$2,981,778

❑ Cost share (in-kind &

cash) of $776,896 (20.7%)

4

23.7%

20.0%

20.2%

$0

$200,000

$400,000

$600,000

$800,000

$1,000,000

$1,200,000

$1,400,000

$1,600,000

BP1(9-m)

BP2(12-m)

BP3(15-m)

DOE funds

Cost Share

5

Project Overview





Biphasic CO2 Absorption Process (BiCAP)

6

Impact on stripper:

❑ Reduced solvent mass to stripper

leads to low sensible heat use and

small equipment size

❑ Enriched CO2 loading leads to high

stripping pressure (i.e., low stripping

heat and CO2 compression work)

Impact on absorber:

❑ Applicable for high-viscosity solvents

via multi-stage LLPS to enhance rate

Flue gas

Cleaned gas

Absorber

(40-50 C)

CO2-rich

solvent

Cross-heat

exchanger Stripper

(120-150 C/

3-8 bar)

Regenerated

rich phase

Combined

CO2-lean solvent

Reboiler

Steam

Reflux

Condenser

CO2

compressor

LLPS (opt.)

Cooler

CO2-rich

phase

LLPS

CO2-lean

phase

(LLPS: liquid-liquid

phase separation)

Novel BiCAP Solvents

Water-lean aqueous/organic

amine blends:

❑ Tunable phase transition

behavior (e.g., vol.% and

loading partitions)

❑ In aqueous form suitable for

humid flue gas application

Lab screening tests of ~80

solvents based on multiple

criteria:

❑ 2 identified meeting all

criteria (BiCAP-1 and

BiCAP-2)

7

Lab experiments for biphasic solvent

screening conducted in previous project

CO2

capacity

Absorption

rate

Oxidative

& Thermal

Stabilities

Viscosity

Corrosion impact

Phase transition behavior

VLE

measurement

CO2 partition

analysis

Viscosity

measurement

WWC

measurement

2 wk O2

bubbling test;

4-8 wk thermal

incubation test

4 wk coupon

incubation

test

Features of BiCAP Solvents and Process

Lab-scale 10 kWe

absorption and stripping

column tests conducted in

previous project:

❑ Absorption rate:

50% > MEA under

respective operating

conditions

❑ Reboiler heat duty:

35-45% < MEA under

respective stripping

conditions

❑ Stripping pressure:

~6 bar (max. ~8.5 bar)

8

Two top-performing BiCAP

solvents developed in

previous project:

CO2

capacity

Absorption

rate

Oxidative

& Thermal

Stability

Viscosity

Corrosion impact

Phase transition behavior

2x MEA

(desorption cap.)

>98% CO2 in

<50%v solution

<45 cP

@ 40 °C

50% > MEA

Th. rate @ 150 °C

= MEA @ 120 °C;

Ox. rate 1/8th MEA

2-3x < MEA

9

Project Overview





Project Scope of Work

10

Solvent & Process Data from Lab-Scale Project

Design of Bench-Scale

Capture Unit (T5)

Fabrication of Bench-Scale

Capture Unit (T6)

Testing of Bench Unit with

(1) Simulated Flue Gas(T8);

(2) Actual Flue Gas (T9)

Solvent Management

Studies (Solvent

Reclamation etc.) (T7)

Solvent Volatility &

Emission Ctrl. Studies (T3)

Process Modeling &

Optimization (T4)

Techno-

Economic

Analysis (T10)

Technology

Gap Analysis

(T11)

EH&S Risk

Assessment

(T12)

Technology

Maturation

Plan (T2)

BP1 (9-mon)

4/5/18-1/5/19)

BP2 (12-mon)

(1/6/19-1/5/20)

BP3 (15-mon)

(1/6/20-4/5/21)

Main Success Criteria and Milestones

11

Basis for Decision/Success Criteria

BP1

Solvent vapor and aerosol emissions assessed

Power plant Host Site Agreement issued

Completion of 40 kWe bench unit design

(Design heat duty ≤ ~2,100 GJ/tonne of CO2 and stripping P ~4 bar)

BP2Identify suitable options for reclamation of biphasic solvents

Fabrication of 40 kWe bench-scale unit

BP3

Bench unit install, commissioning & testing including 6-month

parametric testing with a simulated flue gas and 2-week continuous

testing with a slipstream of power plant flue gas;

Demonstrate continuous operation & total energy use of 0.22 kWh//kg

BP1: All 7 milestones reached on schedule and all 3 criteria fulfilled;

BP2: 2 milestones in progress as scheduled

12

Project Overview





(1) Solvent Volitivity, Emissions and Mitigation (T3)

❑ Aerosols generated (106-

107 #/cm3) to simulate flue

gas

❑ Both vapor & aerosols

monitored:

➢ FTIR for measuring

vapor

➢ Scanning Mobility

Particle Sizer (SMPS)

and Optical Particle

Sizer (OPS) combined

for measuring 10-nm to

10-µm aerosols

➢ Membrane filters for

collecting aerosols for

GC-MS analysis

13

Aerosol

generator

T

T

P

pH

Ven

t

Wash water

reservoir

Ro

tam

ete

r

Feed

gas in

Ro

tam

ete

r

T P

Ar

gas f

or

aero

so

l sam

ple

dilu

tio

n

Aerosol

sizers

Member

filtration

Vapor

FTIR

Aerosol and vapor

sampling & analysis Vacuum pump

Aerosol and vapor

sampling & analysis

Aerosol and vapor

sampling & analysis

MFM

MFM

Absorber Water

Wash

Column

Solvent

tank

Isokinetic

sampling

Aerosol generator

(107 #/cm3)

SMPS (10-420nm)

OPS (300nm-10m)

FTIR

Aerosol

membrane

module

Absorption column

(4’’ID x 9’H: 6’ structured packing)

Water wash column

(4’’ID x 9’H: 3’ packing)

Gas-Phase Amine Emissions during Absorption & Water Wash

❑ MEA mist/droplets visually present at sampling port of absorber exit

❑ BiCAP solvents 2-4 times less emissions from absorber than MEA

❑ ~50-95% of BiCAP amine emissions were vapor in these tests

❑ Water wash removed ~20-70% of total amine emissions14

Emissions from absorber Emissions after WW column(Total emissions: amine vapor + vaporized aerosols (w/o filtration) measured by FTIR;

Vapor emissions: amine vapor only (with filtration) by FTIR)

0

50

100

150

200

0 0.1 0.2 0.3 0.4

Gas p

hase c

on

cen

trati

on

(p

pm

v)

CO2 lean loading (mol/mol amines)

MEA total emissions

MEA vapor emissions

BiCAP1 total emissions

BiCAP1 vapor emissions



WW emissions (L/G=1.0 w/w)

0

50

100

150

200

0 0.1 0.2 0.3 0.4

Gas p

hase c

on

cen

trati

on

(p

pm

v)


MEA total emissions

MEA vapor emissions





Absorber emissions (L/G=3.3 w/w)

Aerosol Emissions during Absorption & Water Wash

❑ Absorber:

➢ Aerosol size grew (agglomeration, condensation, reaction-diffusion, etc.)

➢ Aerosol number concentration reduced significantly (by 60-90%)

❑ WW column

➢ Aerosol size tended to decrease

➢ Particles might be generated/removed depending conditions 15

-

50

100

150

200

250

300

0 0.1 0.2 0.3 0.4

Geo

metr

ic m

ean

siz

e (

nm

)


MEA absorber outletMEA WW outletBiCAP1 absorber outletBiCAP1 WW outletBiCAP1 absorber outletBiCAP2 WW outlet

Absorber inlet: mean dg=52 nm;

number = 8.3 x 106 #/cm3

(2) Biphasic Solvent Degradation and Reclamation

Methods under lab testing to replace / reduce thermal reclamation needs:

❑ Ion exchange adsorption

❑ Activated carbon adsorption

❑ Membrane nanofiltration

❑ Thermal reclamation (baseline)

Model Compound Abbreviation MWAnalytical

technique

Thermal

degradation

products

N,N’-di(2-hydroxyethyl)urea MEA Urea 60GC-MS,

LC-MS

1-(2-hydroxyethyl)-2-

imidazolidinoneHEIA 130

GC-MS,

LC-MS

N-(2-

hydroxyethyl)ethylenediamineHEEDA 179

GC-MS,

LC-MS

Oxidative

degradation

products

Acetic acid AcOH 60 LC-MS

Oxalic acid OA 90 LC-MS

Formic acid FA 46 LC-MS

Selected degradation products as model compounds used in experiments

Adsorption of Thermal Degradation Products with Carbons

❑ Two commercial carbons (microporous and micro/mesoporous) tested

❑ Adsorption of selected thermal HSS products not significant

❑ Work in progress to modify carbon surface polarity and functionalities to

improve HSS adsorption

17

Rotating tumbler used for adsorption

isotherm measurements at 23±1 C

0%

5%

10%

15%

20%

0 1 2 3 4 5

Ad

so

rpti

on

rem

ov

al, %

Carbon dose, g/L

AC1-micro-porous

AC2-micro/meso-porous

HEEDA adsorption

Removal of Oxidative Degradation Products with Ion

Exchange Resins

❑ Isotherms of two resins measured:

➢ Strong base resin showed high

affinity to oxalic acid

➢ Weak acid resin showed some

affinity to formic acid

❑ Ion exchange column

breakthrough tests in progress

18

0%

20%

40%

60%

80%

100%

0 5 10 15 20

Acid

rem

ov

al, %

Resin dose, g/L

Oxalic

Formic

Acetic

Strong base resin;Inital acid: 0.5g/L

0%

20%

40%

60%

80%

100%

0 2 4 6 8 10

Acid

rem

ov

al, %

Resin dose, g/L

Oxalic

Formic

Weak acid resin;Inital acid: 0.5g/L

(3) Design & Fabrication of Bench-Scale BiCAP

Unit: Process Configuration Optimization (T4)

19Simple Stripper

LP steam

Flue gas from

Power plant

Cleaned

flue gas

Absorption

column

High-

pressure

stripper

Reboiler

Cooler

Cross heat

exchanger

Lean

solvent

CO2-rich

phase

CO2-lean

phase

Condensate

to power plant

cooling tower

Inter-

stage

cooler

Water

separator

Rich

solvent

tank

Solvent

makeup

Solvent

tankCondenser

CO2

compressor

LLPS

(opt.)

LLPS

(LLPS: Liquid-Liquid Phase Separation;

LP steam: low pressure steam)

Water

wash

Blow

down

Water

makeup

Cooler

Rich solvent

Contn’d

20Flash + Stripper

LP steam

Flue gas from

Power plant

Cleaned

flue gas

Absorption

column

High-

pressure

stripper

Reboiler

Cooler

Cross heat

exchanger

Lean

solvent

CO2-rich

phase

CO2-lean

phase

Condensate

to power plant

cooling tower

Inter-

stage

cooler

Water

separator

Rich

solvent

tank

Solvent

makeup

Solvent

tankCondenser

LP

steam

Flash

CO2

compressor

Cndnst. to

cooling

towerLLPS

(opt.)

LLPS



Water

wash

Blow

down

Water

makeup

Cooler

Condenser

Rich

solvent

Contn’d

21Cold Bypass

LP steam

Flue gas from

Power plant

Cleaned

flue gas

Absorption

column

High-

pressure

stripper

Reboiler

Cooler

Cross heat

exchanger

Lean

solvent

CO2-rich

phase

CO2-lean

phase

Condensate

to power plant

cooling tower

Inter-

stage

cooler

Heated rich

solvent

Water

separator

Rich

solvent

tank

Solvent

makeup

Solvent

tankCondenser

CO2

compressor

LLPS

(opt.)

LLPS



Water

wash

Blow

down

Water

makeup

Cooler

Cold bypass

rich solvent

Contn’d

22Cold Bypass and Flash + Stripper

LP steam

Flue gas from

Power plant

Cleaned

flue gas

Absorption

column

High-

pressure

stripper

Reboiler

Cooler

Cross heat

exchanger

Lean

solvent

CO2-rich

phase

CO2-lean

phase

Condensate

to power plant

cooling tower

Inter-

stage

cooler

Heated rich

solvent

Water

separator

Rich

solvent

tank

Solvent

makeup

Solvent

tankCondenser

LP

steam

Flash

CO2

compressor

Cndnst. to

cooling

tower

LLPS

(opt.)

LLPS



Water

wash

Blow

down

Water

makeup

Cooler

Condenser

Cold bypass

rich solvent

Energy-Efficient BiCAP Configuration Identified

❑ Cold Bypass: high energy efficiency and low equipment complexity23

Simple

Stripper

Flash+

Stripper

Cold

Bypass

Cold Bypass+

Flash/Stripper

Flash pressure, bar n/a 9.7 n/a 9.7

Flash temperature, C n/a 140 n/a 144.5

Stripper pressure, bar 5.1 5.0 5.1 5.1

Reboiler temperature, C 150 150 ~150 ~150

CO2 release from flash, % 0% 34.50% 0% 28.75%

CO2 release from stripper, % 100% 65.50% 100% 71.25%

IP/LP steam use

Overall heat duty, kJ/kg CO2 2,613 2,649 2,132 2,441

Parasitic power loss, kWh/kg CO2 0.186 0.188 0.152 0.174

Compression work, kWh/kg CO2 0.058 0.053 0.058 0.054

Total energy use, kWh/kg CO2 0.244 0.242 0.209 0.227

* BiCAP-1 solvent (vs. best-performing BiCAP-2) used for modeling

Design Optimization of 40 KWe Bench-Scale Unit

❑ Rigorous rate-based Aspen Plus model developed

❑ BiCAP-1 solvent (vs. best-performing BiCAP-2) used for design modeling

24

(Stripper (4” ID) with 15’ height of Mellapak 250Y packing at fixed rich loading

of 0.73 mol/mol amines in heavy phase and 150°C reboiler)

Contn’d

25

CO2 removal from 40 kWe flue gas in

absorber at fixed L/G of 5.5 (w/w)

Reboiler duty as a function of stripper

packed height (90% CO2 removal)

❑ 27’ packing achieves 90%

capture

❑ Higher L/G leads to shorter

packing requirement, but may

increase stripper heat duty

❑ Stripper packing height

directly affects heat duty: a

taller column achieving better

energy performance

Schematic of 40 kWe Bench-Scale Capture Unit

26

Water Wash will be separate

column from absorber; 10-ft

packing; total height ~16’-0”

Flue gas cooling/

polishing treatment

2 absorption columns:

Each with 8-in ID × 15-ft packing

and total height ~22’-2”

1 stripping column:

4-in ID × 15-ft packing

and total height ~26’-6”

To stack

Gas return to

stack (or vent)

Direct

contact

cooler/

SO2

polisher

NaOH solution

makeup

Abbott coal

flue gas

~71 ACFM

High-

pressure

stripper

(~87.0 psia/

302 F)

Condenser

CoolerCooler

LP steam

Condensate

CO2 bottle

gas

Absorber

(14.5 psia/104 F)

Phase

separator

Water

wash

Blow

down

Solvent

makeup

Cold feed

Heated

feed

Heat

exchanger

Cooler

Water

makeup

Blow

down

Air

Blower

Reboiler

Preliminary Skid Footprint

27

❑ Skid and control panel design by ITG-Henneman

❑ Skid fab/assembly by UIUC Facilities & Services

Location of Bench-Scale Unit at Abbott power plant

Site used for (1) parametric testing with simulated

flue gas for 6 months and (2) continuous testing

with actual flue gas for 2 weeks

28

ESP

STACK

BENCHCARBON CAPTURE

ABBOTT POWER PLANT

JBR FGD BUILDING

29

Project Overview





BP2 and BP3 Work Plan

30

4/5/2021

BP2

(12-m)

BP3

(15-m)

1/6/2019

1/6/2020

T6. Fabrication &

Assembly of Bench-

Scale Unit

T7. Solvent Reclamation

Studies

T8. Parametric Testing

with Simulated Flue Gas

at Abbott Plant

(6 months; 2 solvents)T9. Slipstream Testing

with Abbott Flue Gas

(2-weeks; 1 solvent)

T10. TEAT11. Tech Gap

Analysis

T12. EH&S Risk

Assessment

31

Progression of BiCAP Technology Development

10 kWe Tests,

Laboratory

Solvent study,

Laboratory

0.2-1 MWe,

Power Plant

/Test Center

10 MWe,

Power Plant

33Phase separators

Overview of

experimental

setup

Solvent

thermal

regenerator

Structured

packing

Phase

separator

40 kWe Tests,

Laboratory & Power

Plant Slipstream

Proof-of-Concept

Funding: UI (Part of

Dissertation Research,

2013-2015)

Separate

Absorber /

Stripper

Funding: DOE /

UI (2015-2018)

Bench Scale

Close-Loop Unit

Funding: DOE /

UI (2018-2021)

Small Pilot

Funding: DOE /

UI / Corporate

Partners/ State

Large Pilot

Funding: DOE /

Corporate Partners

/State / UI

Currently

Acknowledgements

32

❑ Funding Support by DOE/NETL

❑ DOE/NETL Project Manager: Andrew Jones

❑ Aspen Tech for providing free aspenONE license

Project Contributors:

Illinois State Geological Survey: Hafiz Salih; Paul Nielsen; Hong Lu; Qing Ye; Justin Mock; David Ruhter; Abiodun Fatai Oki

Illinois Sustainable Technology Center: Kevin O’Brien; Wei Zheng; BK Sharma; Vinod Patel; Stephanie Brownstein

Trimeric Corporation: Ray McKaskle; Katherine Dombrowski; Kevin Fisher; Andrew Sexton; Darshan Sachde

University of Illinois Facilities & Services: Mike Larson (Abbott); Mike Brewer (Abbott); Rick Rundus; Mohamed Attalla; Josh Rubin

ITG-Henneman: Imad Rahman; David Kryszczynski; Scott Prause; Beth Mader

Contact Info: Yongqi Lu

Illinois State Geological Survey

Tel: 217-244-4985; Email: [email protected]

Documents

Development and Bench-Scale Testing of a Novel Biphasic ... · Completion of 40 kWe bench unit design (Design heat duty ≤ ~2,100 GJ/tonne of CO 2 and stripping P ~4 bar) BP2 Identify