Coal-fueled Pressurized Chemical Looping Combustion with a

Coal-fueled Pressurized Chemical Looping

Combustion with a Spouting Fluidized Bed

Award Number

DE-FE0025098

University of Kentucky Research Foundation on Behalf of

Center for Applied Energy Research

University of Kentucky

2540 Research Park Drive

Lexington, KY 40511-8410

DOE Kickoff Meeting October 22, 2015

Outline

• Motivation and Development Pathway

• Project Objective

• Technical Approach

• Project Management Plan and Risk Management

• Schedule and Budget

• Progress


Chemical Looping Combustion (CLC)

Solid OC circulates between two reactors

Oxygen carrier (OC): oxygen, heat and

fuel energy

OC pick up O2 in the Air Reactor

(exothermic)

OC combust fuels in the Fuel

Reactor(endothermic)

Total heat release equal to normal fuel

combustion

OC materials: Fe, Ni, Mn, Cu, Ca, natural

materials, solid waste

Schematic Diagram of CLC Concept


Today’s CLC Facilities

Cyclone

C-1200

Test Section

C-1250

Loop Seal

R-1300

Upper

Riser

R-1150

Lower

Riser

R-1100

Air

Reactor

R-1000

Air Pre-heater and Tee

H-1800 & H-1850Air Pre-heater and Tee

H-1800 & H-1850

L-Valve

Housing

R-1450

Fuel

Reactor

R-1400

50 kWth at US-NETL

3 MWth at ALSTOM

140 kW (Vienna University

of Technology)

10 kWth at C.S.I.C.10 kWth at Chalmers

10 kWth at Chalmers

Gaseous Fuel

Solid Fuel

100 kWth at Chalmers25 kWth at OSU

Juan Adanez, Progress in Energy and Combustion Science 38 (2012) 215-282

CLC Development at UK-CAER

Cost-effective oxygen carrier

development:

- Fe-based: synthesized, ilmenite & solid

waste

System design & technical-economic

evaluation of PCL for power

generation/syngas production

Demonstration of PCLC/CLG (1-50

kWth fixed bed/fluidized bed/spouted

bed)

Fundamental: kinetics of coal char

gasification/OC reaction, pollutant

formation, interaction between OC and

coal ash

Bench-scale fluidized bed

50 KWth Spouted bed reactor

TGA-MS

Plant Efficiency and COE

System Design


Funded Projects on CLC/G at UK-CAER

Cost-effective and High Performance OC Development

• Supported by Carbon Management Research Group consortium at CAER

Novel Carbon Capture Technology Development for Power Generation

Using Wyoming Coal

• Investigation into the use of Wyoming coal as the feed for Solid-Fueled

CLC, State of Wyoming Clean Coal Technologies Research Program

Solid-fueled PCLC with Flue-gas Turbine Combined Cycle for Improved

Plant Efficiency and CO2 Capture

• Supported by DOE- Phase I , system design and economic analysis

Coal-fueled PCLC Combined Cycle for Power Generation and CO2

Capture

• Supported by Kentucky Energy and Environment Cabinet, FB

Application of Chemical Looping with Spouting Fluidized Bed for

Hydrogen-Rich Syngas Production from Catalytic Coal Gasification

• Supported by DOE, CL combined with catalytic gasification


Challenges for CF-CLC

• Oxygen Carrier

- Oxygen & heat carrier (Reactivity, oxygen transport capacity)

- Production cost

- Stability, agglomeration, sintering, attrition

• Slow Gasification

• Heat Balance

- Spontaneous process without the requirement

of any external heat sources

• Fuel Reactor

- Mixing between OC and fuel particles

- High solid fuel conversion

- Controlling OC reduction

- Heat transfer

H2+CO

Hot/Oxidized

OCs

H2O

H2O

Heat

CO2+H2O+H2+CO

Char

Heat

CO2+H2O+minor (H2+CO)

Ash

Heat

Reduced OCs


Coal-fueled Pressurized Chemical Looping

Combustion with a Spouting Fluidized Bed

DE-FE0025098


Project Objectives

Demonstrate an integrated coal-fueled PCLC facility at lab-scale:

design, fabrication, commissioning, hot testing, and performance

evaluation

Techno-economic assessment of the UK-CAER PCLC integrated

power generation at commercial scale

Technical gaps need to be narrow or addressed:

- Cost-effective materials for OCs ( Red mud)

- Overall fast reaction rates in the Fuel Reactor

- Simple & effective ash separation from binary mixtures of OCs & ash

- Suppression of OC agglomeration from the initial coal devolatilization step

- Pollutant mitigation to avoid emission of sulfur/NOx/alkaline metal into the hot

spent air stream


UK-CAER PCLC Facility

Demonstrate coal-fueled PCLC tech. at continuous model & data collection

Narrow the major near-term technical gaps impeding SF-PCLC & its scale up

TEA of UK-CAER PCLC at commercial scale


Fu

el R

eact

or

Air

Rea

ctor

Air Compressor

Loop

-sea

l

Ash cooler

Hot CO2/Steam

Hot Spend Air

Cyclone-1

Cycl

one-

2

Hopper-2

Char/coal

Ash

CO2

To Gas Analyzer-I

Vent to Air

To C

O2 R

ecycl

ing

/Com

pre

ssor

To G

as A

nal

yze

r-II

Cooler-I

Condenser

Vent to Flare

Screw Feeder

R P F

Pre-heater-1 Water Tank

Air

Tank

SG

Hopper-2

Pre-heater-2

Rai

ser

Hot Fluidization

Gas/N2

Hot

Fluidization

Gas/N2

H-Filter

L-Filter

Hea

ting E

lem

ents

To Fuel injectionFuel injection

1. AR & FR;

2. Fuel/OC feeding;

3. Gas supply: Steam; fluidizing gas; Air

4. Furnace

4. Gas clean- up;

5. Gas/solid sampling and measurement

6. P/T/Q measurement;

7. Data acquisition system;

8. Failsafe System

9. Supporting

Strategy to Achieve the Objectives

Cost-effective oxygen carrier from RM

Use of a spouted bed to avoid OC-coal agglomeration and to

improve fuel conversion and CO2 purity

Pulverized fuel injection

Improvement of solid fuel gasification under elevated pressure

CO2 recycling to save energy consumption

Elimination of external ash separation process


Task & Approach: PCLC facility & testing


OC

Performance

Experiments in

Fluidized Bed Reactor

(PCLC, kinetics)

Existing Spouted

Bed (cool model &

fluid-dynamics)

CFD/Aspen Simulation

(Heat-mass

balance/configuration)

Continuous PCLC facility

Design/ commissioning

Performance

Verification of

Major Components

Parametric

Testing

Long Term

Testing

Campaign

Fate of Sulfur &

Fuel Nitrogen

Transfer

Testing

Performance Evaluation

Task & Approach- Aspen Model


• PCLC = CC + PFBC + CLC (550 MWe PCLC Power Plant)– CC: 3-P combined cycle for high efficiency power generation

– PFBC: coal utilization

– CLC: low cost CO2 removal w/o ASU

• H&MB model on Aspen Plus platform to provide information– For plant performance evaluation, and for configuration, integration, and design

consideration

• Detailed reactor model– Reactor design and size with obtained kinetics

Task & Approach: T-E Analysis


Based on system simulation, key component sizing, and cost estimate of major

equipment:

1. A factored estimate of capital costs for power production and

CO2 capture

2. An estimate of operating costs (cooling water, steam, fuel,

oxygen carrier etc.)

3. An estimate of the energy performance and parasitic energy

load of the technology

4. An estimate of the cost of CO2 capture

Project Management Plan & Schedule


Task Name Start Finish Task Cost

1.0 Project Management & Planning 9/1/2015 8/31/2017 $192,437

2.0 Detailed Engineering Design 9/1/2015 2/29/2016 $77,290

3.0 Large Quantity OC Production 11/16/2015 3/21/2016 $59,060

4.0 Fabrication, Installation, & Commissioning of PCLC facilities 3/1/2016 8/31/2016 $195,237

4.1 Modification, fabrication, and installation 3/1/2016 6/30/2016

4.2 Commissioning 7/1/2016 8/31/2016

5.0 Performance Verification of Major Components 9/1/2016 12/2/2016 $69,876

6.0 Parametric Testing 12/2/2016 4/3/2017 $61,907

7.0 Long Term Testing Campaign 4/4/2017 6/5/2017 $46,901

8.0 Fate of Sulfur & Fuel Nitrogen Transfer 12/1/2016 5/31/2017 $46,454

9.0 Process Simulation of 550 MWe PCLC Power Plant 12/1/2016 5/31/2017 $43,843

10.0 Technoeconomic Assessment 6/1/2017 8/31/2017 $82,775

Budget

Period 1

Budget

Period 2

Deliverables

Task 1 Project Management Plan 10/30/2015

Task 2 The engineering design (including P&ID, general

layout, blueprint for Reducer, material and instrument

selection, et.al)

02/29/2016

Task 3 Installation & commissioning 08/31/2016

Task 5 & 6 Effectiveness of major components & optimized

operation conditions04/3/2017

Task 7 – 9 Database of pollutants & stream table from simulation 05/31/2017

Task 10 TEA 08/31/2017


Team Structure

DOE NETL

Center for Applied Energy Research, UKy Trimeric Corporation

Engineering Design

OC Production

Reactor

Fabrication/Installation/

Commissioning

Techno-Eco

Analysis

Process Simulation of

550 MWe PCLC

Budgeting/ Coordinating /Reporting

Test


Risk Management

Description of Risk Probability (Low, Moderate, High)

Impact (Low, Moderate, High)

Risk Management (Mitigation and Response Strategies)

Technical Risks: Performance of OC Low High Addition of supports/additives

Change preparation methods

Catalyst-OC contamination Moderate Moderate Desulfurization sorbent Agglomeration in draft tube Moderate Moderate Re-configuration

Gas leakage between reactors Moderate Moderate Re-configuration of loop-seal Solid circulation & flux estimation

Moderate High Developing model for accurate prediction

Resource Risks: Air permit Low High EH&S Team early involvement

Project cost overrun Low High UKRF Project team assistance Management Risks:

Contract agreement delay Low High Dedicated UKRF staff


Available Instruments & Equipment

TGA/DSC/DTA/MS with WV

FurnaceHitachi S-4800 Philips X’pert


Available Facilities

Bench Scale Fluidized Bed Facility Spouted Bed Reactor


Why Red Mud – The Properties

Physical Characteristics

• Fe2O3:30%-60%

• Al2O3:10%-20%

• SiO2: 3%-50%

• TiO2: 2%-25%

• Na2O: 2%-10%

• CaO: 2%-8%

Chemical Composition(Dry)

Active composition

Support

Bonding

Particle size: 80% particles <10μm

Concentration: 50-65%

pH: 12-13.5(need neutralization)Direct Granulation

(spray dry method)

Cost-effective OC

Calcination

No mechanical grinding

& slurry preparation needed

No additive needed


Red Mud OCs

• SEM images

Chemical composition of raw red mud and OC samples

Composite Red mud OCs (after

calcination)

Raw 1100 oC/6h 1150

oC/6h

Fe2O3 51.14 50.96 51.56

SiO2 9.85 10.51 9.98

Al2O3 17.92 18.54 18.18

TiO2 6.44 6.39 6.47

CaO 8.14 7.96 7.77

MgO 0.49 0.52 0.51

Na2O 1.81 1.91 1.85

K2O 0.2 0.19 0.18

Balance 4.01 3.02 3.5

(a) Fresh particle (b) Fresh (c) used after 20 redox cycle

20 25 30 35 40 45 50 55 60 65 70

Used after 20 cycles

1150 oC/6h

1100 oC/6h

Raw red mud

8 7

11

91

18 7 19 1 11

52

1

1 111

6 133 54 41

11

8

Inte

nsity (

a.u

.)2

1-Fe2O3; 2-AlO(OH); 3-TiO2;

4-SiO2; 5-CaCO3; 6-NaOH;

7-CaTiO3; 8-NaAlSiO4; 9-CaAl2Si2O8

XRD patterns


Chemical Stability

Composite Red mud OCs (after calcination)

Original 1150 ºC/6h 500h 1000h 1500h 2000h 2500h 3000h

Fe2O3 51.14 51.56 50.94 51.01 51.43 50.28 51.27 50.83 SiO2 9.85 9.98 10.44 10.03 10.23 10.33 9.81 10.32 Al2O3 17.92 18.18 18.1 18.24 17.95 18.27 18.45 18.35 T iO2 6.44 6.47 6.39 6.34 6.39 6.35 6.37 6.39 CaO 8.14 7.77 7.79 8.38 7.83 8.35 8.44 8.37 MgO 0.49 0.51 0.44 0.43 0.65 0.66 0.68 0.68 Na2O 1.81 1.85 1.67 1.58 1.88 1.79 1.60 1.68 K2O 0.2 0.18 0.18 0.16 0.17 0.15 0.12 0.13

Balance 4.01 3.5 4.05 3.83 3.47 3.82 3.26 3.25

FG-RM-1150/6h(125-300) Baking under 1100 for 500 h Baking under 1100 for 1000 h

Baking under 1100 for 1500 h Baking under 1100 for 2000 h Baking under 1100 for 2500 h

Experiments in Fluidized Bed Reactor

Oxygen carriers:

Ilmenite

S Red mud OC (FG1150 C/6h)

A Red mud OC (FG1150 C/6h)

Particle size: 125-350 um

Fuels:

EKy coal char (pretreated at 700 C)

WKy coal char (pretreated at 700 C)

PBR coal char (pretreated at 800 C)

Particle size: 180-350 um

Operation condition:

Gasification agent: 50% steam balanced

by N2

OC/Fuel ratio: 150: 1

F F

AirN2

MFC MFC

Pre-pump

Pre

ssu

re T

ran

smit

ter

Fil

ter

Co

ole

rC

on

den

sate

Co

llec

tor

Gas

An

aly

zer

N2

Cycl

one

Sam

ple

Po

rt

Deionized Water Thermocouple-1

Th

erm

oco

up

le-2

Fu

el B

in

Th

erm

oco

up

le-3

Moisture

Trap

Lock

Hooper

Fu

rnac

eD

istr

ibu

tor

Flo

w M

eter

Steam Generator


OC Reduction with Simulated Syngas

Red mud OC

Ilmenite OC

0 200 400 600 800 10000

2

4

6

8

10

Test Condition:

Temperature: 950 oC

CO Flow Rate: 1.0 L/min

Mass L

oss o

f O

xygen F

rom

OC

(g/1

00g F

e2O

3)

Time/s

SRM OC reduced by 20% CO+50% Steam+Balance N2

Fe3O4

0 200 400 600 800 1000 1200 14000

2

4

6

8

10

Test Condition:

Temperature: 950 oC

CO Flow Rate: 1.0 L/min

Mass L

oss o

f O

xygen F

rom

OC

(g/1

00g F

e2O

3)

Time/s

Ilmenite reduced by 20% CO+50% Steam+Balance N2

Fe3O4

0.00 0.01 0.02 0.03 0.04 0.050.75

0.80

0.85

0.90

0.95

1.00

Fe2TiO5

Com

bustion E

ffic

iency

LOxygen

/ moxygen

Ilmenite OC

S Red mud OC

Fe2O3 Fe3O4

FeTiO3

Combustion efficiency

Fixed bed reactor:

(1) Bed material: 600 g ilmenite OC

(2) Fuel: 1.5 L/min CO +1.1 g/min water

+1.5 L/min N2

(3) Temperature: 950 oC


The Effectiveness of Red Mud with

Solid Fuel-2

0.0 0.2 0.4 0.6 0.8 1.00.000

0.001

0.002

0.003

0.004

0.005

0.006

Conditions :

(1) bed material: SRM OC (300g);

(2) Solid fuel: 2g EKY(700)

(3)Temperature: 950 oC

(4) Fluidizing agent: 50 vol% Water Vapor

1 cycle

5 cycles

10 cycles

Insta

nta

neous r

ate

of

convers

ion (

g/g

/s)

Degree of Carbon conversion(Xc)0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.5

0.6

0.7

0.8

0.9

1.0

Conditions :

(1) bed material: SRM OC (300g);

(2) Solid fuel: 2g EKY(700)

(3)Temperature: 950 oC

(4) Fluidizing agent: 50 vol% Water Vapor

1 cycles

5 cycles

10 cycles

Co

nve

rsio

n

Conversion of OC from Fe2O3 to Fe3O4

High Stability in Fuel Conversion


Combustion efficiency of PCLC process

• Combustion efficiencies are independent of operation pressure

and the type of fuels

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.80.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Test conditions:

1. Temperature: 950 oC

2. Steam concentration: 50vol%

3. Fuel: PRB 800 1.0 g

4. OC: ilmenite 150 g

Ga

s C

on

ve

rsio

n


1 bar

2 bar

4 bar

6 bar

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.80.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Test conditions:

1. Temperature: 950 oC

2. Steam concentration: 50vol%

3. Fuel: PRB800 1.0 g

4. OC: ARM 150 g

Ga

s C

on

ve

rsio

n


1 bar

2 bar

4 bar

6 bar

A Red mud OCIlmenite OC


Hydrodynamics in Spouted Bed

0

50

100

150

200

250

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

Inte

rnal

Cir

cula

tion R

ate

(kg/

h)

Fluidizing Gas Flow Rate (m3/h)

Bed Height=20 inch

Bed Height=15 inch

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16

16

18

20

22

24

26

28

2.5" tube height 300

unstable area

stable area

Sp

ou

tin

g g

as v

elo

city (

m/s

)

Fluidizing gas velocity (m/s)

H=350 mm

H=400 mm

H=500 mm

Question/clarification

Path forward

Task modification

Expected deliverables

Discussion


Documents

Coal-fueled Pressurized Chemical Looping Combustion with a