calcium looping - sintef.no · calcium looping – pilot plant (200 kw th) operation conditions...

Technology for a better society

1

Carlos Abanades

[email protected]

CO2 Capture Group

Spanish Research Council (INCAR-CSIC)

Calcium Looping

mailto:[email protected]

mailto:[email protected]


2

Outline

Why post-combustion CO2 capture by CaL ?

Current status of postcomb CaL

CaL for cement plants. WP12 CEMCAP


3

Calc

iner

T>

900ºC

CO2

Carb

on

ato

r

650º-

700ºC

CaO

CaCO3

Flue gas

with CO2

The concept of CaO looping

Heat OUT Heat IN

Flue gas

without CO2

Shimizu et al, Trans IChemE, Vol 77, Part A, January 1999 Hirama T. et al, Patent US005665319A, Feb 1996


4 CaL post-combustion process

Conventional power plant

Calcium looping system

Figure adapted from Dieter et

al (Fuel, 127, 23-37, 2014)

New “oxy-fired CFBC” power plant

Low energy penalty (6-8 net points) and low cost per ton CO2 captured Low cost sorbent precursor Purge of CaO: synergies with cement industry and others (i.e. desulfurization ) Pre-treatment of flue gas no needed (SO2 co-capture) Suitable for retrofitting to existing power plants

Benefits of Ca-looping


5

0,001

0,010

0,100

1,000

10,000

100,000

600 700 800 900 1000 1100

T (º C)

P c

o2

, eq

, atm

The equilibrium of CO2 on CaO


6

Cycle 1

Cycle 2

Cycle 3

Cycle 4

Cycle 10

Cycle 20

CaO

co

nve

rsio

n

Time (s)

Cycle 1

Cycle 2

Cycle 3

Cycle 4

Cycle 10

Cycle 20

CaO

co

nve

rsio

n

Time (s)

Carbonation reaction rates of CO2 with CaO

Reactivity fast enough rapid conversion in

compact gas-solid reactors

Evolution of CaO conversion with time

Value of “useful”

conversion

Grasa et al. AIChE Journal, 2009, 55, 1246-1255.


7 Evolution of sorbent CO2 carrying capacity during cycling

Two reasons for the decay in CO2 carrying capacity:

• Sintering leads to larger pores on calcination

• Thin CaCO3 product layer (~ 50 nm) builds on internal surface of large pores

Barker R. J Appl Chem Biotechnol. 1973, 23, 733–742; D. Alvarez, et al IECR. 2005, 44, 5608-5615

Curran et al, Adv. Chem. Ser., 1967, 69, 141.


8

Chen et al. Energy & Fuels, 2009, 23, 1437-1444.

Residual activity around 0.07-0.10 of CaO molar conversion to CaCO3

Evolution of sorbent CO2 carrying capacity during cycling


9

Carbonator 0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0 10 20 30 40 50

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

High “looping ratios”= (mol CaO/s)/(mol CO2/s) for power plants and CFB reactors

Low sorbent activities MINIMUM LIMESTONE CONSUMPTION


10

Calciner

CO2

Flue gas

w/o CO2

CaO CaCO3

CaO

Flue gas

Carbonator 0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0 10 20 30 40 50

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

High “looping ratios”= (mol CaO/s)/(mol CO2/s) for power plants and CFB reactors

Low sorbent activities MINIMUM LIMESTONE CONSUMPTION


11

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0 10 20 30 40 50

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 100 200 300 400 500

N

XnXN

Low “looping ratios”= (mol CaO/s)/(mol CO2/s) for CEMENT PLANTS

Very high sorbent activities HIGH LIMESTONE CONSUMPTION TO

CLINKER OVEN

Calciner

CO2

Carbonator

Flue gas

Flue gas

w/o CO2

CaO CaCO3

CaCO3

CaO


12

Outline

Why CaL for post-combustion CO2 capture ?




13

http://www.sciencedirect.com/science/journal/17505836

OPEN ACCESS DURING SEPTEMBER 2015


http://www.sciencedirect.com/science/journal/17505836


14 Large CaL pilots in operation (>100 kWth).

From: Emerging CO2 capture systems. Int. J. Greenhouse Gas Control, 2015, vol 40, 126-166, doi:10.1016/j.ijggc.2015.04.018

http://dx.doi.org/10.1016/j.ijggc.2015.04.018

Large CaL pilots in operation (>100 kWth).

La Pereda (Spain) Darmstad (Germany)

IFK (Germany) La Robla (Spain) ITRI (Taiwan)

Thermal input 1.7 MWth referred to carbonator

1 MWth referred to calciner

50-230 kWth referred to carbonator

300 kWth referred to the biomass fed to carbonator

1.9 MWth (1 tCO2/h)

Configuration Calciner: CFB Carbonator: CFB

Calciner: CFB Carbonator: CFB

Calciner: CFB Carbonator: FFB* and TFB*


Calciner: rotary kiln Carbonator: FB

Height Calciner: 15 m Carbonator: 15 m

Calciner: 11.4 m Carbonator: 8.6 m

Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*)

Calciner: 12 m Carbonator: 12 m

Calciner: 5m (length) Carbonator: 2.5m

Diameter Calciner: 0.75 m Carbonator: 0.65 m


Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+)



Control of solid flow

Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed

Flue gas source Integrated with power plant

Flue gas from coal burner

Synthetic flue gas Flue gas generated in carbonator

Integrated with the cement plant

Calciner operation

Oxy-fired with coal Oxy-fired with coal/propane

Oxy-fired with coal and flue gas recycle

Air-fired with biomass Oxy-fired with diesel

Project name or website

http://recal-project.eu/ ; http://cao2.eu

http://www.project-scarlet.eu/

http://cal-mod.eu-projects.de/

MenosCO2 HECLOT

From: Abanades et al, Emerging CO2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018

http://recal-project.eu/




16

Expertise in Lime based Fluidized Bed

Processes

Fluidized Bed Processes

Calcium Looping (CaL)

Chemical Looping (CLC)

Oxy-fuel CFB

Sorption enhanced reforming (SER)

Oxy-fuel SER

Fuels

Biomass

Waste

Lignite / Coal

Measurement techniques

Sorbent Characterization (TGA)

Online gas analysis:

CO2, CO, O2, H2, CH4, SOx, NOx

Non-condensable HC: GC

Tar: wet chemical & online (FID)

H2S, HCl, NH3: wet chemical

200 kWth DFB Pilot

Facility 20 kWth electrically heated

DFB System

5 kWth electrically heated

FB batch System

Calcium Looping – Pilot Plant (200 kWth)

Operation Conditions

Flue Gas Load: 170 - 230 kWth

Sorbent Looping Ratio: 3 - 13 molCaO/molCO2

Total Solid Inventory: 70 - 120 kg CaO/CaCO3

5

CaO

CaCO3

CO2-rich Gas

reci.

Flue Gas

CO2-lean

Flue Gas

O2 + reci.

Flue Gas

O2 + reci.

Flue Gas

O2 + reci.

Flue Gas

Flue

Gas

O2

Operational Results – Oxy-fuel Calcination

7

Large CaL pilots in operation (>100 kWth).

La Pereda (Spain) Darmstad (Germany)

IFK (Germany) La Robla (Spain) ITRI (Taiwan)

Thermal input 1.7 MWth referred to carbonator

1 MWth referred to calciner

50-230 kWth referred to carbonator

300 kWth referred to the biomass fed to carbonator

1.9 MWth (1 tCO2/h)

Configuration Calciner: CFB Carbonator: CFB


Calciner: CFB Carbonator: FFB* and TFB*


Calciner: rotary kiln Carbonator: FB

Height Calciner: 15 m Carbonator: 15 m


Calciner: 10 m Carbonator: 10 m (FFB*), 6 m (TFB*)

Calciner: 12 m Carbonator: 12 m

Calciner: 5m (length) Carbonator: 2.5m

Diameter Calciner: 0.75 m Carbonator: 0.65 m


Calciner: 0.21 m Carbonator: 0.21 m (FFB+), 0.33 m (TFB+)



Control of solid flow

Cone valves Screw conveyors Cone valves On:Off loop seal Kiln rotation speed

Flue gas source Integrated with power plant

Flue gas from coal burner

Synthetic flue gas Flue gas generated in carbonator

Integrated with the cement plant

Calciner operation

Oxy-fired with coal Oxy-fired with coal/propane

Oxy-fired with coal and flue gas recycle

Air-fired with biomass Oxy-fired with diesel

Project name or website

http://recal-project.eu/ ; http://cao2.eu

http://www.project-scarlet.eu/

http://cal-mod.eu-projects.de/

MenosCO2 HECLOT

From: Abanades et al, Emerging CO2 capture systems. Int. J. Greenhouse Gas Control, September 2015 (in press) doi:10.1016/j.ijggc.2015.04.018





Development of CaL technology in la Pereda

Reactions kinetics, sorbent deactivation, reactivation methods

Multicycle testing TG at CSIC

Abanades and Alvarez, 2003.

Conversion limits in the reaction of CO2

with lime. Energy and Fuels, 17- 2, 308

-315

0.03 MWth pilot at INCAR-CSIC

Twin CFB concept validation in lab

pilot plants

Rodriguez et al. 2010. Experimental

investigation of a CFB reactor to capture CO2

with CaO. AIChe Journal, 57, pp. 1356 - 1366

“La Pereda 1.7 MWth” pilot

Arias et al. 2013. Demonstration of steady state CO2 capture

in a 1.7 MWth calcium looping pilot. Int. J. of Greenhouse

Gas Control 18, 237–245

Twin CFB demon at large pilot

scale

1999 2008 2012-

Process

concept Reactor modeling, process integration

Example of steady state of CO2 capture

0

0.2

0.4

0.6

0.8

1

12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00

CO

2 c

aptu

re e

ffic

ien

cy

0

2

4

6

8

10

12

14

CO

2 (

%vo

l)ECO2 eqECO2CO2 outCO2 in

- Inventory of solids in carbonator = 300-400 kg/m2 - Average carbonator temperature= 660 ºC - Xave = 0.3-0.1

>1200 h

Operating in CO2 capture mode

Arias et al. 2013. Demonstration of steady

state CO2 capture in a 1.7 MWth calcium

looping pilot. Int. J. of Greenhouse Gas

Control 18, 237–245

Outline

Why post-combustion CO2 capture by CaL ?



Pre-

heater

Rotary Kiln

Pre-

calciner

Cooler

Fuel Preparation

Fuel

Air

ClinkerF

B C

aro

bn

ato

r

FB

Ca

lcin

er

CO2 lean

Flue GasCO2 rich Gas

Flue Gas

CaCO3

Fuel

O2 CaO

Raw Meal

Marl / Clay

Additive

Cement Plant – CaL Integration

General conditions

Looping Ratio: 2 - 4

Make-up Ratio: > 1

Flue gas

CO2: 15 - 30 %

synergy effect between cement plant and CaL-process

11

M. Hornberger, et al.


24

Secondary air

ROTARY KILNCLINKER COOLER

CLINKER GRINDING

PRE-HEATINGSTAGES

Limestone

CO2-lean flue gas

Coal

Pet cokePrimary air

CaO

Kiln flue gas

Concentrated CO2

ClayShale

Air

Excess air

Hot clinker

Cold clinker

Additives

Cement

CA

RB

ON

ATO

R

CA

LCIN

ER

ASU

CaCO3 CaO

AirO2

CaCO3

Rodríguez, N. et al (2012). CO2 Capture from Cement Plants Using Oxyfired Precalcination and/or Calcium Looping, Environmental Science and Technology, 46, 2460-2466.

Cement Plant – CaL Integration

MAIN OBJECTIVE OF WP12.1: Experimentally demonstrate and optimize at TRL6 the twin CFB reactor configurations for the conditions of a cement plant.

Process variant to integrate a CaL-process in a cement plant (no air-precalciner)

Titolo dello schema 25

M.C. Romano

rotary kiln

pre-calciner

clinkercooler

fuelinlet

fuelinlet

CO2 tostorage

CO2 freeflue gas

rawmealinlet

O2

inlet

raw meal

preheater

carbonator

The proposed concept of Ca-Looping cement plant (POLIMI-ITC patent)

1) The calciner is operated

with oxycombustion.

2) Part of CaO is used as a

sorbent for CO2 capture in

kiln exhaust gases, using a

carbonator placed in a

proper position along the

suspension preheater

3) Carbonator riser has to be

longer than a conventional

riser to ensure proper

contact times and cooled by

heat exchange surface

MAIN OBJECTIVE OF WP12.2: Develop and test entrained bed reactor

configurations to integrate in cement plant.


M.C. Romano

rotary kiln

pre-calciner

clinkercooler

fuelinlet

fuelinlet

CO2 tostorage

CO2 freeflue gas

rawmealinlet

O2

inlet

raw meal

preheater

carbonator

The proposed concept of Ca-Looping cement plant (POLIMI-ITC patent)

Why entrained flow carbonator?

1) Entrained flow hydrodinamics is

suitable for operation with small

size particles (40-50 μm) typical

of cement plants raw meal

2) The cement industry is

experienced in entrained flow

systems (calciner and

suspension preheaters are

entrained flow gas-solid

reactor/contactors)


M.C. Romano

Results

State of the art

cement plant

w/o CO2 capture

Partial oxyfuel

cement plant

Calcium looping

cement plant

Fuel input, kJLHV/kgclk 3231 3866 5573

Gross power production, MWe - 24.4 63.54

Auxiliaries, MWe -9.77 -31.87 -44.45

Net power output, MWe -9.77 -7.44 19.09

Net power output, kWhe/tclk -57.0 -43.4 111.4

CO2 capture efficiency, % - 81.9 95.4

CO2 emission, kg/tclk 854.8 174.2 40.8

CO2 avoided, % - 79.6 95.2

Equivalent(1) CO2 emission, kg/tclk 911.6 217.6 -70.3

Equivalent (1) CO2 avoided, % - 76.1 107.7

Equivalent (1) SPECCA(2), MJ/kgCO2 - 0.71 0.62

(1) Taking into account the CO2 emissions/credits from electric power import/export,

considering external power generation by 35% efficiency coal plant (2) SPECCA: specific primary energy consumption for CO2 avoided.


M.C. Romano

Research needs and future activities for WP12.2

Entrained flow carbonator testing and modelling:

Reactor length

Feasible solids-gas ratio

Sorbent properties

Heat transfer

Heat recovery steam cycle modelling

Romano, M.C., Spinelli M., Campanari S., Consonni S., Marchi M., Pimpinelli N., Cinti G., 2014. The Calcium looping

process for low CO2 emission cement plants. The 6th International Conference on Applied Energy. Taipei, Taiwan.

Marchi, M., Cinti G., Romano M.C., Campanari S., Consonni S., 2012. Improved process for the production of cement

clinker and related apparatus (in Italian). Italian patent MI2012 A00382.

Marchi, M., Cinti G., Romano M.C., Campanari S., Consonni S., 2012. Process and improved plant for the production of

cement clinker (in Italian). Italian patent MI2012 A00383.


29

Concluding remarks

Postcombustion Calcium Looping (CaL) has been tested in continuous large scale pilots by IFK, CSIC (>100 kWth) for more than 2000 hours in standard configurations for power plants.

Capture efficiencies over 90%, energy penalties 7-8 net points and cost about 20-30% lower than oxyfired CFBCs.

Sorbent related issues are “paradoxically” a benefit for cement CaL applications: enhanced attrition and high make up flows of sorbent are needed.

Scope for substantial reductions in penalty and CO2 capture costs by integration of CaL in cement industry

calcium looping - sintef.no · calcium looping – pilot plant (200 kw th) operation conditions...

Documents