options for calcium looping for co capture in the cement ... · pdf file2ikn gmbh, neustadt,...

Technology for a better society

1

G. Cinti1, R. Matai2, S. Becker2, M. Alonso3, C. Abanades3, M. Spinelli4, E De Lena4, S. Consonni4, M. Romano4, M. Hornberger5, R. Spörl5

1Italcementi, Bergamo, Italy 2IKN GmbH, Neustadt, Germany 3Agencia Estatal Consejo Superior de Investigaciones Cientificas (CSIC), Madrid, Spain 4Politecnico di Milano, Milan, Italy 5Institute of Combustion and Power Plant Technology (IFK), University of Stuttgart, Stuttgart, Germany

2nd ECRA/Cemcap workshop:

Carbon Capture Technologies in the Cement Industry

Dusseldorf, 6-7 November 2017

Options for calcium looping for CO2 capture in the cement industry

1


2

WP12 participants

Institute of Power Plant and Combustion technology, University of Stuttgart

Spanish research council, INCAR-CSIC

Italcementi

IKN,

Politecnico di Milano, Department of Energy


3

Calcium Looping process fundamentals

CARBONATION

CaO+CO2→CaCO3

~ 650ºC

Heat

Flue gas (CO2) (FCO2)

CO2-lean flue gas

CaCO3

CaO (FR)

CO2-rich gas to sequestration

CaCO3 make-up

(F0)

CaO purge

CALCINATION

CaCO3→CaO+CO2

~ 900ºC

Heat


4

• Originally proposed by Shimizu et al., 1999. A twin fluid-bed reactor for removal of CO2. Chem. Eng. Res. Des., 77.

• Continuously developed since 1998, mainly for application in power plants

• Several fluidized bed pilot facilities - demonstrated up to 1.7 MW

Calcium Looping for CO2 capture: history

200 kW pilot at IFK, U. Stuttgart 1.7 MW pilot at La Pereda (ES) 1 MW pilot at TU Darmstadt


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Calcium looping for cement plants

1. Cement plant-power plant coupling: CaO-rich spent sorbent from a CaL power plant as feed for the cement plant, as substitute of CaCO3

2. Post-combustion “tail end” configuration: CaL process is integrated in the cement plant with a conventional post-combustion capture configuration

3. Highly integrated CaL configuration: the CaL process is integrated within the cement production process by sharing the same oxyfuel calciner


6

Cement plant-power plant coupling

Bolier

coal

coal

CO2 lean

flue gas

FCO2

F0

clinker

raw meal

preheater

fuel

Calcined

raw meal


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Cement plant-power plant coupling S

ubstitu

tion r

atio

(% o

f C

a fed t

o t

he c

em

ent

kiln

as C

aO

fro

m t

he p

ow

er

pla

nt)

Romano M.C. et al., 2013. The calcium looping process for low CO2 emission cement and power. Energy Procedia, 37, 7091-7099.


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Calcium Looping CO2 capture: Tail-end CaL configuration

clinker

Ca

lcin

er CaCO3

fuel O2

Ca

rbo

na

tor

CO2 depleted

flue gas

CO2 to CPU

CEMENT

plant

Raw

meal

CaO

Flue gas

• Heat from fuel consumption recovered in efficient (~35% efficiency) steam cycle for power generation

• CFB CaL reactors: d50=100-250 μm, vs. particle size for clinker production d50=10-20 μm CaL purge milled in the raw mill at low temperature

General features of the process:

• Carbonator removes CO2 from cement plant flue gas Easy integration in existing cement

• Limestone partly calcined in Calcium Looping calciner CaO-rich purge from CaL calciner used as feed for the cement kiln

• High fuel consumption (double calcination for the mineral CO2 captured)


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Conducted Work:

• Parameter screening at 30 kW scale at CSIC (TRL5)

• Demonstration at semi-industrial scale (200 kWth) at IFK (TRL6)

• Process simulation and integration

Arias et al., 2017. CO2 Capture by CaL at Relevant Conditions for Cement Plants: Experimental Testing in a 30 kW Pilot Plant. Ind. Eng. Chem. Res., 56, 2634–2640.

Hornberger et al., 2017. CaL for CO2 Capture in Cement Plants – Pilot Scale Test. Energy Procedia, 114, 6171–6174.

Spinelli et al., 2017. Integration of CaL systems for CO2 capture in cement plants. Energy Procedia, 114, 6206-6214.

De Lena et al. Process integration of tail-end CaL for CO2 capture in cement plants. Int J Greenh Gas Control. In press.


25 CaO-Rich Meal

18

39 III Air

RAW MILL

ROTARY KILN

CLINKER COOLER

40Inlet Air

COOLER FANS

Limestone +

correctives

20

19

10

11 14

12

1513

97

Coal

16

6

17

5ASU

22 23

24

2CaL Purge

CO2 Compression and Purification

Unit

CO2 FAN

HT CO2 COOLER 1

CALCINER

21

LT CO2

COOLER

3736Kiln primary &

trasport air

35Calciner primary &

transport air

3

PURGECOOLER

26

31

34

27

29

33

41Exhausts fromclinker cooler

28

30

32

PREHEATING TOWER

43CPU Vent Gas

44Liquid CO2

42 II Air

4

Vent

38

COAL SILOS

1

FILTER FAN

RAW MEAL FAN

RAW MEAL SILOS

45Clinker

FLUE GASCOOLER

HT CO2 COOLER 2

LIMESTONE MILL FAN

LIMESTONE MILL

8

CaL CO2 capture island

Conventional cement kiln components

PRECALCINER

ID FAN

CARBONATOR

CaLLimestone


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Active space time design rule:

• τ𝑎𝑐𝑡𝑖𝑣𝑒 =𝑁𝐶𝑎𝑂

𝑁 𝐶𝑂2 𝑓𝑎 𝑋𝑎𝑣𝑒

• τ𝑎𝑐𝑡𝑖𝑣𝑒 > 501

𝑠 for 90 % CO2 capture

NCaO: molar amount of CaO in Carbonator ṄCO2

: molar flow of CO2 entering the Carbonator fa: sorbent fraction reacting in fast reaction regime Xave: average sorbent CO2 carrying capacity


Amount of active sorbent in the bed


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Demonstration at semi-industrial scale:

• High CO2 capture up to 98 % demonstrated

• Favorable CaL operation conditions

• reduced recycle train

• high sorbent activity

• High CO2 capture at carbonator inlet may cause problems of entrainment due to reduction of fluidization gas (~ -25 %)



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General information:

• CaL calciner coincides with the cement kiln pre-calciner

• Calcined raw meal as CO2 sorbent in the carbonator

• Sorbent has small particle size (d50=10-20 μm) entrained flow reactors

Calcium Looping CO2 capture: highly integrated configuration

Marchi M.I., et al., 2012. Procedimento migliorato per la produzione di clinker di cemento e relativo apparato. Patents MI2012 A00382 and MI2012 A00382.

Romano et al., 2014. The calcium looping process for low CO2 emission cement plants. Energy Procedia, 61, 500-503.

Fresh raw meal

Raw meal preheater

II

CO2-lean flue gas

Fuel

O2

Car

bon

ato

r

CO2-rich gas to CPU

Fuel

Cal

cine

r

Recarbonated / fresh sorbent

to calciner

Calcined raw meal to rotary kiln

Calcined raw meal to carbonator

Rotary kiln

CO2 recycle

Fresh raw meal

Raw meal preheater

III Air

Fresh raw meal

Raw meal preheater

III

Raw meal

recycle


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Conducted Work:

• TGA – sorbent characterization

• (Re)carbonation experiment in EF conditions

• EF oxyfuel calcination experiments

• Simulation of entrained flow Calcium Looping

• Preliminary process integration study

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 20 40 60 80 100 120 140

CO

2ca

ptu

re e

ffic

ien

cy

Reactor length, m

Cooled Reactor

Adiabatic Reactor

15 kgsorbent/Nm3gas

10 kgsorbent/Nm3gas

5 kgsorbent/Nm3gas

Calcium Looping CO2 capture: highly integrated configuration


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Tail end vs. highly integrated configuration: preliminary H&M balance

Cement plant w/o capture

Tail-end CaL integrated

CaL

F0/FCO2 -- 0.16 4.1

FCa/FCO2 -- 4.8 4.0

Carbonator CO2 capture efficiency [%] -- 88.8 80.0

Total fuel consumption [MJLHV/tclk] 3223 8672 4740

Rotary kiln burner fuel consumption [MJLHV/tclk] 1224 1210 1180

Pre-calciner fuel consumption [MJLHV/tclk] 1999 1542 3560

CaL calciner fuel consumption [MJLHV/tclk] -- 5920

Net electricity production [kWhel/ tclk] -132 159 -164

Direct CO2 emissions [kgCO2/tclk] 863.1 143.2 71.4

Indirect CO2 emissions [kgCO2/tclk] 105.2 -123.5 128.7

Equivalent CO2 emissions [kgCO2/tclk] 968.3 19.7 200.1

Equivalent CO2 avoided [%] -- 98.0 79.3

SPECCA [MJLHV/kgCO2] -- 3.26 2.32

Spinelli M. et al., 2017. Integration of Ca-Looping systems for CO2 capture in cement plants. Energy Procedia, 114, 6206-6214.

2nd ECRA/Cemcap workshop Dusseldorf, 6-7 November 2017

The CLEANKER project

G. Cintia, M. Fantinib, M. Romanoc, F. Canonicod, S. Consonnib,c

a Italcementi, Heidelberg Group b LEAP c Politecnico di Milano d Buzzi Unicem

Technology for a better society 16

Summary


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• Project objectives

• The demo plant

• The consortium

• Work packages


Primary project objectives


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The ultimate objective of CLEANKER is advancing the integrated Calcium-looping process for CO2 capture in cement plants.

This fundamental objective will be achieved by pursuing the following primary targets:

• Demonstrate the integrated CaL process at TRL 7, in a new demo system connected to the operating cement burning line of the Vernasca 900.000 ton/y cement plant, operated by BUZZI in Italy.

• Demonstrate the technical-economic feasibility of the integrated CaL process in retrofitted large scale cement plants through process modelling and scale-up study.

• Demonstrate the storage of the CO2 captured from the CaL demo system, through mineralization of inorganic material in a pilot reactor of 100 litres to be built in Vernasca, next to the CaL demo system.


Vernasca plant location


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VERNASCA PLANT


Primary project objectives


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• TRL 1 – basic principles observed

• TRL 2 – technology concept formulated

• TRL 3 – experimental proof of concept

• TRL 4 – technology validated in lab

• TRL 5 – technology validated in relevant environment (industrially relevant environment in the case of key enabling technologies)

• TRL 6 – technology demonstrated in relevant environment (industrially relevant environment in the case of key enabling technologies)

• TRL 7 – system prototype demonstration in operational environment

• TRL 8 – system complete and qualified

• TRL 9 – actual system proven in operational environment (competitive manufacturing in the case of key enabling technologies; or in space)


Indicative configuration of the CLEANKER pilot


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TO THE PROCESS FILTER

Temperature about 400°C

Temperature about 650°C

MEAL TO PREHEATER

GAS FROM PREHEATING TOWER

CO2 TO THE PROCESS FILTER

FUEL

OXYGEN

MEAL1 t/hTamb

MEAL TO PREHEATER

CO2

Entrained-flow oxyfuel calciner

Entrained-flow carbonator


Vernasca kiln preheater and rendering of CaL pilot


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The consortium


22

5EU member states + Switzerland


Work packages


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WP3 – Demonstration of CaLprocess

WP4 – Comparative characterization of raw meals

for CaL

WP2 – Demonstration systemdesign

WP5 – Process integration and modelling

WP6 – Scale up, economics, LCA

WP8 – Exploitation

WP1 - Management

WP9 - Dissemination

WP7 – Transport and storage


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Conclusions and Outlook

Ca-LOOPING PROCESS INTEGRATION OPTIONS: 1. Cement plant-power plant coupling:

• Excellent expected performance

• Easily retrofittable with low cost

• Logistic problem: a very large power plant has to be built next to the cement plant

2. Post-combustion capture configuration:

• Low uncertainty in the feasibility of the process (very similar to application in power plants)

• Very high CO2 capture expected

• Two calciners are present in the system, leading to high fuel consumptions

3. Integrated CaL configuration:

• High CO2 capture efficiency without modifying rotary kiln operation (no need of kiln oxyfiring).

• Higher thermal efficiency and lower fuel consumptions expected (compared to option 2)

• New carbonator design and fluid-dynamic regime: fluid-dynamics, heat management and sorbent performance need validation


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Thank you for your attention!

Acknowledgement

This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreements

n. 641185 (Cemcap) and n. 764816 (Cleanker)

www.sintef.no/cemcap

Twitter: @CEMCAP_CO2

Disclaimer: The European Commission support for the production of this publication does not constitute endorsement of the contents which reflects the views only of the authors, and the Commission cannot be held responsible for any use which may be made of the information contained therein

http://www.sintef.no/cemcap

options for calcium looping for co capture in the cement ... · pdf file2ikn gmbh, neustadt,...

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