TCCS-10 17-19th June 2019, Trondheim

Matteo Romano Politecnico di Milano, Department of Energy

CLEANKER – Clean clinker by calcium looping process for low-CO2 cement production – Overview and current stage

Technology for a better society 2

Calcium looping for CO2 capture: history and process fundamentals

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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

• 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 at size > 1 MW (La Pereda, Oviedo, ES; Darmstadt University, D)

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«Tail-end» CaL configuration

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• Carbonator removes CO2 from cement plant flue gas highly suitable for retrofit

• CaO-rich purge from CaL calciner used as feed for the cement kiln

• High fuel consumption due to double calcination of the mineral CO2 (air-blown precalciner + oxy-blown CaL calciner)

clinker

Ca

lcin

erCaCO3

fuelO2

Ca

rbo

na

tor

CO2 depleted

flue gas

CO2 to CPU

CEMENT

kiln

Raw

meal

CaO

Flue gas

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.

De Lena et al., 2017. Process integration of tail-end CaL in cement plants. Int J Greenh Gas Control 67, 71-92.

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«Integrated» CaL configuration

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CaL cement plant

CO2 to storage or utilization

Rotary kiln: CaO + heat -> clinker

Pre-calciner: CaCO3 + heat -> CaO

+ CO2

Fuel ClinkerAir

Flue gas (with CO2) to environment

Existing pre-heating tower

Raw mealCaCO3

Raw mealCaCO3

Raw meal preheater

Flue gas (poor in CO2) to the

environment

O2

Carbonator: CaO (from calciner) + CO2 (from kiln fuel) ->

CaCO3 (to calciner) + heat

Calciner: CaCO3 (fresh + from carbonator) + heat ->

CaO + CO2 (to storage)

Recarbonated sorbent (CaCO3 - rich) + fresh preheated raw meal

to calciner

Calcined raw meal to rotary kiln (CaO

rich)

Calcined raw meal to carbonator (CaO-rich)

Rotary kiln:CaO (from calciner) + heat -> clinker + flue gas

Car

bon

ator

Cal

cine

r

CO

2

Clinker cooler

ClinkerAir

Clinker cooler

III Air

Fuel

FuelFuel III Air

CO2 from:

calciner fuel

fresh raw meal

kiln fuel

CO2

CO2

CO

2

CO2

CO2

CO

2

CO

2

CO

2

CO

2

Conventional cement kiln Integrated CaL cement kiln

CO

2

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«Integrated» CaL configuration

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• CaL carbonator integrated in the preheater, treats the rotary kiln gas only

• CaL calciner coincides with the cement kiln pre-calciner single calcination step and reduced fuel consumption

• Calcined raw meal as CO2 sorbent in the carbonator

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

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

Alonso et al., 2018. Capacities of Cement Raw Meals in Calcium Looping Systems. Energy & Fuels, 31, 13955–13962.

Spinelli et al., 2018. One-dimensional model of entrained-flow carbonator for CO2 capture in cement kilns by calcium looping process. Chemical Engineering Science, 191, 100-114.

De Lena et al., 2019. Techno-economic analysis of Calcium Looping processes for low CO2 emission cement plants. Int J Greenh Gas Control, 82, 244-260.

Technology for a better society 6

Tail-end vs. Integrated CaL configurations

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De Lena et al., 2019. Techno-economic analysis of Calcium Looping processes for low CO2 emission cement plants. Int J Greenh Gas Control, 82, 244-260.

Cement plant w/o capture

Tail-end CaL (20% integration)

Tail-end CaL (50% integration)

Integrated CaL

Carbonator CO2 capture efficiency [%] -- 88.8 90.0 82.0

Total fuel consumption [MJLHV/tclk] 3240 8720 7100 5440

Rotary kiln fuel consumption [MJLHV/tclk] 1230 1220 1220 1150

Pre-calciner fuel consumpt. [MJLHV/tclk] 2010 1550 850 4290

CaL calciner fuel consumpt. [MJLHV/tclk] -- 5950 5040

ASU electric consumption [kWh/tcem] -- 85 73 62 CPU electric consumption [kWh/tcem] -- 110 101 89 Steam turbine production [kWh/tcem] -- 413 260 150 Other auxiliaries consumption [kWh/tcem] 97 137 128 116 Net electricity consumpt. [kWhel/ tcem] 97 -81 42 117 Direct CO2 emissions [kgCO2/tclk] 865 119 79 55 Indirect CO2 emissions [kgCO2/tclk] 35 -29 15 46 Equivalent CO2 emissions [kgCO2/tclk] 900 90 94 101 Equivalent CO2 avoided [%] -- 90.0 89.5 88.8 SPECCA [MJLHV/kgCO2] -- 4.42 4.07 3.16

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-30

-20

-10

0

10

20

30

40

50

60

70

80

Co

st o

f CO

2av

oid

ed, €

/tC

O2

Fuel Electricity Other var. Opex Fixed Opex Capex

Tail End CaL (IL=20%) Tail End CaL (IL=50%) Integrated CaL

Total CCA

Tail-end vs. Integrated CaL configurations

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De Lena et al., 2019. Techno-economic analysis of Calcium Looping processes for low CO2 emission cement plants. Int J Greenh Gas Control, 82, 244-260.

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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 1.300.000 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

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The consortium

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Starting date: October 1st 2017

Duration: 4 years

Total budget: € 9.237.851,25

UE co-financing: € 8.972.201,25

Chinese governement founding: 265.650 €

Partner: 13 from 5 EU member states + Switzerland and China

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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Vernasca kiln preheater and rendering of CaL pilot

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Preheater tower

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CLEANKER pilot plant configuration

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Rotary kiln

Raw Meal Inlet

Raw Meal Preheater

Flue gas

Fuel input 1

Carbonator

CO2-rich gas to filters

Fuel Inlet

Calciner

Carbonated sorbent to

calciner

Fresh raw mealto CaL Calciner

Calcined raw meal to

carbonator

Pneumatic transport air

Pre-calciner

Raw meal to preheater

1

3

5

7

9

2

4

6

8

10

11

1315

17

21

12

14

16

19

20Flue gas

to carbonator

Air leakAir leak

O2 Inlet18

Tertiary air

HX 3

Cooling Air

CO2 lean flue gas

Control Air

23

24

CO2 recycle

26

25

22

Fuel input 2

27

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER pilot 3D

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CLEANKER timeline

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2021 2020 2019 2018 2017

1st

Oct

ob

er 2

01

7

30

th S

epte

mb

er

20

21

17-18 October 2017 Kick-off meeting

July 2018 Pilot Plant H&M balances defined

December 2019 Erection completed

March 2020 Running tests and data analysis

September 2021 Strategic conclusions

April 2021 Casting concrete results

and full economic analysis of cement plant with CaL

March 2019 Fabrication begins

January 2020 Inspection

July 2018 Raw meal

characterization

June 2018 Measuring points

and instrumentation defined

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Acknowledgments

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

under Grant Agreement n. 764816

This work is supported by the China Government (National Natural Science Foundation of China) under contract

No.91434124 and No.51376105

CCUS in cement industry: CLEANKER project - CO2GeoNet Open Forum - S.Servolo, Venice - 6-9 May 2019

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