www.LC3.

ch

LC3: A breakthrough technology

to reduce CO2 emissions from
cementitious materials

Professor Karen Scrivener, FREng, EPFL, Switzerland

Professor Fernando Martirena, UCLV, Cuba
Alberto Putin, IPIAC, Portugal
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
 Portland based cements
will continue to dominate

Blended cements are the most realistic option to reduce CO2

and extend resources
Availability of SCMs
silica fume
waste glass Classic SCMs – fly ash and slag are only
Vegetable ashes around 15% of current cement production,
will drop to < 10% in near future
Natural Pozzolan
Used Available
Slag
Fly ash
Portland cement
Filler
limestone
Calcined Clay
0 2000 4000 6000

Mt/yr
There is no magic solution
§ Blended with SCMs will be best solution for sustainable cements for
foreseeable future

§ Only material really potentially available in viable quantities is

calcined clay.

§ Synergetic reaction of calcined clay and limestone allows high levels

of substitution:
EPFL led LC3 project supported by SDC. Started 2013
What is LC3 70
Gypsum
60
Limestone

Compressive strength
100 Calcined clay 50
1 day
Clinker 40
80
Mass proportion (%)

7 days

(MPa)
30
60 20 28 days
10 90 days
40
0
20
PC LC3-50
0 • 50% less clinker
PC PPC30 LC3-50 LC3-65 • 40% less CO2
• Similar strength
LC3 is a family of cements, • Better chloride resistance
the figure refers to • Resistant to alkali silica reaction
the clinker content
Comparison of calcined kaolinitic clay, slag and fly ash

Binary systems 70% clinker, 30% SCM

Ternary systems, with limestone 50% clinker, 30% SCM, 15% limestone
The LC3 project team

2 not for profit Technical Resource Centres (TRCs):

Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
Process to produce LC3 / LC2 LC3
Blend
/intergrind
calcined clay
with clinker
limestone
and gypsum

Find suitable Process Use in

Calcine clay
clay clay Concrete
Blend
/intergrind
calcined clay
Expertise with limestone
coming more and gypsum
from brick OPC
industry LC2
What kinds of clay are
suitable?
Clays and Clay minerals
Clay is a fine-grained natural rock or soil material that
combines one or more clay minerals with other minerals
and organic matter. Clays are plastic at appropriate water
content and become hard, brittle and non–plastic upon drying
or firing (AIPEA, CMS)

Clay minerals are hydrated phyllosilicates minerals, typically

smaller than 2 μm, mostly displaying sheet-like morphology,
which impart plasticity to clay and which harden upon drying or
firing

Common associated minerals: Feldspars, quartz,

(hydr)oxides of iron and aluminium, carbonates, …
Common associated phases: organic matter, hydrated
aluminosilicates with no long-range order (allophanes,
imoglite),…
 Classification of rocks containing Kaolinite
R.J
.P
ru
ett
/A
pp
lie
dC
lay

• (Kaolin-bearing rocks of
Sc

economic interest)
ien

• Kaolinitic clays deposits

ce

not suitable for paper, ceramic,

20 (

pigment or refractory industry

15
)

• Mine tailings
% Kaolinite (>40%) is the most important • Uncharted kaolinitic clay
parameter for highly reactive pozzolans deposits
Slide Adrian Alujas
Three basic clay structures
Kaolinite (1:1) Montmorillonite (2:1) Illite (Micas)
(Smectites) (2:1)

Na+, Ca++, H2O

aluminium
silicon

“Metakaolin”, sold as high purity product for paper, ceramic, refractory industries
Requirements for purity, colour, etc, mean expensive 3-4x price cement

Clays containing metakaolin available as wastes

– over or under burden NOT agricultural soil
Much much less expensive often available close to cement plants
Over 70 clays studied from around the world

Different calcination conditions

Different compositions,
impurities
Different physical properties

0% 17.0% 35.0%
38.9% 50.3% 66.2% 79.4% 95%

Quartz % of calcined kaolinite in the calcined clay Pure kaolinite

Benchmark test of clay strength
Ø Compressive strength EN 196-1 at 1, 3, 7, 28, 90 d
Ø Linear increase of strength with the MK content
of calcined clays
Ø Similar strength to PC for blends containing 40%
of calcined kaolinite from 7d onwards
Ø At 28 and 90 days, little additional benefit >60%
Ø Minor impacts of fineness, specific surface and
secondary phases

Calcined kaolinite content overwhelming parameter

Ideal kaolinite content
40-60%
Higher contents, possible to use more limestone
Even better economics and ecology

Lower contents can be enriched by separation

separated fine quartz
can be sold as separate product
 How to assess clays – not the same as good clays for clinker
» Weight loss between 400°C and 600°C – simple oven protocol available
» Guidelines for chemical analysis,

• % Al2O3 > 18
• % Al2O3 / % SiO2 > 0,3
• % LOI > 7,0

19
World soil map gives a rough indication,
yellow pink and light green regions, very good
but other areas have also have good deposits
Suitable clays presently stockpiled as waste
Process to produce LC3 / LC2 LC3
Blend
/intergrind
calcined clay
with clinker
limestone
and gypsum

Find suitable Process Use in

Calcine clay
clay clay Concrete
Blend
/intergrind
calcined clay
Expertise with limestone
coming more and gypsum
from brick OPC
industry LC2
Calcination of clay
Temperature window 700-850°

ideal
range
700-850

>1000
<600 600-700 850-1000 crystalline
Not reactive dehydroxlation Surface area phases
complete but reduced formed
reactivity reactivity no
increases decreases reactivity
Impact of calcination temperature
• Agglomeration occurs at 600°C
higher temperatures
Safe zone Danger
•
30 50
Specific surface zone 45
25
decreases (reactivity) 925°C

Specific Surface
40

Median diameter
• Above 950 oC 20
35
30
re-crystallization occurs 15 800°C 25

(BET)
(d50) 20
10
15
10
5
Ref. 5
0 0
-100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200

Temperature (°C)
Calcination methods:
Rotary kiln Flash calcination
» Advantages » Advantages
» Robust » Reputed more energy efficient
» Tolerant to moisture content up to 20%
» Fairly large particles (few mm) can be calcined » Disadvantages
efficiently » Very low moisture (<5%)
» Easy colour control technology » Dryer and dry storage silo required
» Small particles
» Disadvantages » crusher
» Reputed to have higher energy consumption

But real kiln built in Ivory Coast has energy of

550 kCal/ kg, 2.3 MJ/kg

Testing many clays indicates no significant difference in reactivity

Cuba – 1st Industrial trial
Jan 2013: Clay sourcing
Pontezuela (300 t)

March 2013: Clay calcination

Siguaney (110 t)

August 2013: Cement

grinding (130 t)

Sept-Dec. 2013: Cement use in

construction

Jan-July 2014: Evaluation of

concrete made with LC3
Industrial block manufacture plant
Prefabrication plant Cuba
House built at Santa Clara, Cuba with LC3
INDIA: Calcination
Industrial production
KJS Concrete Pvt. Ltd., Dadri
Demonstration structure

Around 14 tonnes of CO2 saved

Compared to existing solutions
Clay calcination in a double shaft rotary kiln
Two stage process:
calcination
1. Removal of absorbed water
(first shaft) H2O
2. Removal of chemically Dehydration oC

bound water(second shaft) Structural 1400

OH

Weight
Dehydroxilation 1200
The heat generated in the 1000
firing chamber is used to dry 800
the incoming material. 600
Flexibility for moisture content 400
200
(change rotation speed first
shaft) and output 1 5 10 15 20 25 30 35 40 min
New Calcination plant Ivory Coast
Colour control at Ivory Coast plant
Eco solution pilot plant for trial calcinations
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
Comparison of calcined kaolinitic clay, slag and fly ash

This example comes from the

lab with simple blending of
powders.

Industrial production allows

better optimisation of grinding
for early strength

Separate grinding will favour

the good combination of fine
clinker and not over ground
limestone and calcined clay.

Binary systems 70% clinker

Ternary systems, with limestone 50% clinker
Comparison to commercial pozzolanic cements
90
Control
80 LC3-50 63%MK
Compressive Strength (MPa)

70 LC3-50 47%MK

LC3-35 63%MK
60
CemCL General Use 40%
50 CemCL High Strength 20%
Normo4 PPC50 Pozz
40

30

20

10

0
1 2 3 7 28 90
Sample Age (d)
 Key Advantages

• Chloride resistance
• Suppression of alkali silica reaction
Chloride ponding ASTM

Apparent diffusion coeffs.

Perceived problems
• Workability
• Carbonation
 LC3
Ø Limestone and calcined clay are both much softer than clinker
Ø With intergrinding, high blaine and clinker is likely to be
underground. But situation can be improved by separate
grinding or addition of calcined clay at separator
Ø However effect of limestone and impurities in clay has positive
influence
Ø Good flowable concrete
can be obtained with use of
superplasticizers
Ø Better adapted SPs now being developed by admixture
companies
Ø In some formulation admixture dosage may even be less
Ø No segregation, no bleeding
Ø Further improvements possible with PSD optimisation,
grinding aids, etc
Carbonation
Indoor Outdoor
3D 28D 3D 28D

PC PC

PPC30 PPC30

LC3-50 LC3-50

2 years natural conditions : similar to other blends

Carbonation
Reducing calcium content; reduces buffer to carbonation
this is the same for all low carbon cements,
performance similar to blends with fly ash and slag
+H2O
CaO Ca(OH)2

CO2Ý +CO2

CaCO3
All CaO content can react with CO2,
not just portlandite
Leemann, et al(2015) :
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
CO2 reduction Cement: CSI System Calculations 2016 calcs
§ Only direct emissions are considered.
§ Emissions and energy consumption during extraction and transportation of raw materials (other than
limestone) and all fuels are excluded.
§ Emissions and energy consumed due to the production of electricity (both purchased and produced) is
excluded.
§ Provides data for comparison with CSI database
§ Based on measurable quantities at the plant level and avoids almost all assumptions that are not
relevant to local conditions and materials.
§ The energy cost of calcination assumed was
higher than the real energy seen in the Ivory Coast plant

Impact OPC PPC LC3 CSI (India, 2012): 70.5%

clinker factor
Emission of CO2 695 520 475 580*
(kg/tonne of cement)

*values shown for comparison

 Indian study in Concrete 2016
Clinker + SCM
Binder Mix ID Limestone %
gypsum %
OPC OPC 100 - -
• OPC Phase-1 FA30 FA30 70 30 -
LC3 LC3 54 31 15
• FA30
30% fly ash replacement
• LC3
50% clinker, 30% calcined clay, 15%
limestone, 5% gypsum
• M30 & M50
30 and 50 MPa design compressive
strength grades
 Again note LC3 figure would be
significantly lower with real energy
consumption

0.16 0.20
M30 M50
0.14 0.18
0.16
0.12 Others Others
0.14
0.10 Electricity Electricity
0.12
kg COշ eq./kg
kg COշ eq./kg

0.08 Transportation
0.10 Transportation
0.06 Aggregates
0.08 Aggregates
0.06
GGBS GGBS
0.04
0.04
Sand Sand
0.02 0.02
Cement Cement
0.00 0.00
OPC OPC with LC³ OPC with OPC OPC with LC³ OPC with
30% fly ash 15% GGBS 30% fly ash 15% GGBS
Potential global impact of LC3 technology
Global cement
Clinker
factor,
Global SCM Global CO2 IEA: International Energy
production volume reduction
global
average
Agency study for
Billion
tons/year
Billion
tones/year
Million
tones/year CSI: Cement Sustainability
%
Initiative
2006 2.6 79 0.5
of WBCSD: World Business
2050
(CSI study)
4.4 73 1.2 200 Council for Sustainable
2050
4.4 60 1.8 600 Development
(with LC3)
2050 with LC3
4.4 45 2.4 1000
2009
Developped

Global potential of LC3

∆ = 400 million
tonnes per yr

> 10 x entire
emissions
of Switzerland
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
Regulation: Cement
» EN 197
» Currently CEM II B category allows down to 65% clinker
with substitution by a combination of calcined clay and limestone CEM II B-M(Q-LL) – LC3-65
» New extension in a few months will allow CEM II C with down to 50% clinker – LC3-50
» ASTM C595
» Pozzolan content: ≤ 40%
» Limestone content: ≤ 15%
» Minimum clinker content: 45%

» Allows LC3-50
» But strength requirement is at constant slump with very fine sand and without admixture
» Even so successful conformity with LC3-50

» Many other countries are more flexible

» Indian, specific standard out for consultation soon

Regulation: Concrete
» Local codes much more complex

» Generally will require work on national level

Financial Feasibility
 Lower cost: Cementis study
50 OPC ref
clay close to plant
45
clay @ 200 km from plant
40

35 OPC ref
US $ / tonne

30

25

20

15

10
Report available:
5
[Link]
0 content/uploads/2020/10/2019-
Integrated Plant Grinding Plant [Link]
Overview
» Introduction and context
» Processes in Manufacturing
» Clay selection
» Calcination process
» Performance Characteristics
» Potential for CO2 reduction
» Regulatory obstacles
» Challenges
Challenges
» Finding the right clays – the TRCs are there to help you
» Evaluating financial feasibility – contacts available to help
» Calcination equipment – Many suppliers
» Use in Concrete – Increasing experience in the TRCs
» Changing standards and codes – also possibilities for collaboration
Concluding remarks

Ø Future cements will be based on Portland cement clinker with

increasing levels of incorporation of SCMs
Ø Calcined clays are the only realistic option
for extending the use SCMs
Ø Possible to obtain similar mechanical properties to OPC / CEM I with
50% clinker and clays with >40% kaolinite
Ø If we are serious about avoiding drastic climate change
we need to use cements with lower CO2 emissions,
e.g LC3 clinker/ calcined clay / limestone blends
Thank you
More information on: [Link]
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@LC3Cement EPFL STI IMX LMC MXG 233
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LC3-Low Carbon Cement Swiss Federal Institute of Technology
Lausanne
LC3-Low Carbon Cement 1015 Lausanne, Switzerland
LC3@[Link]
LC3-Limestone Calcined Clay Cement

Support from SDC is gratefully acknowledged