www.LC3.

ch

What do I need to start LC3 production?

LC3 day Cairo, Egypt

Prof Fernando Martirena

November 30, 2021

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Affiliation

Professor and Director of CIDEM

Universidad Central de las Villas
Cuba

Main Consultant
Switzerland

Chair of the Technical Committee

TC 282-CCL – Calcined Clays as
Supplementary Cementitious Materials
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Closing the innovation loop

Fundamental
Research

Applied
Implementation Research

Technology
Development
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Collaboration with Prof. Karen Scrivener and LC3 Project

2005-2008 2009-2012 2013-2020
SDC-SNSF Project SDC-SNSF Project SDC-Climate Change
Calcined clays for Ternary blend cement Low Carbon
pozzolans calcined clay-limestone Cement

The pursuit of sustainable alternatives to replace Clinker with

Supplementary cementitious Materials
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Important steps in the introduction of LC3

Questions from the industry
• Choice of the right clay
• Clay activation
• The calcination process
• LC3 formulation

• Where can I go and ask for help?

• Are there real cases in operation?
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How to choose the clay?

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How to choose the right clay? Kaolinite content

» Similar strength to PC for blends containing 40% of
calcined kaolinite from 7d onwards
» At 28 and 90 days, little additional benefit >50%

• Still some deviations are observed, especially for clays

between 30 and 60% of calcined kaolinite
• What could be the reasons for such deviations?
• Fineness PC strength

• Specific surface
• Amorphous content
• Iron content
7
Francois Avet
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Criteria for screening clays

Theoretical criteria Empirical criteria
• % Al2O3 = 15,8 • % Al2O3 > 18
60% Quartz
• % Al2O3 / % SiO2 = 0,2 • % Al2O3 / % SiO2 > 0,3
40% Kaolinite
• % OH- = 5,6 • % LOI > 7,0

8
Alujas, Almenares, 2016
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Kaolinitic clay deposits

● Representative sampling is a critical

stage, due to the relatively large
variability of clay deposits

Slide A. Alujas, MOOC course EPFL, 2018

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How to choose the right clay? Collecting information

% Al2O3 > 18,0

Al2O3 / SiO2 > 0,3
% LOI > 7,0
% Na2Oeq < 3.0

% CaO < 3,0 (low calcite)

% SO3 < 3.0 (low sulfate / sulfide)
Slide A. Alujas, MOOC course EPFL, 2018
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How to choose the right clay? Preliminary Survey

Slide A. Alujas, MOOC course EPFL, 2018

Previous studies
Preliminary Survey (1-3m)
Detailed Exploration (~20m)
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How to choose the right clay?

Detailed exploration

Previous studies
Preliminary Survey (1-3m)
Slide A. Alujas, MOOC course EPFL, 2018 Detailed Exploration (~20m)
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How to choose the right clay? Technological types

0-2m

2 - 12 m

12 - 16
m

16 - 22
m Slide A. Alujas, MOOC course EPFL, 2018
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How to choose the right clay? Clay characterization

+ Kaolinite minerals
Low Sulfate / Sulfide / Carbonate
Mineralogical
composition (XRD)
% Al2O3 > 18,0
Al2O3 / SiO2 > 0,3
Mineralogical Chemical % LOI > 7,0
description composition % Na2Oeq < 3.0
% CaO < 3,0 (low calcite)
% SO3 < 3.0 (low sulfate / sulfide)
% Kaolinite group
minerals (TGA)
% Kaolinite minerals > 40
Low Sulfate / Sulfide / Carbonate Slide A. Alujas, MOOC course EPFL, 2018
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Quantification of kaolinite minerals by TGA Kaolinite + Bohemite

Δm
Dry
Weigh
t

Al2Si2O5(OH)4 → Al2O32SiO2 +
H2O(g)↑
(13.96 %) Resolution can be improved by
using derivative curves

• Sample size: ~ 100 mg

• Furnace atmosphere: Air
Proposed standard experimental
conditions for TA of minerals
• Heating rate: 10 ºC/min
Slide A. Alujas, MOOC course EPFL, 2018
• Packing: Loose packed
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Clay activation
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Importance of calcination temperature

• Calcination temperature must be high

enough to completely remove water and
hydroxyls from the structure
• Structural disorder created
(enhances reactivity)
• BUT too high temperatures will decrease
reactivity by loss of surface and then
crystallisation
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Calcination window
• The calcination window for
kaolinite is theoretically
between • ~ 14 %

500 and 650 oC

• But normally calcination • ~5%

should take place at slightly

higher temperatures
• ~5%

• Optimal range is temperatures

700-800oC
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Principle for clay activation

V
Kaolinite
IV VI %wt Al2O3 : 36.4
%wt Fe2O3 : 0.8

800°C

* *
600°C * Metakaolinite , Al2Si2O7
*
Kaolinite (1:1) Al2(OH)4Si2O5
RT * *
200 150 100 50 0 -50 -100 -150 -200 * : spinning sidebands
(ppm)
27Al NMR shows that the structural disorder increases between 600 and 800 oC
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Impact of calcination temperature

• Agglomeration occurs at 600°C

higher temperatures 30 50
Safe zone Danger zone
• Specific surface decreases 45

Specific Surface (BET)

25

Median diameter (d50)

(reactivity) 925°C 40

•
35
20
Above 950 oC 30
re-crystallization occurs 15 800°C 25
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)
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The calcination process

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Clay extraction

Clay extraction
• Material with moisture content 20-30%
• Must be transported and stored indoors
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Clay preparation
For particle size below
2 mm full
dehydroxylation is
guaranteed
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Equipment for clay preparation

Roll Crusher Stone Separator

Box Feeder

Roller Mill Mixer Extruder

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Clay processing
Clay processing
• Moisture must be
under 20%
• Clumps must be
reduced aided by
blade mills
• Maximum size of
clay clumps 20 mm
• Material should be
fed in original state
to the kiln

Dynamis, 2015 Belt Conveyor for Kiln

Feeding
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Calcination

• Firing temperature calcination

850-900 oC
H2O

• Residence time in burning Deshidratación oC

zone around 20-25 min 1400

1200

Weight proportion
1000
800
600
400
200
Clay
Calcined clay
1 5 10 15 20 25 30 35 40 min
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Rotary kiln, double body

Feeding
Drying Calcination Cooling
material

10-15 min 5-10 min 3-5 min

800ºC
drying cooling
Temperature

calcination
500ºC

70ºC
20ºC
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Operation of a flash calciner in clay calcination

Hot gas from burner dries material

Raw material drops through to burner
Raw material should be lifted 50-65 m

Clay gets dehydroxilated

Two stage process:
1. Removal of absorbed
water (calcination tower)
2. Removal of chemically
bound water(calcination
tower)

Calcined clay

Graph taken from CEMCAP Report “Status Report on Calciner Technology”, EU Horizon 2020, 2016
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Options for color control during calcination

850 Iron oxide 850
(Magnetite) Firing temp Iron oxide
range (Magnetite)

cooling
650 650

(Magnetite)
Iron oxide
Decomposition of

Temperature ºC

Temperature ºC
Fe-hydroxides

(Hematite)
Iron oxide

(Magnetite)
Iron oxide
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)

(Hematite)
Iron oxide
In the firing chamber due to
combustion and the high calcination

Iron oxi-hidrates

Iron oxi-hidrates
300 300
temperature (T≥ 600ºC)

(Goethite)

(Goethite)
formation of magnetite prevails

However, during cooling, if the

material reaches 600ºC and 0 0
below in a O2 rich environment, In the presence In the absence In the presence In the absence
hematite can form again of O2 of O2 of O2 of O2
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Implementing color control at Pilot Plant

No color control

With color control

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Monitoring reactivity. The R3 protocol

orimetry(at(40°C(
Paste composition: H2O
Portlandite +Alkali
grade(of(calcined(clays(
Calcined clay +Sulfate
mestone( (Limestone)

: ve(strength(results(

Isothermal calorimetry at Oven thermal treatment at 400°C

40°C Heat release Bound water
With limestone
1d Slices stored
at 400°C for 2 h

Mass
Stabilization
<0.5% in 24 h
4Development
mm slices cutof a new rapid, relevant and reliable (R3) test method to
stored at 110°C
evaluate the pozzolanic reactivity of calcined kaolinitic clays; François Avet
Francois Avet 31
et al, Cement and Concrete Research 85 (2016) 1–11
Bound water
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LC3 formulation
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Factors impacting early strength in LC3 systems

• Clinker mineralogical composition
• C3S
• C3A
• Naequiv
• Particle size distribution, with special emphasis on fineness of clinker
• Use of chemical admixtures
• During grinding
• During concrete mixing
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Impact of clinker mineralogical composition Unpublished results K. Duverger, Jinan, 2020

Sample clk2 clk7 clk11

C2S 8.6 3.7 9.4
C3S content: S2 ≥ S7 ≥ S11 C3A
C3S
1.1
61.8
4.2
60.3
2.6
32.8
C3A content: S7 ≥ S11 ≥ S2 C4AF 14.4 10.5 4.2
crystalline 89.2 81.1 50.9
amorphous 10.8 18.9 49.1

Impact of the clinker composition. Impact of the clinker composition.

Hydration
• Higher C3S brings about higher heat of
hydration
• Higher C3A brings about a broader alumina
peak
• These effects associated with reactivity of
the entire system (calcined clay!!)
• Best case is the combination of high C3S
Strength
• Higher C3S brings about higher strength
at 24h and 3d
• The combination of high C3S and high
C3A brings about impact after 3d
• Kaolinite content in the clay very
important!
• Dropped strength in filler system
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Grinding ternary binders

Ternary binders
have components
that are present in
small quantities and
grinding could
eventually become
a problem
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Co-grinding on LC3
Coarser
Calcined clay Clinker
Quartz (over 90
µm

Clinker Finer
the Rest

Limestone  Separator gauge was set for around 10% of

cement retained at 90 µm sieve (coarser
than normal practice)
 Most material retained at 90 µm (9%) sieve
was coarse clinker
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Grinding
 Electrically charged calcined clay Clinker
particles stick to the steel balls and
Calcined clay
prevent clinker from further grinding
Limestone
 Calcined clay and limestone as a result
end up ground in excess

Bola de acero
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Impact of grinding on clay agglomeration

25 µm 50 µm 30 µm Agglomeration
(calcination)
• 600ºC attraction forces
• 800ºC sintering
600ºC 800ºC 900ºC • 900ºC melting
Clay agglomeration during calcination (source: PhD thesis A. Alujas)

Co-grinding separate-grinding

Agglomeration
25 µm
15 µm (grinding)
• Co-grinding: smaller
agglomerates
• Separate grinding:
larger agglomerates
Impact of grinding on agglomerates (source: PhD L. Vizcaino)
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Impact of grinding aids. Co-grinding

CC 1h no GA CC 1h PCE 1 0.45% CC 1h Amine 0.13% CC 1h Glycol 0.12%

39 Franco Zunino, 2018

 NOTE: This test is a modification of the standard
ASTM C109/109M which includes adding SP to
www.LC3.ch achieve a Flow that enables having a water to
cement ratio similar to that of Portland cement
Impact of grinding aids. Co-grinding
Clinker content Co-grinding
60
7µm ≤ D ≤ 33 µm 50.00
D ≥ 33
45.00
50 µm
40.00

Compressive strength Mpa

35.00
40
30.00
D ≤ 7 µm
25.00
% mass

30
20.00

15.00
20 10.00

5.00
10 0.00
LC3 +
LC3 GA (TEA-A)
LC3 no GA + SP GA(4,5gINT Cemento tipo HE
3g +SP
(TEA-A)) + SP
0
Fine Medium Coarse 1d 8.09 6.10 12.51 10.30
no GA 29.42 55.09 51.27 3d 18.30 16.10 19.96 23.30
3g TEA 30.36 54.37 48.49 7d 31.70 22.40 34.14 32.20
4.5g TEA 32.68 55.22 41.4 28d 45.30 38.30 41.12 40.50
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Separate grinding (LC2)

BELT 1: calcined
clay
BELT 2: gypsum

BELT 3: limestone
SEPARATOR LC
2
PNEUMATIC
PUMP

SEONDARY PRIMARY
GRINDER GRINDER

CLK CCL LS GYP

Total SO3
100.00
LC2 2:1 0.00% 63.00% 30.00% 7.00% % 2.80%
 NOTE: This test is a modification of the standard
ASTM C109/109M which includes addingque
www.LC3.ch incluye añadir SP to achieve a Flow that enables
having a wáter to cement ratio similar to that of
Impact of grinding aids Portland cement

Limestone content
27
Separate grinding
50.00
26
25
% mass

45.00
24
40.00
23
22

Compressive strength Mpa

35.00
21
Fine Medium Coarse 30.00
no GA 26.55 26.1 26.64
GA 26.61 23.48 22.95 25.00

Calcined clay content) 20.00

60
15.00
50
10.00
40
% mass

30 5.00

20
0.00
LC2 + CPO+GA (3gINT LC3 + GA(4,5gINT
10 CPO + LC2 fine + SP Cemento tipo HE
(TEA-A))+SP (TEA-A)) + SP
0 1d 7.96 11.56 12.51 10.30
Fine Medium Coarse 3d 19.27 21.67 19.96 23.30
no GA 52.54 42.52 45.04 7d 24.25 32.51 34.14 32.20
GA 53.77 46.98 47.84 28d 35.24 43.49 41.12 40.50
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Where can I get help?

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The LC3 project team

2 not for profit Technical Resource Centres (TRCs):

Slide Karen Scrivener

www.LC3.ch

TRC LATAM
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Protocol to assist companies introduce LC3

Clay deposit 1
Screening clay Lithology
�

months
Clay deposit 2 Suitable

1-2
candidates Chem composit. candidate
Clay deposit 3

Bound water
Reactivity of
R3 protocol � Kaolinite

months
clay candidate Heat hydration

2-3
content
Std. Mortar

Non-profit company

8-12 months
PSD raw feed Std. Mortar
Calcination
registered in Switzerland, �
Calcination

months
Temperature
parameters technology

2-3
Heat hydration
with the goal of providing Residence time

advisory service to Grinding strategy Std mortar

companies in the cement Cement Market

months
Sulphate/alkalis rheology
2-3 formulation products
sector C. Clay/LS ratio Heat hydration

(www.ecosolutions.gl)
Feasibility
months

CAPEX/OPEX
1-2

Decision
making
46
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LC3 plant Cuba

Fully sensor-
equipped
calcined clay
calciner and
grinding facilities
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Real projects?
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Cemento Verde ARGOS, Colombia

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CIMPOR, Ivory Coast

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Thank you!!
José Fernando Martirena Hernández (Prof. Dr.Sc.
Ing.)
Director CIDEM
Faculty of Constructions. Universidad Central de las
Villas
e-mail: martirena@uclv.edu.cu/fmartirena@ecosur.org
skype: fmartirena@ecosur.org
Whatsup: +53 5 2637716 or +41 7 9710 2146
website: www.ecosur.org / www.lc3.ch
/www.ecosolutions.gl