Course instructor: HUNH NGC MINH

CONTENT
Cementing property, lime and hydraulic materials.
Portland cement: Compositions, Properties
An Overview of the Portland Cement Manufacturing
Process
Clinker formations and clinker chemistry
Hydration of Portland cement
Introduction to other cements and cement products:
slacked lime, plaster of Paris
Introduction to concrete
Learning outcomes
Know cementing property, lime and hydraulic
materials.
Understand Portland cement (OPC, PCB)
Understand Portland cement manufacturing process
Know main raw materials for PC
Understand the purpose of the stages in Portland
cement process
Know various grinding equipments and cement kilns
Know various stages of firing and various factors
related to firing operation of PC
Know some other cements: composition, properties
and making
WHAT IS CEMENT
A cement is a binder, a substance that sets and
hardens and can bind other materials together.
The word "cement" can be traced back to the Roman
term opus caementicium, used to describe masonry
resembling modern concrete that was made from
crushed rock with burnt lime as binder.
Cements used in construction can be characterized
as being either hydraulic or non-hydraulic,
depending upon the ability of the cement to set in the
presence of water
WHAT IS CEMENT
Non-hydraulic cement will not set in wet conditions
or underwater; rather, it sets as it dries and reacts
with carbon dioxide in the air. It can be attacked by
some aggressive chemicals after setting.
Hydraulic cements (e.g., Portland cement) set and
become adhesive due to a chemical reaction
between the dry ingredients and water.
Mineral hydrates are quite durable in water and safe
from chemical attack.
This allows setting in wet condition or underwater and
further protects the hardened material from chemical
attack.
A non-hydraulic cement: slacked lime
Calcium hydroxide mixed with water, hardens by carbonation
in the presence of carbon dioxide which is naturally present in
the air.
First calcium oxide is produced by lime calcination at
temperatures above 825 C (1,517 F) for about 10 hours at
atmospheric pressure: CaCO3 CaO + CO2
The calcium oxide is then spent (slaked) mixing it with water
to make slaked lime: CaO + H2O Ca(OH)2
Once the excess water is completely evaporated (this process
is technically called setting), the carbonation starts:
Ca(OH)2 + CO2 CaCO3 + H2O
This reaction takes a significant amount of time. The
carbonation reaction requires the dry cement to be exposed to
air, for this reason the slaked lime is a non-hydraulic cement
and cannot be used under water.
A non-hydraulic cement: gypsum cement

(Plaster of Paris)

It is often called plaster of Paris, because of the large deposits of pure gypsum at
Montmartre hill in Paris
A hydraulic cement: Portland cement
HISTORY

Oldest Concrete Found To Date:

dates around 7000 BC: a lime concrete floor found
during the construction of a road at Yiftah El in Galilee,
Israel.
Beginning of the Industry:
Portland cement was first patented in 1824
Named after the natural limestone quarried on the Isle
of Portland in the English Channel
Portland Cement First Produced:
North America: 1871 Coplay, Pennsylvania
The cement industry of Vietnam
In Vietnam, the cement industry is the earliest
development (to serve the process of French rule),
from 1899 in Hai Phong.
According to statistics of 2012, production capacity
(design capacity) is about 68.50 million tons:
68 rotary kiln lines with a total capacity design 67.32
million tons.
13 shaft kiln lines with a total design capacity of 1.18
million tons.
Domestic consumption reached 45.20 million.
High oversupply, so in 2012 to limit production at 55
million tonnes (82% extraction capacity).
Portland cement
Xi mng Portland (PC: Portland cement)
l bt v c c tnh kt dnh thy lc, sn phm nghin mn
ca hn hp clinker XMP v ph gia thch cao (3-5% kl
clinker)
PC = PC clinker + gypsum (3-5%)
Xi mng hn hp (PCB: Blended portland cement)
l sn phm nghin mn ca xi mng Portland v nhng
ph gia khc (ph gia y, ph gia hot tnh,...)
PCB = PC + Additives ( 20 40%)
Clinker l bn thnh phm trong qu trnh sn xut XMP:
c c bng cch nung kt khi hh nguyn liu t nhin
nh vi, t st qung st nhit cao (14500C) sau
lm ngui nhanh. 12
Primary Components of Raw Materials
SiO2
16 26%

Silicon dioxide

CaO Al2O3 Clinker

59 67% 4 8%

Calcium Aluminum oxide

oxide

Fe2O3
2 5%
Iron oxide

Jan 2009
CLINKER
Raw materials

grinding

mixing

raw meal

kiln feed

firing 14500C

cooling

8 March 2017 clinker 14

Materials: Raw Mix Components
Main Raw Mix Components
Calcareous (Calcium/Lime) Materials -- CaCO3
(Limestone)
Argillaceous Materials -- SiO2, Al2O3 & Fe2O3
(Clay, Marl)
Main Components (Chemistry):
CaO = Lime / C SiO2 = Silica / S
Al2O3 = Alumina / A Fe2O3 = Iron / F

Raw Mix Corrective Materials

Materials rich in C, S, A, F to correct the rawmix

Jan 2009
Influences of Major and Minor Phases
of clinker on Cement Properties
Major Phases
C3S - very reactive compound, high heat of hydration,
high early strength
C2S - low heat of hydration, slow reaction, late stage
strengths, durability
C3A - Initial set, high heat of hydration, problems with
sulfate attack
C4AF - Color

Minor Phases
CaOfree (free lime) - Setting time, early strengths
Alkali / sulfates - Early strengths
MgO - Expansion
Contribution of clinker phases on
strength development of PC
ASTM Portland Cements
Type I General Purpose
Type II moderate heat of hydration and sulfate
resistance (C3A < 8%) : general construction, sea
water, mass concrete
Type III high early strength (C3A < 15%) :
emergency repairs, precast, winter construction.
Type IV low heat ( C3S < 35%, C3A < 7%, C2S >
40%) : mass concrete
Type V sulfate resistant ( C3A < 5%) : sulfate in
soil, sewers.
Blended Portland Cement (PCB)
a hydraulic cement consisting of two or more
inorganic constituents, which contribute to the
strength gaining properties of cement.

Clinker
Gypsum
(Portland cement)
Blended
cement
Fly ash
Slag
Silica Fume
Portland Calcined Clay
cement
What do PC 50 and PCB 40 mean?
Cement Manufacturing Processes
Mechanical Processes Thermal & Mechanical Processes
Chemical
Raw Processes
Materials
Calcareous Alternative
Argillaceous
Silica correctives Fuels
Raw
Iron correctives
Meal Gypsum

Mineral
Clinker Components
Quarrying
Crushing
Pre-blending Burning...
Cement
Grinding
Homogenizing...
Grinding Dispatch
Blending...
4 different basic processes
Dry process: Dry raw meal is fed to a cyclone preheater or
precalciner kiln or, in some cases, to a long dry kiln with
internal chain preheater.
Semi-dry process: Dry raw meal is pelletised with water and
fed to a travelling grate preheater prior to the rotary kiln or in
some cases, to a long kiln equipped with internal cross
preheaters.
Semi-wet process: Raw slurry is first dewatered in filter
presses. The resulting filter cake is either extruded into pellets
and fed to a travelling grate preheater or fed directly to a filter
cake drier for (dry) raw meal production prior to a
preheater/precalciner kiln.
Wet process: The raw slurry is fed either directly to a long
rotary kiln equipped with an internal drying/preheating system
(conventional wet process) or to a slurry drier prior to a
preheater/precalciner kiln (modern wet process).
Dry process: modern technology
Wet process allowed for an easier handling and
homogenisation of the raw materials, especially in cases
when the raw materials are wet and sticky or exhibit large
fluctuations in the chemical composition of the individual
raw mix components.
With more advanced modern technology however, it is
possible to prepare a homogeneous raw meal using the
dry process, i.e. without addition of water to prepare a
raw slurry. The main advantage of a modern dry process
over a traditional wet system is the far lower fuel
consumption and thus, lower fuel cost.
Today, the selection of the wet process is only feasible
under very specific raw material and process conditions.
27
 Thermodynamics of Clinker Formation
Heat balance of wet and dry kiln
(kJ/kg clinker; approximate values)
Dry kiln Wet kiln
Evaporation of H2O 20 (0.6%) 2100 (38%)
(0.4 % dry kiln and 35 % wet kiln)
Heat of reaction 1765 (54%) 1765 (32%)
Heat losses through 840 (26%) 1250 (23%)
gas, clinker, dust, etc.
Heat losses by radiation 650 (20%) 360 (7%)
and convection
3275 kJ/kg 5475kJ/kg
Cement Manufacturing Process
https://www.youtube.com/watch?v=m8U76Bm8kDY

5 parts
1. Raw material
2. Raw meal preparation
3. Clinker production
4. Cement production
5. Cement design

30
1. RAW MATERIAL
1. Raw material
Materials Limestone, marl Ca
Clay, shale, iron ore Si, Al, Fe

Mining Blasting
Excavation

Proportioning 9 Ca, 3 Si, 1 Al, 0.5 Fe

(t l thnh phn) Minor elements: alkali, sulfur, MgO, Cl

Selective exploitation
Preparation / Chemical control of composition of
Homogenization mix bed, e.g. online analyzer
PGNA
Pre-blending bed
Addition of correctives

Raw material composition & preparation has strong

impact on cement quality e.g. early strength,
efflorescence, expansion, grindability
Raw material quarry

Key issues:
Homogeneity of deposit
Control of critical minor
elements
Color
Raw material longitudinal pre-
blending bed
stacking

reclaiming
Raw material circular pre-
blending bed
Raw material chemical composition
Example:

Limestone [%] Clay [%] Clinker [%]

L.O.I. 43.2 12.5 <1
SiO2 1.4 45.9 16 26
Al2O3 0.23 23.9 48
Fe2O3 0.29 15.5 25
CaO 52.9 0.72 59 67
MgO 1.3 0.33 13
SO3 0.29 0.03 0.5 2
K2O 0.08 0.01 0.1 1.3
Na2O 0.01 0.11 0.05 0.7
2. RAW MEAL PREPARATION
Raw meal / kiln feed
Moisture content of raw material
Drying between 8 12%
Hot air from kiln is used

Vertical roller mill (VRM), sometimes

ball mill (BM)
VRM higher drying and grinding
Grinding capacity
Required fineness 1018% R90 mm
Different grindability of raw
materials (e.g. quartz) might effect
clinker reactivity
Multi-compartment silo
Homogenization
Through fluidization

Good kiln feed uniformity results in

Uniformity
more uniform & more reactive
clinker
 Raw meal / kiln feed

Dosage of correctives
2. Drying and grinding kiln feed
with ball mill
Drying and grinding kiln feed
with vertical roller mill
42
Dust Collection (To clean gas streams)
Bagfilter

Electrostatic Precipitator with

Conditioning Tower
3. Raw Meal Homogenisation
In The raw meal is homogenised by a
FR
Filter FR combination of the way it is added to /
extracted from the silo and the air mixing
in the silo.

Out

HS
Bypass

GKA GKJ

Active Inactive

GAS
3. CLINKER PRODUCTION
Process of Clinker Production

(1)
Process of Clinker Production

(2)
Process of Clinker Production

(3)
Sequence of Reactions Occurring
in a Rotary Kiln
20 - 100C Evaporation of free H2O
100 - 300C Loss of physically adsorbed water
400 - 900C Removal of structural H2O from clay minerals
>500C Structural changes in silicate minerals
600 - 900C Dissociation of carbonates
>800C Formation of C2S
~1450C Completion of
reaction and re-crystallization
of C3S and C2S

>1250C Formation of C3S 1300 - 1240C Crystallization of liquid

phase into mainly aluminate and ferrite
Cyclone-preheater
Clinker

Contribution of clinker phases

on strength development

Formation of clinker phases

during burning process
 CNG NGH SN XUT XI MNG
nung: l nung

DRYING

COOLING
PREHEATING

PREHEATING
SINTERING
 Clinker Production Line
80 340 C; to raw mill
C and / or EP

Pre heater

900 C
Calciner

Tertiary Air Duct

fuel
55 60
%
1700 C fuel 280 C; to EP
860 C Rotary kiln
40 45
%
350 C
1400 C
Clinker cooler
80 - 100 C

Ambient air temp.

Clinker cooling
Rapid cooling to freeze clinker phases
Cooling Slow cooling: decomposition of C3S in C2S;
Lm ngui nhanh large crystals & less reactive clinker
Uniform kiln feed
Appropriate* alkali/sulfur ratio
Controlled & balanced AFR addition
Right burning & cooling conditions
Reactivity Small crystal size C3S, C3A
Kh nng p CaOf < 2% supports early strength;
> 2% CaOf might cause expansion
P2O5, SrO, V2O5, Mn2O3 unfavorable**

SR 2.4 2.8 and AR 1.0 1.8 suitable to

achieve good reactivity
Parameters LSF > 95 might increase reactivity;
Gii hn cc > 100 in case of mineralized clinker
modul
Grate cooler

57
Grate cooler
Clinker production

Combustibles

Clinker storage
Outdoor storage causes
prehydration
Short storage time might lead to
high grinding temperature
CLINKER STORAGE (1)

Outdoor storage causes

prehydration
Short storage time might lead
to high grinding temperature
CLINKER STORAGE (2)
What does make good clinker?
1. Chemistry

Burn-ability
2. Meal Fineness

3. Correct Burning Conditions:

Temperature
Time
Atmosphere (oxidizing)
Cooling
Reasons for free CaO

Possible reasons Countermeasurements

too high LSF check chemistry
clinker underburnt burn harder
oversize limestone grains grind finer
homogeneity poor improve homogeneity
alite decomposed cool faster
4. CEMENT PRODUCTION
Cement grinding
Ball mill, roller press, vertical roller mill
Mill type Grinding energy required
Particle shape, particle size
distribution

Particle size distribution

Separator Effect on cement properties &
production capacity of mill

Accurate & reliable installation

Dosage system Effect on cement composition &
performance

Grinding Degree of gypsum dehydration

temperature Cement performance e.g. set time
Lump formation
Cement grinding
Pre-determined fineness & particle
Compound size distribution (PSD) by grindability
grinding of individual cement constituents
Common practice in most plants

Independent adjustable fineness &

Separate
grinding PSD of cement constituents
Easier to perform with VRM

Separate grinding: effect on

PSD
Cement grinding
+ 5% Gypsum
90% Clinker Grinding Portland
+ 5% Mineral Compt Cement

Ball mill

Note Composite
Cements contain >
5% mineral
components as a
clinker replacement

Jan 2009
Cement grinding
Vertical roller mill
(VRM)

Weigh
feeder
Cement grinding
Ball mill
(BM)

Vertical pre-grinder

Roller
press
(RP)
Cement storage, packaging & dispatch
Layout of dispatch / shipping station

Cement from the mills

Storage

Cement Cement
Silo Silo

Dispatch/Transport
Packing & Loading
5. CEMENT DESIGN
Cement design
Usually most reactive component
Clinker High uniformity required
Properties can directly be influenced
by the plant

Required amount & modification

depends on clinker reactivity &
Gypsum composition
Should be optimized after each
change in composition or fineness
Not only influence on setting time

Fly ash, pozzolan, slag, silica fume

MIC are most common
Used amount & properties strongly
influence cement properties
Cement design
Reduce grinding energy
Admixture Influence cement performance, e.g.
accelerator, air entrainer

Influence on
Setting time
Fineness Water demand
Strength development
Workability
Shrinkage

Long storage increase L.O.I.

reduced cement reactivity
Storage Lump formation might be caused by
high grinding temperature

high amount of gypsum

high potassium content

Summary
Influencing factor on cement performance
Raw material preparation
Chemical composition of used raw materials (minor
elements)
Raw meal fineness and kiln feed uniformity
Clinker production
Combustibles AFR, alkali/SO3 ratio
Burning and cooling conditions
Cement production
Clinker reactivity
Gypsum content and modifications
Fineness, PSD
MIC
Cement admixtures
 The main environmental impacts
Dust: stack emissions and fugitive sources (dust
from dispersed sources)
Gaseous atmospheric emissions: NOx, SO2, VOCs
(volatile organic compounds), CO, ammonia, HCl,
and heavy metals. CO2 as the main greenhouse gas
is released in considerable quantities.
Other emissions: noise and vibrations, odour,
process water, production waste, etc.
Resources consumption: energy, raw materials.

CEMBUREAU - the European Cement Association, Best available techniques for the cement
industry, December 1999
The positive impacts
When water is added to cement,
what happens?
Dissolution of cement grains
Growing ionic concentration in water (now a solution)
Formation of compounds in solution
After reaching a saturation concentration, compounds
precipitate out as solids (hydration products)
In later stages, products form on or very near the surface
of the anhydrous cement
Setting and Hardening
Setting: Solidification of the plastic cement paste
Initial Set: Beginning of solidification (point in time
when the paste has become unworkable) (>45 min.)
Final Set: Final solidification (< 375 min.)

Hardening: strength gain

Hydration of C3S and C2S
Depending on the reaction conditions, hydrated
products are different , an example:

Both produce C-S-H and CH as reaction products

C2S produces less CH (important for durability in
sulfate rich environments)
More heat is evolved during C3S hydration
C3S hydration is more rapid, contributing to early age
strength (2-3h to 14 days)
C2S hydration occurs more slowly to contributing to
strength after ~7-14 days.
SEM micrographs of the evolution of the
surface of C3S at various hydration times
500nm

10min 1h

85
3h 10h
Hydration of C3A and C4AF

(ettringite)
ettringite

Ca(OH)2

C-S-H

87
Dimensional range of solod and
pores in a hydrated cement paste
QUESTIONS
Silicate glasses

THANK YOU