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16-Jan-24

Course instructor: HUỲNH NGỌC MINH

CONTENT
1. Introduction to cement
2. An overview of the Portland cement manufacturing
process
3. Hydration of Portland cement
4. Environment and cement industry

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Learning outcomes
4.1 Introduction to cement
4.1.1 Define Portland cement (PC) and Blended
Portland cement (PCB).
4.1.2 Note the technical advantages the
environmental advantages of PCB compared to PC.
4.2 Composition and properties of Portland cement
4.2.1 List the phase composition of PC clinker.
4.2.2 Note the characteristics of each phase.
4.2.3 Note the required properties of Portland
cement.

Learning outcomes
4.3 An overview of the Portland cement
manufacturing process
4.3.1 Briefly describe / diagram the Portland cement
manufacturing process
4.3.2 Understand the purpose of each stage in the
Portland cement manufacturing process.
4.3.3 Explain why the dry process for Portland
cement production is preferred over?
4.4 Raw materials for Portland cement
4.4.1 List the name of main components and
corrective materials of clinker raw mix.

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Learning outcomes
4.5 Raw meal preparation
4.5.1 Explain why it is important to grind raw meal
into a fine powder.
4.6 Clinker production
4.6.1 Note the stages of firing and various factors
related to firing operation of PC
4.6.2 Why does clinker have to be cooled down
rapidly?
4.6.3 What does make good clinker?
4.7 Cement production
4.7.1 Explain why it is important to grind cement into
a fine powder.
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Learning outcomes
4.8 Cement design
4.8.1 List the Influencing factors on cement performance.
4.9 Hydration
4.9.1 Briefly describe/diagram the hydration process from
a paste to hardened cement.
4.9.2 What main constituent does the content of gypsum
additive used in cement production depend on? Explain
the role of gypsum additive.
4.10 Environment and cement industry
4.10.1 Note the environmental pollution in cement
technology
4.10.2 Note the ability to handle the environment of
cement technology 6

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4.1. INTRODUCTION TO CEMENT


What is cement?
 Cement is a binder that sets and hardens and can
bind other materials together.
 Types of cement used in construction can be
characterized as being either hydraulic (thủy lực /
bền nước) or non-hydraulic (phi thủy lực / bền
không khí), depending upon the ability of the cement
to set in the presence of water.

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4.1. INTRODUCTION TO CEMENT


What is cement?
 Non-hydraulic cement (e.g., slacked lime, gypsum
cement) will not set in wet conditions or underwater;
rather, it sets as it dries and may react with carbon
dioxide in the air. It can be attacked by some
aggressive chemicals after setting.
 Hydraulic cement (e.g., Portland cement) set (đóng
rắn) 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 attacks.
 This allows setting in wet condition or underwater and
further protects the hardened material from chemical
attack. 9

4.1. INTRODUCTION TO CEMENT


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 for about 10 hours at atmospheric
pressure: CaCO3 → CaO + CO2
 The calcium oxide is then spent mixing with water (slaked) to
make slaked lime (vôi tôi): 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 underwater. 10

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4.1. INTRODUCTION TO CEMENT


A non-hydraulic cement: gypsum cement

Plaster (of Paris)


Phản ứng đóng rắn của
bột thạch cao xây dựng:
hòa tan, kết tinh

It is often called plaster of Paris, because of the large deposits of


pure gypsum at Montmartre hill in Paris.
The setting of unmodified plaster starts about 10 minutes after mixing
and is complete in about 45 minutes; but not fully set for 72 hours.
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4.1. INTRODUCTION TO CEMENT


A hydraulic cement: Portland cement

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4.1. INTRODUCTION TO 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

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4.1. INTRODUCTION TO CEMENT


The cement industry of Vietnam
 In Vietnam, the cement industry is the earliest development
from 1899 in Hai Phong (to serve the process of French rule).
 2005-2009: marked the continuous growth of cement
consumption in Vietnam due to the development of
infrastructure.
 The total design capacity of Vietnam's cement industry has
doubled in 5 years, from 25 million tons in 2006 to 50 million
tons in 2010.
 In 2022, the total cement consumption in the domestic market
will reach 62.68 million tons, equivalent to 2021.
 It is expected that the supply of cement will reach about 120.7
million tons, while the domestic demand for cement is
forecasted at only 63-65.5 million tons.
http://sxd.dongnai.gov.vn/Pages/newsdetail.aspx?NewsId=2554&CatId=38
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4.1. INTRODUCTION TO CEMENT


World Wide Cement Production 2018 &
Forecast 2030

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4.2. COMPOSITION AND PROPERTIES OF PC


Define Portland cements
 Portland cement (PC) is a hydraulic cement. It is
made by heating a mixture of limestone and clay or
other materials of similar bulk composition and
sufficient reactivity, ultimately to a temperature of about
1450oC. Partial fusion occurs, and nodules of clinker
are produced. The clinker is mixed with a few percent
(3-5%) of gypsum and finely ground to make the
Ordinary Portland Cement (OPC). In the grinding
process, it is possible to use limestone additives up to
5%; organic technology additives up to 1% (TCVN
2682:2020).
OPC = PC clinker + gypsum (3-5%)
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4.2. COMPOSITION AND PROPERTIES OF PC


Define Portland cements
 Blended Portland cement (PCB) is obtained by mixing
PC with mineral admixtures or additives (fly ash, slag
or silica fumes….).
PCB = PC + additives ( to 50%)
(TCVN 6260:2020)

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4.2. COMPOSITION AND PROPERTIES OF PC


Define Portland cements
Xi măng portland (OPC, PC: Ordinary Portland Cement), Xi măng Portland
hỗn hợp (PCB: Blended portland cement), Clinker là gì?
 Xi măng Portland:
Bột vô cơ có tính kết dính thủy lực, sản phẩm nghiền mịn của hỗn hợp
clinker XMP và lượng phụ gia thạch cao cần thiết (3-5% kl clinker). Trong
quá trình nghiền có thể sử dụng bổ sung thêm phụ gia đá vôi lên tới 5 %;
phụ gia công nghệ hữu cơ lên tới 1 % (TCVN 2682:2020).
PC = PC clinker + gypsum (3-5%)
 Xi măng Portland hỗn hợp:
sản phẩm nghiền mịn của xi măng Portland và những phụ gia khác (phụ
gia đầy, phụ gia hoạt tính,...) cho phép lên tới 50 %kl XM, với điều kiện
nhà sản xuất phải sử dụng xỉ hạt lò cao với tỷ lệ lớn hơn 10 % trở lên.
PCB = PC + additives ( to 50%) (TCVN 6260:2020).
 Clinker là bán thành phẩm trong quá trình sản xuất XMP: có được bằng
cách nung kết khối hh nguyên liệu tự nhiên như đá vôi, đất sét quặng
sắt ở nhiệt độ cao (1450oC) sau đó làm nguội nhanh. 19

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4.2. COMPOSITION AND PROPERTIES OF PC


Primary components of clinker raw materials
SiO2
16 – 26%

Silicon dioxide

CaO Al2O3 Clinker


59 – 67% 4 – 8%

Calcium Aluminum oxide


oxide

Fe2O3
2 – 5%

Iron oxide

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4.2. COMPOSITION AND PROPERTIES OF PC


CLINKER
Raw materials

grinding

mixing

raw meal

kiln feed

firing 14500C

fast cooling

clinker 21

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4.2. COMPOSITION AND PROPERTIES OF PC


Phase composition of PC clinker
▪ Major Phases
▪ C3S (alite: 3CaO.SiO2): 40 – 60%, very reactive compound, high
heat of hydration, high early strength
▪ C2S (belite: 2CaO.SiO2): 15 – 35%, low heat of hydration, slow
reaction, late stage strengths, durability
▪ C3A (aluminate: 3CaO.Al2O3): 4 – 14%, initial set, very high heat of
hydration, problems with sulfate attack
▪ C4AF (ferrite: 4CaO.Al2O3.Fe2O3): 10 – 18%, color
▪ Glassy phase: 15 - 25 % and other minerals

▪ Minor Phases
▪ CaOfree (free lime) - Setting time, early strengths
▪ Alkali / sulfates - Early strengths
▪ MgO - Expansion
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4.2. COMPOSITION AND PROPERTIES OF PC


Contribution of clinker phases on strength
development of PC

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4.2. COMPOSITION AND PROPERTIES OF PC


E.g. A blended Portland Cement (PCB)
Calcined Clay

Silica fume
Slag

Clinker
Blended cement
(PCB)
Fly ash
Gypsum

Portland cement
(OPC)

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4.2. COMPOSITION AND PROPERTIES OF PC

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https://civiltoday.com/civil-engineering-materials/cement/111-properties-of-cement-physical-chemical-properties

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4.2. COMPOSITION AND PROPERTIES OF PC


Physical properties (khi ở trạng thái bột)
1. Fineness of cement (độ mịn bột XM) is very important: The
hydration rate of cement is directly related to the cement particle
size.
2. Loss of Ignition (Mất khi nung của bột XM): Heating a
cement sample at 900 - 1000°C (that is, until a constant weight
is obtained) causes weight loss. This loss of weight upon heating
is calculated as loss of ignition. Improper and prolonged storage
or adulteration during transport or transfer may lead to pre-
hydration and carbonation, both of which might be indicated by
increased loss of ignition.
3. Bulk density (khối lượng thể tích bột XM): Cement has a
varying range of density depending on the cement compositions.
4.Specific gravity (khối lượng riêng bột XM) : is generally used
in mixture proportioning calculations (2.90 – 3.15 g/cm3)
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https://civiltoday.com/civil-engineering-materials/cement/111-properties-of-cement-physical-chemical-properties

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4.2. COMPOSITION AND PROPERTIES OF PC


Physical properties (khi ở trạng thái hồ vữa)
5. Consistency (độ dẻo của hồ xi măng) is the ability of cement
paste to flow.
6. Cement sets and hardens when water is added. The setting
time (thời gian đóng rắn / ninh kết / đông kết của hồ XM) can
vary depending on multiple factors, such as fineness of cement,
cement-water ratio, chemical content, and admixtures. Cement
used in construction should have an initial setting time that is not
too low and a final setting time not too high.
When water is added to cement, the reaction that takes place is
called hydration (thủy hóa).
 Hydration generates heat, which can affect the quality of the
cement and also be beneficial in maintaining curing
temperature during cold weather.
 On the other hand, when heat generation is high, especially in
large structures, it may cause undesired stress. 28

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4.2. COMPOSITION AND PROPERTIES OF PC


Physical properties (khi ở trạng thái đã đóng rắn / đá XM)
7. Strength (compressive and flexural) (độ bền nén, uốn của
đá XM): Various factors affect the strength, such as water-
cement ratio, cement-fine aggregate ratio, curing conditions,
size and shape of a specimen, the manner of molding and
mixing, loading conditions and age.
8. Soundness (độ ổn định thể tích của đá XM) refers to the
ability of cement to not shrink upon hardening. Good quality
cement retains its volume after setting without delayed
expansion, which is caused by excessive free lime and
magnesia.
9. The heat of hydration (nhiệt thủy hóa) is affected most by
C3S and C3A present in cement, and also by water-cement
ratio, fineness and curing temperature.
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https://civiltoday.com/civil-engineering-materials/cement/111-properties-of-cement-physical-chemical-properties

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4.2. COMPOSITION AND PROPERTIES 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.

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Typical compound composition of various


types of portland cement available in USA

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4.2. COMPOSITION AND PROPERTIES OF PC


E.g. A blended Portland Cement (PCB)
Calcined Clay

Silica fume
Slag

Clinker
Blended cement
(PCB)
Fly ash
Gypsum

Portland cement
(OPC)

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Chỉ tiêu kỹ thuật của XMP (PC) TCVN 2682:2020


What do “PC 50” and “PCB 40” mean?
Mức
Tên chỉ tiêu
PC40 PC50
1. Cường độ chịu nén, MPa, không nhỏ hơn: Compressive strength
- 3 ngày ± 45 min 21 25
- 28 ngày ± 8 h 40 50
2. Thời gian đông kết, min Setting time
- Bắt đầu, không nhỏ hơn. initial 45
- Kết thúc, không lớn hơn. final 375
3. Độ mịn, xác định theo :- Bề mặt riêng, phương pháp Blaine, Finess
2.800
cm2/g, không nhỏ hơn Surface area
4. Độ ổn định thể tích, xác định theo phương pháp Le Chatelier, mm,
10
không lớn hơn Soundness
5. Hàm lượng anhydric sunphuric (SO3), %, không lớn hơn 3,5
6. Hàm lượng magie oxít (MgO), %, không lớn hơn 5,01)
7. Hàm lượng mất khi nung (MKN), %, không lớn hơn:
- Khi sử dụng phụ gia đá vôi: 3,5
- Khi không sử dụng phụ gia đá vôi: 3,0
8. Hàm lượng cặn không tan (CKT), %, không lớn hơn 1,5
9. Hàm lượng kiềm quy đổi 2) (Na2Oqđ)3), %, không lớn hơn 0,6

CHÚ THÍCH :
1) Cho phép hàm lượng MgO tới 6,0 %, nếu độ nở autoclave (xác định theo TCVN 8877:2011) của xi

măng không lớn hơn 0,8 %.


2) Chỉ áp dụng giới hạn này trong trường hợp sử dụng xi măng với cốt liệu có khả năng xảy ra phản

ứng kiềm-silic mà không có sự lựa chọn nào khác để bảo vệ bê tông. 33


3) Hàm lượng kiềm quy đổi (Na O ) tính theo công thức: %Na O
2 qđ 2 qđ = %Na2O + 0,658 %K2O.

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Chỉ tiêu kỹ thuật của XMP hỗn hợp (PCB) TCVN 6260:2020
What do “PC 50” and “PCB 40” mean?
Mức
Tên chỉ tiêu
PCB30 PCB40 PCB50
1. Cường độ chịu nén, MPa, không nhỏ hơn: Compressive strength

- 3 ngày ± 45 min 14 18 22
- 28 ngày ± 8 h 30 40 50
2. Thời gian đông kết, min Setting time
- Bắt đầu, không nhỏ hơn initial 45
- Kết thúc, không lớn hơn final 420
3. Độ mịn, xác định theo: Finess
- Phần còn lại trên sàng 45μm, %, không lớn hơn
theo công bố nhà sản xuất
- Bề mặt riêng, phương pháp Blaine, cm2/g, không nhỏ hơn
Surface area

4. Độ ổn định thể tích, xác định theo phương pháp Le Soundness 10


Chatelier, mm, không lớn hơn
5. Hàm lượng anhydric sunphuric (SO3), %, không lớn hơn 3,5

6. Hàm lượng mất khi nung (MKN), %, không lớn hơn:


- Khi sử dụng phụ gia đá vôi: 10
- Khi sử dụng phụ gia pozzolan: 4
7. Độ nở autoclave1), %, không lớn hơn 0,8
CHÚ THÍCH:
1) Đây là chỉ tiêu tùy chọn, có thể thỏa thuận giữa bên mua và bên bán. 34

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4.2. COMPOSITION AND PROPERTIES OF PC


What do “PC 50” and “PCB 40” mean?

Why?

Advantages of blended cement (PCB)?


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4.2. COMPOSITION AND PROPERTIES OF PC


Advantages of blended cement (PCB)
Technical advantages
 The incorporation of pozzolanic materials in PCB improve its
properties such as rheology and cohesiveness, lower heat of
hydration, lower permeability, and higher resistance to chemical
attack.
 It improves workability for the same water content.
 The blended cements are finer as compared to PC, therefore the
permeability of concrete is less => improved durability.
Environmental advantages
 Energy-saving: by adding mineral admixtures with PC.
 Conservation of natural resources: by using the waste products of
thermal and steel plants as additives.
 Pollution control: By reducing the production of clinker, pollution is
also controlled as clinker is an energy-intensive product. 36

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4.3. 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...
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4.3. CEMENT MANUFACTURING PROCESSES


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 pelletized with water and fed
to a traveling 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
traveling 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).
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4.3. CEMENT MANUFACTURING PROCESSES


Dry process: modern technology
 “Wet” process allowed for easier handling and
homogenization 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.
 However, with more advanced modern technology, 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.
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4.3. CEMENT MANUFACTURING PROCESSES


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%)
(moisture: 0.4 % for dry kiln and 35 % for 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  5475 kJ/kg
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Aerial view of a cement plant

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Cement Manufacturing Process (2’21’’)


 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

File: Cement Manufacturing Process – YouTube.mkv


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4.4. Raw materials


 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
(high-grade limestone, silica, bauxite, ion ore)
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4.4. Raw materials


Materials • Limestone, marl ➔ Ca
• Clay, shale, iron ore ➔ Si, Al, Fe

Mining • Blasting
• Excavation

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


(tỉ lệ thành phần) • 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
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4.4. Raw materials –


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 4–8
Fe2O3 0.29 15.5 2–5
CaO 52.9 0.72 59 – 67
MgO 1.3 0.33 1–3
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
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4.4. Raw materials – Quarry

Key issues:
• Homogeneity of deposit
• Control of critical minor
elements
• Color

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4.4. Raw materials – longitudinal pre-


blending bed (đồng nhất sơ bộ trong kho dài)

Tbi phân tích nhanh thành Stacking (rải liệu vào kho)
phần hóa trên băng tải

Reclaiming
(cào liệu để lấy
liệu đưa đến định
lượng vào máy
nghiền) 51

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4.4. Raw materials – circular pre-blending


bed (đồng nhất sơ bộ trong kho tròn)

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4.5. Raw meal / kiln feed preparation


➢ 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 10–18% R90 m
➢ 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
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4.5. Raw meal / kiln feed preparation


Drying and grinding kiln feed with ball mill

55

55

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4.5. Raw meal / kiln feed preparation


Drying and grinding kiln feed with
vertical roller mill

56

56

4.5. Raw meal / kiln feed preparation


Dust Collection (To clean gas streams)
Bagfilter

Electrostatic Precipitator with


Conditioning Tower
57

57

28
16-Jan-24

4.5. Raw meal / kiln feed preparation


Raw Meal Homogenisation
In
FR The raw meal is homogenized by a
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 58

58

59

59

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16-Jan-24

4.6. CLINKER PRODUCTION


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

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


phase into mainly aluminate and ferrite
60

60

4.6. CLINKER PRODUCTION


Clinker formation

Contribution of clinker phases


on strength development

Formation of clinker phases


during burning process

64

64

30
16-Jan-24

Thermodynamics of Clinker Formation


DTA curves of typical cement raw meals
The greatest heat
requirement occurs
between 850 - 900 °C,
i.e. for the
decomposition of the
carbonate minerals.
The total heat
requirements for
dehydration,
decarbonization, and
melting exceed the
heat liberated by the
formation of belite and
the intermediate and
final products.

65

4.6. CLINKER PRODUCTION


The kiln in Dry process

DRYING

PREHEATING COOLING

CALCINING
SINTERING
66

66

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16-Jan-24

4.6. CLINKER PRODUCTION


The kiln: 1- cyclone-preheater

67

67

4.6. CLINKER PRODUCTION


The kiln in Dry process
80 °C 340 °C; to raw mill
and / or EP
Pre heater
Calciner

900 °C
Tertiary Air Duct
fuel
55 – 60 %
1700 °C fuel 280 °C; to EP
860 Rotary kiln
40 – 45 %
°C
350 °C
1400 °C
Clinker cooler
80 - 100 °C

Ambient air temp. 68

68

32
16-Jan-24

4.6. CLINKER PRODUCTION


The kiln: 2- Calciner

Main function:
+ decarbonisation of raw meal
+ combustion of fuel
+ heat transfer (gas/solid)

➔ Polysius Precalcining System -


PREPOL® 69

69

4.6. CLINKER PRODUCTION


The kiln: 3- Rotary kiln

70

70

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16-Jan-24

4.6. CLINKER PRODUCTION


Why does clinker have to be cooled down rapidly?

71

71

4.6. CLINKER PRODUCTION


Why does clinker have to be cooled down rapidly?
 Rapid cooling prevents undesired reactions in the
clinker: C3S → C2S + CaO (12500C)
 - C2S →  -C2S (6750C)
 Fast cooling prevents the growth of crystals, causing
part of the liquid phase to solidify as glass (the
grinding of this clinker is easier than grinding of
slowly cooled clinker).
 This process recovers heat from the clinker back to
the kiln by preheating the air used for combustion in
the main burner and in any secondary firing.
 Hot clinker has a negative effect on cement grinding.
 72

72

34
16-Jan-24

4.6. CLINKER PRODUCTION


Grate cooler (thiết bị làm nguội kiểu ghi)

73

73

4.6. CLINKER PRODUCTION


Grate cooler

74

74

35
16-Jan-24

4.6. CLINKER PRODUCTION


Clinker storage

➢ Outdoor storage causes prehydration


➢ Short storage time might lead to high grinding temperature

75

75

4.6. CLINKER PRODUCTION


What does make good clinker?
1. Chemistry

Burn-ability
2. Meal Fineness

3. Correct Burning Conditions:


▪ Temperature
▪ Time
▪ Atmosphere (oxidizing)
▪ Cooling

76

76

36
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4.6. CLINKER PRODUCTION


Reasons for free CaO

Possible reasons Counter measurements


• too high LSF • check chemistry
• clinker underburnt • burn harder
• oversize limestone grains • grind finer
• homogeneity poor • improve homogeneity
• alite decomposed • cool faster

77

77

4.6. CLINKER PRODUCTION


◼ SR 2.4 – 2.8 and AR 1.0 – 1.8 suitable to
achieve good reactivity
Parameters ◼ LSF > 95 might increase reactivity;
Giới hạn các modul > 100 in case of mineralized clinker
(tỉ lệ các oxide) phải
nằm trong giá trị ◼ Uniform kiln feed
thích hợp để pứ gần ◼ Appropriate* alkali/sulfur ratio
như hòa toàn
◼ Controlled & balanced AFR addition
◼ Right burning & cooling conditions
Reactivity ◼ Small crystal size – C3S, C3A
Khả năng pứ ◼ CaOf < 2% supports early strength;
> 2% CaOf might cause expansion
◼ P2O5, SrO, V2O5, Mn2O3 – unfavorable**

◼ Rapid cooling – to freeze clinker phases


Cooling ◼ Slow cooling: decomposition of C3S in
Làm nguội nhanh C2S; large crystals & less reactive clinker
78

78

37
16-Jan-24

79

79

4.7. 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 80

80

38
16-Jan-24

4.7. CEMENT PRODUCTION


Cement grinding ➢ Pre-determined fineness & particle
Compound grinding size distribution (PSD) by grindability
of individual cement constituents
(nghiền chung XM và phụ gia) ➢ Common practice in most plants

➢ Independent adjustable fineness &


Separate grinding PSD of cement constituents
➢ Easier to perform with VRM
(nghiền riêng)

Separate grinding: effect on PSD


81

81

4.7. CEMENT PRODUCTION


Cement storage, packaging & dispatch
Layout of dispatch / shipping station
Cement from the mills
Storage

Cement Cement
Silo Silo

Dispatch/Transport
Packing & Loading
82

82

39
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83

83

4.8. CEMENT DESIGN


E.g. A blended Portland Cement (PCB)
Calcined Clay

Silica fume
Slag

Clinker
Blended cement
(PCB)
Fly ash
Gypsum

Portland cement
(OPC)

84

84

40
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4.8. 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 & composition
Gypsum ➢ Should be optimized after each change in
composition or fineness
➢ Not only influence on setting time

➢ Fly ash, pozzolan, slag, silica fume are


Mineral Components most common
➢ Used amount & properties strongly
influence cement properties

85

85

4.8. 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

86

86

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SUMMARY
Influencing factors on cement performance
 Raw material preparation
 Chemical composition of used raw materials (minor elements)
 Raw meal fineness and kiln feed uniformity
 Clinker production
 Fuels (ash (tro), Q (nhiệt lượng), combustibles (chất bốc),…)
 Burning and cooling conditions
 Cement production
 Clinker reactivity
 Gypsum content and modifications
 Fineness, particle size distribution
 Mineral components
 Cement admixtures

87

87

88

88

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16-Jan-24

4.9. HYDRATION OF PORTLAND CEMENT


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

89

89

4.9. HYDRATION OF PORTLAND 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
(< 420 min.)
 Hardening: strength gain

90

90

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4.9. HYDRATION OF PORTLAND CEMENT


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. 91

91

4.9. HYDRATION OF PORTLAND CEMENT


Hydration of C3A and C4AF

(ettringite) slow setting

92

92

44
16-Jan-24

SEM micrographs of the evolution of the


surface of C3S at various hydration times

500nm

10min 1h

93
3h 10h 93

93

ettringite

Ca(OH)2

C-S-H

94

94

45
16-Jan-24

4.9. HYDRATION OF PORTLAND CEMENT


Dimensional range of solid and pores in a
hydrated cement paste

95

95

4.9. HYDRATION OF PORTLAND CEMENT


Composition of concrete mixes

- Cement paste: 25 - 40% volume of concrete mix


- Aggregate (fine + coarse): 25 - 40% volume of concrete mix
96

96

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16-Jan-24

97

97

Schematic representation of the total


materials cycle

William D. Callister and David G. Rethwisch, Materials Science And Engineering: An Introduction, 9th
98
ed. John Wiley & Sons, 2013, pp. 871.

98

47
16-Jan-24

Inputs/outputs for the life-cycle


assessment of a product

William D. Callister and David G. Rethwisch, Materials Science And Engineering: An Introduction, 9th
99
ed. John Wiley & Sons, 2013, pp. 871.

99

The main environmental impacts of


cement technology
 Dust: stack emissions and 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 (1kg clinker =>~1kg
CO2).
 Solid wastes: refractories, …
 Other emissions: noise and vibrations, odour, process
water, production waste, etc.
 Resources consumption: energy, raw materials (=>
destroying landscapes, causing ecological imbalance).

CEMBUREAU - the European Cement Association, “Best available techniques” for the cement
100
industry, December 1999

100

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16-Jan-24

The positive impacts: Waste utilization in


cement industry

101
http://www.aso-cement.jp/en/sustainable/waste.html

101

Different types of waste used as fuel by the


largest international cement companies/groups

Source: Increasing the use of alternative fuels at cement plants: International


best practice, IFC, 2017 102

102

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16-Jan-24

The positive impacts

103

103

104

104

50
16-Jan-24

105

105

New ways for cement and concrete to contribute


to a low carbon and circular economy

Only a combination of different ways to reduce emissions


can achive substantial reductions.
Chỉ khi có sự kết hợp nhiều cách khác nhau để giảm phát
thải thì mới có thể đạt được mức giảm đáng kể
Theo: THE EUROPEAN CEMENT ASSOCIATION 106

106

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16-Jan-24

Silicate glasses

THANK YOU 107

107

52

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