Manufacture Process of Cement

The manufacturing procedure for Portland cement is as follows:

1. Mixing of raw material
2. Burning
3. Grinding
4. Storage and packaging

1. Mixing of raw material

The raw materials needed to produce cement (calcium carbonate, silica, alumina,
and iron ore) are generally extracted from limestone rock, chalk, shale, or clay.
These raw materials are won from the quarry by either extraction or blasting.
 
These naturally occurring minerals are then crushed through a milling process. At
this stage, additional minerals are added to ensure the correct chemical
composition for making cement. These minerals can be obtained from the waste
or by-products of other industries, such as paper ash. Milling produces a fine
powder, known as raw meal, which is preheated and then sent to the kiln for
further processing.
The major raw materials used in the manufacture of cement are Calcium,
Silicon, Iron and Aluminum. These minerals are used in different form as per
the availability of the minerals.

Table shows the raw materials for Portland cement manufacture

The mixing procedure for the manufacture of cement is done via 2 methods

 Dry process
  Wet process

a)  Dry Process

In this process, both calcareous and argillaceous raw materials are first
crushed in the gyratory crushers to get 2-5cm size pieces separately. The
crushed materials are again ground to get fine particles into ball or tube mill.

Each finely ground material is stored in hopper after screening. Now these
powdered minerals are mixed in required proportion to get dry raw mix
which is then stored in silos and kept ready to be sent into rotary kiln. Now
the raw materials are mixed in specific proportions so that the average
composition of the final product is maintained properly.
 Fig: Manufacture of Cement by Dry Process

b)  Wet Process

The raw materials are first crushed and made into powdered form and stored
in silos. The clay is then washed in washing mills to remove adhering organic
matters found in clay.

The powdered limestone and water washed clay are sent to flow in the
channels and transfer to grinding mills where they are completely mixed and
the paste is formed, i.e., known as slurry.

The grinding process can be done in ball or tube mill or even both. Then the
slurry is led into collecting basin where composition can be adjusted. The
slurry contains around 38-40% water that is stored in storage tanks and
kept ready for the rotary kiln.

Fig: Manufacture of Cement by Wet Process

Comparison of dry process and wet process of Cement Manufacture

Criteria Dry process Wet process

Hardness of raw
Quite hard Any type of raw material
material

Fuel consumption Low High

Time of process Lesser Higher

Quality Inferior quality Superior quality

Cost of production High Low

Overall cost Costly Cheaper

Physical state Raw mix (solid) Slurry (liquid)

2. Burning of Raw Materials

The kiln is at the heart of the manufacturing process. Once inside the kiln, the raw
meal is heated to around 1,500 degrees C - a similar temperature to that of
molten lava. At this temperature, chemical reactions take place to form cement
clinker, which contains hydraulic calcium silicates.
The burning process is carried out in the rotary kiln while the raw materials
are rotated at 1-2rpm at its longitudinal axis. The rotary kiln is made up of
steel tubes having the diameter of 2.5-3.0 meter and the length differs from
90-120meter. The inner side of the kiln is lined with refractory bricks.

The kiln is supported on the columns of masonry or concrete and rested on

roller bearing in slightly inclined position at the gradient of 1 in 25 to 1 in 30.
The raw mix of dry process of corrected slurry of wet process is injected into
the kiln from the upper end.
In order to heat the materials to this very high temperature, a 2,000-degree C
flame is required, which can be produced through the use of fossil and waste-
derived fuels. The kiln itself is angled by 3 degrees to the horizontal to allow the
material to pass through it, over a period of 20 to 30 minutes.
The kiln is heated with the help of powdered coal or oil or hot gases from the
lower end of the kiln so that the long hot flames is produced.

As the kiln position is inclined and it rotates slowly, the material charged
from upper end moves towards lower end at the speed of 15m/hr. In the
upper part, water or moisture in the material is evaporated at 400oC temp,
so this process is known as Drying Zone.

The central part i.e. calcination zone, the temperature is around 1000 0C,
where decomposition of lime stone takes place. The remaining material is in
the form of small lumps known as nodules after the CO2 is released.
CaCO3 = CaO + CO2
The lower part (clinkering zone) have temperature in between 1500-1700 0C
where lime and clay are reacts to yielding calcium aluminates and calcium
silicates. This aluminates and silicates of calcium fuse together to form small
and hard stones are known as clinkers. The size of the clinker is varies from
5-10mm.

2CaO + SiO2 = Ca2SiO4 (declaim silicate (C2S))

3CaO + SiO2 = Ca3SiO5 (tricalcium silicate (C3S))
3CaO + Al2O3 = Ca3Al2O6 (dicalcium aluminate (C2A))
4CaO + Al2O3 + Fe2O3 = Ca4Al2Fe2O10 (tetracalcium aluminoferrite(C4AF))

Upon exiting the kiln, the clinkers coming from the burning zone are very hot; they
are cooled. To bring down the temperature of clinkers, air is admitted in counter
current direction at the base of the rotary kiln. The cooled clinkers are collected in
small trolleys and stored, ready for grinding, to produce cement.
3. Grinding of Clinkers
The cooled clinkers are received from the cooling pans and sent into mills.
The clinkers are ground finely into powder in ball mill or tube mill. Powdered
gypsum is added around 2-5%) as retarding agent during final grinding. The
mixture is then very finely ground to obtain "pure cement." During this
phase, different mineral materials, called "additions," may be added
alongside the gypsum. Used in varying proportions, these additions, which
are of natural or industrial origin, give the cement specific properties, such
as reduced permeability, greater resistance to sulfates and aggressive
environments, improved workability, or higher-quality finishes. The final
obtained product is cement that does not settle quickly when comes in
contact with water.

After the initial setting time of the cement, the cement becomes stiff and the
gypsum retards the dissolution of tri-calcium aluminates by forming
tricalcium sulfoaluminate which is insoluble and prevents too early further
reactions of setting and hardening.

3CaO.Al2O3 + xCaSO4.7H2O = 3CaO.Al2O3.xCaSO4.7H2O

4. Storage and packaging

The ground cement is stored in silos, from which it is marketed either in
container load or 50kg bags.

Classes of Cement
Cements used in construction are usually inorganic, often lime or calcium
silicate based, and can be characterized as being either hydraulic or non-
hydraulic, depending upon the ability of the cement to set in the presence of
water (see hydraulic and non-hydraulic lime plaster).
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 is resistant to attack by
chemicals after setting.
Hydraulic cements (e.g., Portland cement) set and become adhesive due to
a chemical reaction between the dry ingredients and water. The chemical reaction
results in mineral hydrates that are not very water-soluble and so 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. The chemical process for hydraulic cement found by ancient
Romans used volcanic ash (pozzolana) with added lime (calcium oxide).
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. The volcanic ash and pulverized brick
supplements that were added to the burnt lime, to obtain a hydraulic binder,
were later referred to as cementum, cimentum, cäment, and cement. In modern
times, organic polymers are sometimes used as cements in concrete.
Non-hydraulic cement, such as slaked lime (calcium oxide mixed with water),
hardens by carbonation in the presence of carbon dioxide which is naturally
present in the air. First calcium oxide (lime) is produced from calcium
carbonate (limestone or chalk) by 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
(calcium hydroxide):
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 because the partial pressure of
carbon dioxide in the air is low. The carbonation reaction requires the dry cement
to be exposed to air, and for this reason the slaked lime is a non-hydraulic cement
and cannot be used under water. This whole process is called the lime cycle.
Conversely, hydraulic cement hardens by hydration when water is added.
Hydraulic cements (such as Portland cement) are made of a mixture of silicates
and oxides, the four main components being:
Belite (2CaO·SiO2);
 Alite (3CaO·SiO2);
Tricalcium aluminate (3CaO·Al2O3) (historically, and still occasionally, called
'celite');
Brownmillerite (4CaO·Al2O3·Fe2O3).
The silicates are responsible for the mechanical properties of the cement, the
tricalcium aluminate and the brownmillerite are essential to allow the formation
of the liquid phase during the kiln sintering (firing). The chemistry of the above
listed reactions is not completely clear and is still the object of research.

Health and Safety Issues

Bags of cement routinely have health and safety warnings printed on them
because not only is cement highly alkaline, but the setting process is exothermic.
As a result, wet cement is strongly caustic (water pH = 13.5) and can easily cause
severe skin burns if not promptly washed off with water. Similarly, dry cement
powder in contact with mucous membranes can cause severe eye or respiratory
irritation. Some trace elements, such as chromium, from impurities naturally
present in the raw materials used to produce cement may cause allergic
dermatitis. Reducing agents such as ferrous sulfate (FeSO4) are often added to
cement to convert the carcinogenic hexavalent chromate (CrO42−) into trivalent
chromium (Cr3+), a less toxic chemical species. Cement users need also to wear
appropriate gloves and protective clothing.

Environmental Impacts:
Cement manufacture causes environmental impacts at all stages of the process.
These include emissions of airborne pollution in the form of dust, gases, noise and
vibration when operating machinery and during blasting in quarries, and damage
to countryside from quarrying. Equipment to reduce dust emissions during
quarrying and manufacture of cement is widely used, and equipment to trap and
separate exhaust gases are coming into increased use. Environmental protection
also includes the re-integration of quarries into the countryside after they have
been closed down by returning them to nature or re-cultivating them.
CO  emissions
2

Global carbon emission by type to 2004. Attribution: Mak Thorpe

Carbon concentration in cement spans from ≈5% in cement structures to ≈8% in

the case of roads in cement. Cement manufacturing releases CO2 in the
atmosphere both directly when calcium carbonate is heated,
producing lime and carbon dioxide, and also indirectly through the use of energy
if its production involves the emission of CO2. The cement industry produces
about 10% of global man-made CO2 emissions, of which 60% is from the
chemical process, and 40% from burning fuel.
Nearly 900 kg of CO2 are emitted for every 1000 kg of Portland cement produced.
In the European Union the specific energy consumption for the production of
cement clinker has been reduced by approximately 30% since the 1970s. This
reduction in primary energy requirements is equivalent to approximately 11
million tons of coal per year with corresponding benefits in reduction of
CO2 emissions. This accounts for approximately 5% of anthropogenic CO2. The
majority of carbon dioxide emissions in the manufacture of Portland cement
(approximately 60%) are produced from the chemical decomposition of limestone
to lime, an ingredient in Portland cement clinker. These emissions may be
reduced by lowering the clinker content of cement.
To reduce the transport of heavier raw materials and to minimize the associated
costs, it is more economical for cement plants to be closer to the limestone
quarries rather than to the consumer centers.
In certain applications, lime mortar reabsorbs some of the CO2 as was released in
its manufacture, and has a lower energy requirement in production than
mainstream cement (citation needed). Newly developed cement types from
Novacem and Eco-cement can absorb carbon dioxide from ambient air during
hardening. Use of the Kalina cycle during production can also increase energy
efficiency.

Heavy metal emissions in the air

In some circumstances, mainly depending on the origin and the composition of
the raw materials used, the high-temperature calcination process of limestone
and clay minerals can release in the atmosphere gases and dust rich in
volatile heavy metals, e.g, thallium, cadmium and mercury are the most toxic.
Heavy metals (Tl, Cd, Hg, ...) and also selenium are often found as trace elements
in common metal sulfides (pyrite (FeS2), zinc blende (ZnS), galena (PbS), ...)
present as secondary minerals in most of the raw materials. Environmental
regulations exist in many countries to limit these emissions. As of 2011 in the
United States, cement kilns are "legally allowed to pump more toxins into the air
than are hazardous-waste incinerators."

Heavy metals present in the clinker

The presence of heavy metals in the clinker arises both from the natural raw
materials and from the use of recycled by-products or alternative fuels. The high
pH prevailing in the cement porewater (12.5 < pH < 13.5) limits the mobility of
many heavy metals by decreasing their solubility and increasing their sorption
onto the cement mineral phases. Nickel, zinc and lead are commonly found in
cement in non-negligible concentrations. Chromium may also directly arise as
natural impurity from the raw materials or as secondary contamination from the
abrasion of hard chromium steel alloys used in the ball mills when the clinker is
ground. As chromate (CrO42−) is toxic and may cause severe skin allergies at trace
concentration, it is sometimes reduced into trivalent Cr(III) by addition of ferrous
sulfate (FeSO4).
Use of alternative fuels and by-products materials
A cement plant consumes 3 to 6 GJ of fuel per ton of clinker produced, depending
on the raw materials and the process used. Most cement kilns today use coal and
petroleum coke as primary fuels, and to a lesser extent natural gas and fuel oil.
Selected waste and by-products with recoverable calorific value can be used as
fuels in a cement kiln (referred to as co-processing), replacing a portion of
conventional fossil fuels, like coal, if they meet strict specifications. Selected
waste and by-products containing useful minerals such as calcium, silica, alumina,
and iron can be used as raw materials in the kiln, replacing raw materials such as
clay, shale, and limestone. Because some materials have both useful mineral
content and recoverable calorific value, the distinction between alternative fuels
and raw materials is not always clear. For example, sewage sludge has a low but
significant calorific value, and burns to give ash containing minerals useful in the
clinker matrix.
Normal operation of cement kilns provides combustion conditions which are
more than adequate for the destruction of even the most difficult to destroy
organic substances. This is primarily due to the very high temperatures of the kiln
gases (2000 °C in the combustion gas from the main burners and 1100 °C in the
gas from the burners in the precalciner). The gas residence time at high
temperature in the rotary kiln is of the order of 5–10 seconds and in the
precalciner more than 3 seconds.
Due to bovine spongiform encephalopathy (BSE) in the European beef industry,
the use of animal-derived products to feed cattle is now severely restricted. Large
quantities of waste animal meat and bone meal (MBM), also known as animal
flour, have to be safely disposed of or transformed. The production of cement
kilns, together with the incineration, is to date one of the two main ways to treat
this solid effluent of the food industry.