Instituto Tecnológico y de Estudios Superiores de Monterrey

Campus Monterrey

Design of Chemical Reactors

(Gpo 402)

Draft: State of the art

Professors:
Dr. Yasmany Mancilla Méndez
Dr. José Luis López Salinas

Team 3

Fernanda Quevedo Maluy A01571027

Regina España Ramírez A00832222
Jocelyn Grisel García González A01368290
María Fernanda Ponce de León Amador A01412723
Ariadna Noli Aguilar A00572363

September 3rd 2023, Monterrey, N.L

A. Investigate information about the global and national production and
consumption of cement. Include prices, trend and some of the most important
companies that produce cement.

Cement or Hydraulic binder is an inorganic material composed mainly of lime,

alumina, iron and silica when these components are mixed with water they form
calcium silicate. This material is very popular within the construction sector.
According to OEC (The observatory of Economic Complexity), global cement
statistics show that it was the 271 most traded product with a total of $14.8MM,
among the main exporters of 2021 are Vietnam, Turkey, United Arab Emirates,
Germany and Thailand and the main importers of 2021 are United States, China,
Bangladesh, France and Philippines.

Figure 1. Global Exporters of cement

DENUE (National Statistical Directory of Economic Units) states that the statistics on
the cement industry in Mexico 2019 had a total gross production of $121,640M MAX,
and the main states with the highest production were Hidalgo ($17,280M MX) and
Puebla ($11,520M MX ).

Figure 2. National distribution of total gross production of cement

The most important companies that produce cement

1. Holcim group / LafargeHolcim (Switzerland)
○ Annual Cement Production: 286.6 million tonnes/yr
○ Cement Production Capacity: 386.5 mt/yr
2. Anhui Conch Cement (China)
○ Annual Cement Production: 217.2 mt/yr
 ○ Cement Production Capacity: 288 mt/yr
3. Heidelberg Cement (Germany)
○ Annual Cement Production: 121.11 mt/yr
○ Cement Production Capacity: 129 mt/yr
4. Cemex (Mexico)
○ Annual Cement Production: 87.09 mt/yr
○ Cement Production Capacity: 93 mt/yr

B. Investigate different processes for cement production and describe them. Here
focus the chemical reaction(s) and kind of reactor that is used for each
process.

1. Wet Process of Cement Manufacturing

The wet process is an older way of manufacturing cement as by now it has been improved,
however since it’s of simple operation, low dust and easy conveying it’s still used in some
countries. The procedure is as follows:

a. Quarrying and Crushing: Extraction of raw materials from quarries and

crushed into smaller pieces.
b. Mixing and Grinding: They form a slurry, adding water to the crushed
materials in a grinding mill.
c. Blending and Homogenization: To adjust the chemical composition,
sand or shale is added to the slurry in a storage tank.
d. Preheating and Pre-calcining: The slurry is moved into a preheater in
order to remove the moisture and preheat, then to start the calcination
process the mix is moved into a pre-calciner.
𝐶𝑎𝐶𝑂3 −−> 𝐶𝑎𝑂 + 𝐶𝑂2
𝑀𝑔𝐶𝑂3 −−> 𝐶𝑎𝑂 + 𝐶𝑂2
e. Burning and Clinkerization: The preheated slurry is moved into a kiln
where it is heated to very high temperatures and it reacts, forming a
clinker.
f. Cooling: The clinker is cooled by air or water in a rotary cooler.
g. Grinding: The clinker is grounded with Gypsum and additional additives
to finally produce cement powder.
h. Storage and Packaging: The cement powder is stored in silos and
finally packed in bags for distribution.

2. Dry Process for Cement Production

This process involves grinding and mixing raw materials, usually limestone and clay, into a
powder and then heating the mixture to a temperature that causes the raw materials to react
and form a clinker material. The process occurs in four main stages:
 a. Mixing of raw materials: The raw materials are crushed in gyratory
crushers, once crushed, they are again grinded to get fine particles into
ball or tube mill. 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 a rotary kiln.
b. Burning: It is carried out in the rotary kiln, the raw mix of dry process of
corrected slurry of wet process is injected into the kiln from the upper
end. The kiln is heated with either powder coal or oil from the lower end
of the kiln so that the long hot flames are produced. The material charged
from the upper end moves towards the lower end, in the upper part water
is evaporated, this process is known as the Drying Zone. In the
calcination zone is where the decomposition of limestone takes place, the
remaining material is in the form of small lumps known as modules after
the 𝐶𝑂2 is released.
𝐶𝑎𝐶𝑂3 = 𝐶𝑎𝑂 + 𝐶𝑂2
In the lower part, lime and clay react to yielding calcium aluminates and
calcium silicates which then fuse together to form small and hard stones
known as clinkers.
2𝐶𝑎𝑂 + 𝑆𝑖𝑂2 = 𝐶𝑎2𝑆𝑖𝑂4 (𝑑𝑒𝑐𝑙𝑎𝑖𝑚 𝑠𝑖𝑙𝑖𝑐𝑎𝑡𝑒 (𝐶2𝑆))
3𝐶𝑎𝑂 + 𝑆𝑖𝑂2 = 𝐶𝑎3𝑆𝑖𝑂5 (𝑡𝑟𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝑠𝑖𝑙𝑖𝑐𝑎𝑡𝑒 (𝐶3𝑆))
3𝐶𝑎𝑂 + 𝐴𝑙2𝑂3 = 𝐶𝑎3𝐴𝑙2𝑂6 (𝑑𝑖𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝑎𝑙𝑢𝑚𝑖𝑛𝑎𝑡𝑒 (𝐶2𝐴𝑙))
4𝐶𝑎𝑂 + 𝐴𝑙2𝑂3 + 𝐹𝑒2𝑂3 = 𝐶𝑎4𝐴𝑙2𝐹𝑒2𝑂10 (𝑡𝑒𝑡𝑟𝑎𝑐𝑎𝑙𝑐𝑖𝑢𝑚 𝑎𝑙𝑢𝑚𝑖𝑛𝑜𝑓𝑒𝑟𝑟𝑖𝑡𝑒 (𝐶4𝐴𝑙𝐹))
To bring down the temperature of the clinkers, air is admitted in the
countercurrent direction at the base of the rotary kiln.
c. Grinding: the clinkers are grinded finely into powder in ball mill or tube
mill. Powdered gypsum is added as a retarding agent during final
grinding, the final product is cement that does not settle quickly when it
comes in contact with water. After the initial setting time of the cement, it
becomes stiff and the gypsum retards the dissolution of tricalcium
aluminates by forming tricalcium sulfoaluminate which is insoluble and
prevents too early further reaction of setting and hardening.
3𝐶𝑎𝑂. 𝐴𝑙2𝑂3 + 𝑥𝐶𝑎𝑆𝑂4. 7𝐻2𝑂 = 3𝐶𝑎𝑂. 𝐴𝑙2𝑂3. 𝑥𝐶𝑎𝑆𝑂4. 7𝐻2𝑂
d. Storage and packaging: The grinded cement is stored in silos, from
which it is then marketed in container loads.

3. Semi-dry Process for Cement production

In the same way that the dry-process are built for cement production, in the semi-dry
process, the raw materials are crushed and then fed into the grinding mill in
proportionate quantities; then, this raw materials are to be dried in the first kiln and
reduced to a fine powder so it could be strained meticulously and fed into the rotating
dish of a semi-dry process on a granulator; the corresponding quantity of water
would be 12% of the feed added and it should be added and the same time. In this
phase of the process, a hard kind and size of a marble (15 mm of a diameter) is
formed which is considered important and it follows the procedure as a cold powder
is fed into the kiln.
These marbles enter the kiln at 1450°C and the total coal used in this process is
 between 100-200 kg but it depends on the elements and specifications in producing
a ton of cement in the wet process. After a series of chemical reactions, the
dry-material will be introduced to the hottest part of the kiln. And so, 20-30% of it will
become liquid while lime, silica and alumina are recombining. At the end, the fused
mass is turned into pellets of 3-25 mm of diameter and it is called clinker.

4. Semi-wet Process for Cement production

This process is very similar to the wet process, the raw meal got shaped into wet
cakes but it is necessary to reduce the water content about 15- 20 percent before
feeding it into the kiln. This process has a heat consumption of 1000-1200 kcal/kg
clinker.

The advantage of using this method is the fuel saving that even wet grinding is
necessary, because of the characteristics of the raw material used. However, this method
has not been used much in industry since the additional energy required and the high
maintenance cost of slurry filtration units.

C. Investigate the different unit operations and elaborate a general PFD for the
cement process
Stage of the cement manufacture
1. Material Exploitation: The raw cement necessary for the production of
cement are limestone (calcium), sand and clay (silicon, aluminum, iron),
quarries are exploited and extracted.
2. Raw Material Transportation: They are transported to the plant by means of
dump trucks.
3. Crushing: In this process, the size of the limestone and marl is reduced to a
granulometry of 1.5 inches.
4. Pre Homogenization: The crushed matter is prepared with additives and to
have a fine and homogeneous mixture.
5. Transportation and storage: It is stored in a silio and taken to a raw mill and
dosed depending on the desired properties of the cement (Generally,
limestone is 80%, and the remaining 20% is clay)
6. Raw material grinding: Vertical steel mill, by means of pressure the rollers
pulverize.
7. Homogenization: Silos equipped to achieve a homogeneous mixture, it is
introduced above the exchanger tower.
8. Calcination: Clinker (calcium and silicon dioxide) is produced, by means of
which the mixture advances into the interior of the kiln, which has the
following process:
9. Calcination: Clinker (calcium and silicon dioxide) is produced, by means of
which the mixture advances into the interior of the kiln, which has the
following process:
a. Water evaporation (100ºC)
b. Dehydration and formation of silicon, aluminum and iron oxides
(100°C -430°C):
c. Cement clinker is formed 1510 °C
10. Cooling Chamber: After leaving the kiln, the clinker is rapidly cooled from
2000°C to 100°C to 200°C by passing air over it.
 11. Clinker grinding: Additives such as plaster are combined to give it
resistance and avoid agglomeration and the final product is cement.
12. Cement storage: stored in silos (packaged in 20-40 kg bags)

Figure 3. Diagram of cement process

D. Investigate rate laws and kinetic parameters for the reactions that you are
going to use for this challenge; this must be a multiple reaction system.

Decarbonation
Equation:
𝐶𝑎𝐶𝑂3 → 𝐶𝑎𝑂 + 𝐶𝑂2
where 𝐶𝑎𝐶𝑂3 is limestone and 𝐶𝑎𝑂 is Lime; this reaction can be performed by Superheat
influence
rate law and kinetic parameters
∆𝑀𝑐
− 𝑟𝐴 = 𝑡
∆𝑀𝑐
where the 𝑡
represented the decarbonization weights against time
Calcination:
−1
The activation energy and exponential factor for the reaction is 19.7 kJ 𝑚𝑜𝑙 and 295.8 min
−1
𝑘𝑃𝑎 respectively and to express the calcination reaction it exits a linear fit:
1/3
𝐺(𝑥) = 1(1 − 𝑥) .
According to the paper “Determination of carbonation/calcination reaction kinetics of a
limestone sorbent in low CO2 partial pressures using TGA Experiments” leaded by the
Research Centre for Frontier Energy Technologies & Utilisation, different investigators have
determined the different systems and order of reaction for the development of cement, this
information is presented on the next table:

Building this analysis, the research program could interpret the function for the change of
molar fractions of the components for calcination according on the variation of pressure is:
𝑑𝑥 𝑛
𝑑𝑡
𝑘 𝑓(𝑥) (𝑃𝐶𝑂2 − 𝑃𝐶𝑂2,𝑒𝑞)
Where n is the reaction order, f(x) and represents the mechanism of the reaction and k is the
rate constant; applying this model to the arrhenius-type equation we get:
−𝐸
𝑘 = 𝑘0𝑒𝑥𝑝( 𝑅𝑇 )

Hydration
It is known that cement hydration is a complex process; therefore, many researchers have
obtained different empirical formulas to predict its behavior. It has been established that to
describe the process it is necessary to suppose that cement and water passes through a
two-stage consecutive reactions.
Quantity of hydration product as a function of time can be described as

Where
m0= mass of initial cement paste

Although there is no a method to determine the quantity of hydrated cement, it exists the
possibility to study the change of properties, like compressive strength or the heat
generation in that time, and they can’t described with the following formula:

Where:
A and A0=compressive strengths
t=time
The Budapest Technical University did experiments with Portland cement, which has a
composition of 45% C3S 24.5% of C2S 12.9% of C3A and 7.1% of C4AF obtaining the
following graph:

Figures 4 and 5: Calorimetry data 70% blast furnace and 30% clinker. the curve indicates temperature vs time,
which is the heat evolution using Eq(2)

References
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manufacturing?optionsSelector1=Total%20Gross%20Production
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