DESIGN OF A PRODUCTION REACTOR: MAGNESIUM OXIDE

DANIEL MORENO CAÑAVERAL

Chemical engineering student
Universidad de Antioquia

KAREN DAHIANA RENDÓN ARBELÁEZ

Chemical engineering student
Universidad de Antioquia

VALENTINA PACHÓN LEAL

Chemical engineering student
Universidad de Antioquia

Professor: Aida Luz Villa Holguín

Chemical reaction engineering, Chemical engineering department, Engineering faculty.
________________________________________________________________________________
ABSTRACT
In the following work the main production processes of Magnesium Oxide (MgO) available are
consulted; the routes analyzed were (1) calcination of magnesite, (2) calcination of magnesium
hydroxide, and (3) Magnesium Chloride Pyrohydrolysis (Aman Process). Once the main processes
were identified together with their respective reagents and products, their physical and chemical
properties were consulted. Once the nature of the substances to be handled and the reactions involved
are known, the three routes are compared taking into account parameters such as efficiency, costs,
complexity, energy use, safety, added value, among others, in order to define the most convenient,
Magnesium is selected. Chloride Pyrohydrolysis (Aman Process) as production process. Once the
above is defined, the reaction rate equation and the reaction rate constants as a function of temperature
are consulted, the annual production capacity is defined based on similar processes, the national
demand and the operating conditions are defined (temperature, pressure, concentration, conversion)
based on a design at the laboratory level, finally the reactor to be used is defined as a non-isothermal
and isobaric semibatch.
Keywords:
Magnesium oxide, Reaction kinetics, Process design, Chemical routes.
________________________________________________________________________________
INTRODUCTION
Magnesium oxide has long been an important industrial material. The major tonnage outlet for
magnesia has been the refractories industry in which it is employed as 'dead-burned' grain magnesite
for the construction and maintenance of the hearths or bottoms of open-hearth steel furnaces.
Magnesia is also used in the form of calcined refractory magnesite brick and as a chemical addition
in the manufacture of chrome, olivine and other refractories, another uses include areas as medicine,
cosmetics, heating industry and animal feed. (Shand, M. A. ,2006) Magnesium is the eighth most
abundant element in Earth’s crust, at ~2.3% by weight, present in a range of rock formations such as

Design of a production reactor: Magnesium oxide 1

dolomite, magnesite and silicate, is also the third most abundant element in solution in seawater, with
concentrations of ~1300 ppm, this is why, worldwide, the most used production processes focus on
the magnesium sources mentioned above (Nobre et al., 2020). It is reported that in Colombia, the
amount of this compound imported compared to exported is much higher, so it is advisable to consider
strengthening the national industry in this area by producing it locally. Due to its importance in
industry and the associated benefits, the design and optimization of a reactor to produce magnesium
oxide is of great interest.
1. INFORMATION ABOUT THE PROCESS/PRODUCT OF INTEREST.

1.1. At least three chemical routes to obtain the product of interest, that is, the reactions and
operating conditions of the reaction system (such as reagents, products, catalyst, temperatures,
pressure).
The main processes to produce the magnesium oxide include the following routes:
1.1.1. Route 1: Calcination of Magnesite
Magnesite is a white mineral composed of magnesium carbonate crystals, it can be found in nature
between layers of metamorphic rock and the regolith of the earth. However, it is obtained on a large
scale from the decomposition of dolomite, a mixed calcium and magnesium carbonate
(𝐶𝑎𝑀𝑔(𝐶𝑂3 )2 ) that is burned at temperatures between 800 and 850°C in a CO 2 atmosphere to
separate the carbonates. Magnesite is a white mineral composed of magnesium carbonate crystals, it
can be found in nature between layers of metamorphic rock and the regolith of the earth. However, it
is obtained on a large scale from the decomposition of dolomite, a mixed calcium and magnesium
carbonate (𝐶𝑎𝑀𝑔(𝐶𝑂3 )2 ) that is burned at temperatures between 800 and 850°C in a CO2 atmosphere
to separate the carbonates. (Viswanathan et al., 1979)

𝐶𝑎𝑀𝑔(𝐶𝑂3 )2 → 𝐶𝑎𝐶𝑂3 + 𝑀𝑔𝐶𝑂3

Then from the decomposition of magnesium carbonate, magnesium oxide is obtained:

𝑀𝑔𝐶𝑂3 → 𝑀𝑔𝑂 + 𝐶𝑂2

For calcination, a shaft, rotary or multiple hearth furnace is used at a controlled temperature that
operates between 700 and 1000°C (Nobre et al., 2020b), the calcination temperature influences the
reactivity of the compound. obtained and the product of light calcination (870-1000 °C) is called
caustic magnesia, this has a greater surface area and greater reactivity, or very calcined (1550 - 1650
°C). To magnesium oxide (Al-Tabbaa, A. (2013). Eco-efficient concrete: 19. Reactive magnesia
cement. Elsevier Inc. Chapters.)
Calcination conditions must be carefully tailored to the contaminants in the feed, otherwise overfiring
results in excessive growth of reactive MgO crystals, reducing their activity.
Its MgO content ranges from ca. from 65 to 99% by weight, and may even reach 99.9%, this depends
on the purification to which the stone is subjected before or after calcination, in addition to the MgO
content in the mineral. The patent (Russell Pearce, 1967) explains some methods to obtain magnesium
oxide with a high purity, approximately 97% wt.
The full decomposition of 1.0 kg of pure magnesite yields 0.48 kg magnesium oxide and 0.52 kg of
carbon dioxide. It will, therefore, require 2.08 kg of pure magnesite to yield 1.0 kg of magnesium
oxide. There are three essential factors in the kinetics of magnesite decomposition.

Design of a production reactor: Magnesium oxide 2

1. The magnesite rock must be heated to the decomposition temperature.
2. This minimum temperature must be maintained for a certain duration, that is, until the magnesite
has been essentially decomposed to magnesium oxide.
3. The carbon dioxide gas evolved during the decomposition must be removed from the kiln to
increase the rate of decomposition.
If the temperature and pressure are in equilibrium, then dissociation is static. However, if there is a
small change in either of these variables, such as a decrease in CO 2 pressure or concentration, or an
increase in temperature, dissociation proceeds immediately with the evolution of CO2 gas and the
simultaneous formation of magnesium oxide. The temperature at which the dissociation pressure of
MgCO3 reaches one atmosphere has been reported to be between 402 and 7508°C. In practice, to
accelerate the dissociation of magnesite, temperatures significantly above the minimum dissociation
temperature are maintained until all the CO2 has been expelled (Shand, M. A. ,2006).
1.1.2. Route 2: Calcination of magnesium hydroxide
Obtaining magnesium oxide from magnesium hydroxide by calcination can be represented by the
following chemical reaction:
𝑀𝑔(𝑂𝐻)2(𝑠) + 𝐻𝑒𝑎𝑡 → 𝑀𝑔𝑂(𝑠) + 𝐻2 𝑂(𝑔)

The reaction occurs at high temperatures, around 350-400°C, in a carbon dioxide (CO2) free
environment. Magnesium hydroxide thermally decomposes into magnesium oxide and water, and
removal of carbon dioxide is necessary to prevent the formation of magnesium carbonate in the final
product. The reaction is exothermic and therefore does not require a catalyst. Operating conditions
include an inert atmosphere, typically nitrogen or argon gas, to prevent oxidation of the material and
contamination of the final product. (Shand, M. A. ,2006).
It is important to mention that the purity of the magnesium hydroxide used in the reaction directly
affects the purity of the magnesium oxide obtained. Therefore, the use of high purity magnesium
hydroxide is recommended. (Chadwick, S. S. ,1988).
High pressures are not required to carry out this reaction. The reaction is carried out at atmospheric
pressure, and in some cases, it can be carried out under vacuum or in inert atmospheres such as
nitrogen or argon.
Heat exchange furnaces are also used for magnesium hydroxide; where the dehydrated filter cakes
are generally calcined in the form of lumps at about 950 °C in multiple hearth furnaces (The
decomposition reaction starts from 350 °C). The material is continuously introduced into the upper
part of the kiln and its residence time can be adjusted through the rake that rotates on each hearth. In
modern gas slurry furnaces, Mg (OH)2 or flotation concentrate can be converted into homogeneous
caustic magnesia, energy consumption is low. (Chadwick, S. S.,1988).
Operating conditions:
Temperature: Calcination is performed at high temperatures, typically between 350-400°C, which
allows the magnesium hydroxide to thermally decompose into magnesium oxide and water.
Residence time: The residence time depends on the amount of magnesium hydroxide and the capacity
of the furnace used for calcination. Usually, a time of 1-2 hours is considered.

Design of a production reactor: Magnesium oxide 3

Atmosphere: It is necessary to carry out calcination in an inert atmosphere to prevent oxidation of the
material and contamination of the final product. The most common gas used is nitrogen or argon.
Removal of carbon dioxide: Carbon dioxide can affect the reaction and lead to the formation of
magnesium carbonate, so complete removal of this gas is required during calcination.
Agitation: Agitation of the material in the oven is important to ensure even temperature distribution
and to avoid the formation of lumps or agglomerates.
1.1.3. Route 3: Magnesium chloride pyrohydrolysis (Aman Process)
In this process, the primary source of magnesium is brine obtained from seawater. This brine must be
purified beforehand to separate the other electrolytes present in the mixture. This is done to prevent
the formation of potassium chloride in the reactor during pyrohydrolysis, as other salts can reduce the
efficiency of the process and the quality of the produced MgO. Seawater can be considered in this
case as a mixture of potassium, calcium, and magnesium chlorides from which magnesium is to be
purified.
There are different methods for the extraction of MgCl2. One method involves the use of mixed ionic
extraction systems with quaternary and primary ammonium naphthenes in toluene as extractive
substances. Another method involves the use of solar energy to vaporize a dynamic stream of pre-
concentrated seawater flowing along an Inclined Salt Preferential Separator. Other methods include
spray atomization, two-stage dehydration, and electrolysis of molten salts. Some methods involve the
use of carbonaceous material and a mixture of chlorine and air to purify magnesium chloride. In
addition, a modified multistage flash evaporation system and the Dow process can be used to extract
magnesium chloride from seawater (Nalajala et al., 2022).
Reaction: The MgCl2 brine is fed into a high-temperature reactor (usually around 600°C) for
pyrohydrolysis. During pyrohydrolysis, MgCl2 thermally decomposes into magnesium oxide (MgO)
and hydrogen chloride (HCl), according to the following reaction:
MgCl2 (ac) + H2O (l) → MgO (s) + 2HCl (g)
Cleaning of products: The produced MgO and HCl generated in the reactor are cooled and passed
through a washing system with water to remove by-products. The water is agitated in a tank, and the
MgO settles at the bottom. The water is decanted, and the MgO is recovered.
It is important to note that no catalyst is used in this process. The reported operating conditions for
this process are 5.5 atm and 550°C. Additionally, it may be necessary to add a dehydrating agent,
such as calcium chloride (CaCl2), to the MgCl2 brine to reduce water content and prevent the
formation of hydrated complexes during pyrohydrolysis.

Design of a production reactor: Magnesium oxide 4

1.2. Complete tables 1,2 and 3 for each of the processes required for the chemical pathways identified in the synthesis of the product of interest
and include the respective flow chart for each process.
Route 1
Table 1 Properties of the calcination magnesite route

Compoud 𝐶𝑎𝑀𝑔(𝐶𝑂3 )2 𝐶𝑎𝐶𝑂3 𝑀𝑔𝐶𝑂3 𝐶𝑂2

Uses It can be used as a It is used as a It is used in It has various uses,
stone for buildings; filler for paper industries such in security (fire
due to their chemical and plastics, in as extinguishers), as a
properties, we can the basic pharmaceutical, supercritical
use them in the chemical beauty, health medium (liquid
manufacture of industry, in and medicine, liquid extractions),
Portland cement or paint, adhesives, acts as an for food, in
lime; plastics; the glass absorbent, agriculture,
paintings; tooth industry, binder, anti- medicine, energy,
powders; antacid; in ceramics, caking agent, cleaning and water
the removal of sulfur cosmetics, and bleaching agent treatment.(¿Qué
dioxide from the and opacifying usos tiene el CO2,
combustion gases and pharmaceutical agent, is used in 2023)
production of carbon industry; It is a variety of
dioxide; among also used for personal care
others. The variety of animal feed. products,
black dolomite is (Blancaley, s. f.) including hair
used mainly in the care, skin care
glass industry and and general body
iron foundry; while care. (Las
white dolomite, in principales
addition to being aplicaciones y
used in the glass usos del
industry and iron carbonato de
foundry, is also used magnesio, 2021)
in the balanced food

Design of a production reactor: Magnesium oxide 5

 and ceramics
industry. (Secretaria
de economía &
Subsecretaría de
minería, s. f.)
Updated price per kg of the compound 0.018 US$ (White 250,43 US$ 118,29 US$ 26 US$ (Food
Dolomite Powder, (Calcium (Magnesium grade CO2,s.f.)
s. f.) Carbonate, s. f.) carbonate, s.f.)
Purity with which it is obtained in the market 99% (White Dolomite ≥99.0%, powder heavy, ≥40% 99% (Food grade
Powder, s. f.) (Calcium (MgO) CO2,s.f.)
Carbonate, s. f.) (Magnesium
carbonate, s.f.
Phases present during the reaction (gas, liquid and/or solid) Solid Solid Solid Gas
Molecular weight 184 g/mol 100.0869 g/mol 84.31 g/mol 44.01 g/mol
Identification C.A.S 16389-88-1 471-34-1 546-93-0 124-38-9
Normal melting point 730-760 °C 1339°C 350°C -55.6 °C (at 5.2
(Yaws,2015) (Yaws,2015) (Perry,1994) atm) (Perry,1994)
Normal boiling point Not reported 2850°C 1185°C -78.46 °C
(Yaws,2015) (Kobayashi,2003 (Perry,1994)
)
Standard enthalpy of formation [kJ/mol] -2338.0192 -1211.268 -641.0724 -393.5135
(Perry,1994) (Perry,1994) (Perry,1994) (Perry,1994)
Gibbs free energy of standard formation [kJ/m -2161.7 (Perry,1994) -1133.0272 -601.5336 -394.3838
(Perry,1994) (Perry,1994) (Perry,1994)
Vapor pressure in terms of temperature Not reported Not reported 0.0000026 𝑃𝑣𝑎𝑝 [𝑃𝑎]
mmHg 𝐶2
(Yaws,2015) = exp [𝐶1 + ( )
𝑇
+ 𝐶3 𝑙𝑛(𝑇)
+ 𝐶4 𝑇 𝐶5 ]
C1 = 124389
C2 = 140.54
C3 = -4735
C4 = 4.0909E−02

Design of a production reactor: Magnesium oxide 6

 C5 = 1
Tmin = 216.58K
Tmax = 304.21K
T in K (perry)
Density in terms of temperature 1 167 lb/ft3 a 25°C 2.7-2.9 g/cm3 3.0500 g/mL 𝑘𝑚𝑜𝑙
(Perry,1994) (sólido) (sólido) 𝜌[ 3 ]
𝑚
(Yaws,2015) (Yaws,2015) 𝐶1
= 𝐶4
𝑇
[1+(1−𝐶 ) ]
3
𝐶2
C1 = 2.768
C2 = 0.26212
C3 = 304.21
C4 = 0.2908
Tmin = 216.58K
Tmax= 304.21K
T in K
(Perry,1994)
Heat capacity in terms of temperature 1 Figure 6 shows 𝑐𝑎𝑙 𝐽 𝑐𝑎𝑙
𝐶𝑝 [ ] 𝐶𝑝 [ ] 𝐶𝑝 [ ]
values of the 𝑚𝑜𝑙°𝐶 𝑚𝑜𝑙𝐾 𝑚𝑜𝑙°𝐶
behavior of the = 19.68 = 𝐴 + 𝐵𝑇 = 10.34
calorific capacity + 0.01189𝑇 + 𝐶𝑇 2 + 𝐷𝑇 3 + 0.00274𝑇
2
with the change of − 307600𝑇 + 𝐸𝑇 4 + 𝐹𝑇 5 195500
−
temperature. (Stout & T in K + 𝐺𝑇 6 𝑇2
Robie, 1963) In a range of A = -42.0596 T en K
273-1033K B = 0.9331 In a range of 273-
(Perry,1994) C = -0.0032 1200K
D = 7.1995e-6 (Perry,1994)
E = -8.9232
F = 5.7728e-12
G = -1.5147e-15
T in K
(Perry,1994)

Design of a production reactor: Magnesium oxide 7

Heat of vaporization in terms of temperature Not reported Not reported Not reported 𝐽
∆𝐻𝑣 [ ]
𝑘𝑚𝑜𝑙
= 𝐶1 (1
− 𝑇𝑟 )𝐶2 +𝐶3 𝑇𝑟 +𝐶4𝑇𝑟𝑇𝑟
C1 = 2.1730 e+7
C2 = 0.382
C3 = -0.4339
C4 = 0.42213
𝑇
𝑇𝑟 =
𝑇𝑐
Tmin = 216.58K
Tmax = 304.21K
T in K
(Perry,1994)
Temperature Not reported Not reported Not reported 304.21
(Yaws,2015)
Critical properties Pressure Not reported Not reported Not reported 7.39 e+6 Pa
(Yaws,2015)
Volume Not reported Not reported Not reported 0.095 m3/kmol
(Yaws,2015)
Density Not reported Not reported Not reported 0.468 g/cm³
(Yaws,2015)
Thermal conductivity in terms of temperature 1 1.0 Btu/(hft2) (°F/ft) 2.4-3 W/mK 1.63 W/mK a 0.0129 W/mK a
(Yaws,2015) (Yaws,2015) 25°C 250K
(Perry,1994) 0.0166 W/mK a
300K
0.0244 W/mK a
400K
0.0323 W/mK a
500K
0.0403 W/mK a
600K
(Perry,1994)
Viscosity in terms of temperature 1 Not reported Not reported Not reported 0.126 Pa.s a 250K

Design of a production reactor: Magnesium oxide 8

 0.150 Pa.s a 300K
0.196 Pa.s a 400K
0.239 Pa.s a 500K
0.278 Pa.s a 600K
*Viscosity values
are 10-6 (multiply
by 106
Diffusivity in terms of temperature 2 Not reported 0.01-0.015 cm2/s Not reported 0.138 cm2/s a 0°C
(a 20°) (Perry,1994)
(Yaws,2015)
Toxicity Inhalation may cause It does not cause May cause Carbon dioxide
sneezing and mild eye or skin irritation to eyes can affect you
irritation. Very high irritation, and respiratory when inhaled.
concentrations can however, high tract. Lungs may Contact can irritate
irritate the respiratory calcium levels be affected by and burn the skin
system. Ingestion of can cause serious prolonged or and eyes. Direct
large amounts may heart rhythm repeated contact with liquid
result in intestinal disturbances, as exposure to dust or solid (dry ice)
obstruction. well as kidney particles. (Safety can cause frostbite.
Considered low stones and Data Sheet, Exposure to carbon
toxicity. Dolomite damage to Magnesium dioxide can cause
may cause dry skin, kidney function. Carbonate, headache,
abrasions, Long-term 2010) dizziness,
discomfort, and overuse is often shortness of breath,
irritation. Tearing and more serious and tremors.
slight irritation, than a single Higher exposure
Redness and overdose.(Safety can cause seizures,
temporary Data Sheet coma, and death.
pain.(Ficha de datos Calcium Acute poisoning
de seguridad, Carbonate, can affect the brain
Dolomite, 2021) 2021) causing personality
changes and loss of
vision. (Safety
Data Sheet, CO2,

Design of a production reactor: Magnesium oxide 9

 2008)
Reactivity Stable. Avoid contact Stable under This material is The product is
with incompatible normal not reactive chemically stable
materials, dissolves conditions, avoid under normal under standard
in Hydrofluoric Acid, high environmental environmental
producing corrosive temperatures, it conditions. The conditions (room
gaseous Silicon is incompatible material is stable temperature).
Tetrafluoride. with strong under normal Risk of explosion
Silicates can react oxidizing agents environmental with: Powdered
with powerful and acids.(Safety conditions and metals Peroxides
oxidants, such as Data Sheet under (sodium salt)
Fluorides, Boron Calcium foreseeable Risk of ignition or
Trifluoride, Chlorine Carbonate, conditions of formation of
Trifluoride and 2021) temperature and flammable gases or
Manganese pressure during vapors with:
Trifluoride and storage and acetylidene barium
Oxygen Difluoride. handling. (Safety peroxide metal
(Ficha de datos de Data Sheet, oxides lithium
seguridad, Dolomite, Magnesium lithium aluminum
2021) Carbonate, hydride sodium
2010) exothermic
reaction with:
amines ammonia
strong bases
polymerizable
acrylic aldehyde.
(Safety Data Sheet,
CO2, 2008)
Recommendations for storage and transport Caution with Keep containers Keep away from When transporting
incompatible tightly closed in heat. by road and/or by
products and avoid a dry, cool and It is an oxidising vehicle, secure the
excess heat. (Ficha well-ventilated material and can pallets with ropes
de datos de place. Do not have a strong and unique sheets
seguridad, Dolomite, transport with reaction in the so that the

Design of a production reactor: Magnesium oxide 10

 2021) incompatible presence of shipment does not
materials.(Safety acids. shift. Similarly, the
Data Sheet The material is car or truck must
Calcium stable under have good
Carbonate, normal ventilation and
2021) environmental enough space for
conditions and an electric forklift.
under At the same time,
foreseeable when it comes to
conditions of storage, it is vital
temperature and to keep the bottles
pressure during out of direct
storage and sunlight to avoid a
handling. rise in temperature,
Keep containers which will
tightly closed in eventually cause
a cool, dry and an increase in
well-ventilated pressure. You
place. (Safety should also keep
Data Sheet, bottles away from
Magnesium corrosive
Carbonate, atmospheres and
2010) make sure they are
properly labeled.
(Clindros
CO2,2022)
Inflamability Flash point Not reported (solid) Not reported Not reported Not reported
(solid) (solid)
LFL (Lower flamability Not reported (solid) Not reported Not reported Not reported
limit) (solid) (solid)
UFL (Upper flamability Not reported (solid) Not reported Not reported Not reported
limit) (solid) (solid)
Particle size No aplica No aplica No aplica No aplica

Design of a production reactor: Magnesium oxide 11

1
In the state in which it is found in the reaction.
2
For liquid substances respecting to water, for gaseous substances respecting to air.
3
For the catalyst

Figure 1 Flow chart of the calcination process of magnesite to obtain MgO. (Russell Pearce, 1967)

Route 2
Table 2 . Properties of the calcination route of magnesium hydroxide to obtain MgO.

Compound Mg (OH)2 MgO H2 O

Uses Active phase and Solvent
It is used in the catalyst support Facilitator of life on earth
manufacture of Manufacture of Raw material for the
halogen-free refractory materials production of green
thermoplastic and Additive in the hydrogen

Design of a production reactor: Magnesium oxide 12

 thermosetting manufacture of
compounds to obtain concrete (Nobre et al.,
properties of fire 2020)
resistance and low
smoke emission, as
well as a reduction in
the toxicity of the gases
generated during
combustion.
It can also be used as
an antacid or laxative
and as a neutralizing
agent in food
production. (Chadwick,
S. S. ,1988).
Updated price per kg of the compound Analytical
16-24US$ per Kg grade:14400 $USD
In the city of Medellín, the
.(99.5% of purity) (>99.99% w/w,
price per cubic meter of
(Alibaba, n.d) Sigma Aldrich)
aqueduct water at
industrial rate is 5262.08
Alimentary
$COP (EPM data, March
grade:6,25 $USD
2023).
(~50% w/w,
PipingRock.Com)
Purity in which it is obtained in the market EPM© certifies that the
According to your
≥ 95% water from its aqueducts
requirements, up to
Product of synthetic contains amounts below
99.99% purity by
manufacture of 99% the maximum regulated by
weight can be
purity. law of: CaCO3, Cl2, Cl-,
obtained as a
nitrates, nitrites, Sulfates,
laboratory reagent.
Aluminum and Iron
Phases present during the reaction (gas, liquid and/or Solid
solid) Solid Gas
Molecular weight 58.3197 g/mol 40.3044 g/mol 18.01528 g/mol

Design of a production reactor: Magnesium oxide 13

Identification C.A.S 1309-42-08 1309-48-4 7732-18-5
Normal melting point 350 °C 2850°C 0°C
Normal boiling point Not reported 3600°C 100°C
Standard enthalpy of formation [kJ/mol] -924.7 kJ/mol (NIST) Liquid: -285.83
-601.24 kJ/mol
Steam: -241.83
(NIST)
(NIST)
Gibbs free energy of standard formation [kJ/m -833.7 kJ/mol (NIST) Liquid: -237.14
-596.30 kJ/mol
Steam: -228.613
(NIST)
(NIST)
Vapor pressure in terms of temperature Not reported log10 (𝑃𝑣𝑎𝑝 ) 𝐵
log10 (𝑃𝑣𝑎𝑝 ) = 𝐴 −
𝐵 𝑇+𝐶
=𝐴−
𝑇+𝐶
With Pvap in bar and T in
With Pvap in bar and K, the constants are:
T in K, the constants A = 3.5596
are:A = 6.9228 B = 643.748
B = 13826.21 C = -198.043
C = -170.464 Temperatures between 379
Temperatures and 573K (Nist)
between 2832 and
5677°C
(Yaws, 2015)
Density in terms of temperature 1 2.3446 g/cm3 (solid) 3.58 g/cm3 (solid) 𝑔
𝜌: 0.7986 @250°𝐶
𝑐𝑚3
Heat capacity in terms of temperature 1 𝐽 𝐽 𝐽
𝐶𝑝 [ ] 𝐶𝑝 [ ] 𝐶𝑝 [ ] = 𝐴 + 𝐵𝑇
𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐶𝑇 2
+ 𝐷𝑇 3 + 𝐸𝑇 −2 + 𝐷𝑇 3 + 𝐸𝑇 −2 + 𝐷𝑇 3
+ 𝐸𝑇 −2
A = 84.9034 A = 47.26
B = 74.44005 B = 6.682 A = -203.606
C = -68.92805 C = -0.87 B = 1529.290
D = 26.63242 D = 0.104 C = -3196.41
E = -2.174907 E = -1.054 D = 2474.455

Design of a production reactor: Magnesium oxide 14

 E = 3.855326
For temperatures For temperatures
between 298 and 1000 between 298 and For temperatures between
K (NIST) 3105K (NIST) 295 and 500K (NIST)
Heat of vaporization in terms of temperature Not reported 𝐽
∆𝐻𝑣 [ ]
𝑘𝑚𝑜𝑙
= 𝐶1 (1
− 𝑇𝑟 )𝐶2 +𝐶3 𝑇𝑟+𝐶4 𝑇𝑟 𝑇𝑟

C1 =5.2053 e+7
C2 = 0.3199
C3 = -0.212
Not reported (Solid) C4 = 0.25795
𝑇
𝑇𝑟 =
𝑇𝑐
Tmin = 273.16K
Tmax = 647.13K
T in K
(Yaws, 2009)
40,67 kJ/mol at 100 °C
and 1 atm

Temperature Not reported (solid) Not reported (solid) 647.2 K

Critical properties Pressure Not reported (solid) Not reported (solid) 220.64 bar
Volume Not reported (solid) Not reported (solid) 0,0578 m3/mol
Density Not reported (solid) Not reported (solid) 0.322 g/cm3
Thermal conductivity in terms of temperature 1 Not reported 𝑊 𝑊
𝑘 [ ] = 2.2442 ∙ 𝑘𝑙𝑖𝑞 [ ] = 𝐴 + 𝐵𝑇
𝑐𝑚 𝐾 𝑚𝐾
−5
10 𝑇 + 7.2095 ∙ + 𝐶𝑇 2
−3
10 Adjusted data Parameters of (Yaws,
from 2009) with T in K
(Touloukian et al., A = 0.29875
1971) B = 4.70537E-3
with T in K C = -5.6209E-6

Design of a production reactor: Magnesium oxide 15

 Range: 480 – 680K
For temperatures between
273.15 and 633.15 K
Viscosity in terms of temperature 1 Not reported
𝑠𝑙𝑢𝑔
𝜇[ ] = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2
𝑓𝑡 𝑠

Does not apply as it is A = -36.826

solid B = 4.29e-1
C = -1.62e-5

T between 280 and 1073K

(Yaws, 2009)
Diffusivity in terms of temperature 2 𝐷 = 2.29 ∙ 10−9 𝑚2 ⁄𝑠
Not reported
Not reported At 25°C with a
concentration of 0.001M
(N/A, s. f.) .
Toxicity
May cause defatting of
the skin, causing non-
allergic contact It presents a low risk
This compound is not
dermatitis and product of toxicity for humans
toxic to humans or the
absorption through the since it is easily
environment.
skin. Splashes in the digested
eyes can cause
irritation and reversible
damage.
Reactivity It exhibits high
It does not present a thermal and chemical
H2O is thermally and
danger due to its stability under dry
chemically stable
reactivity. It is unstable conditions, but readily
in contact with acids. reacts with water to

Design of a production reactor: Magnesium oxide 16

 form Mg (OH)2
Recommendations for storage and transport Keep away from food Store under normal
and drinks. It should be conditions in tanks, it can
stored in a dry place be transported in pipelines
Keep away from food
and later in a with pumps or
and drinks. It should
hermetically closed compressors depending on
be stored in a dry
container. Hygroscopic the phase in which it is
place and later in a
solid. transported. It is
hermetically closed
recommended to ensure
container.
the chemical and
Hygroscopic solid.
mechanical resistance of
the pipe, especially in case
it is transported as steam
Inflammability Flash point Not reported (solid) Not reported (solid) Not reported
LFL (Lower flamability limit) Not reported (solid) No inflamable No inflamable
UFL (Upper flamability limit) Not reported (solid) No inflamable No inflamable
Particle size Not applied Not applied Not applied

1
In the state in which it is found in the reaction.
2
For liquid substances with respect to water, for gaseous substances with respect to air.
3
For the catalyst

Design of a production reactor: Magnesium oxide 17

 Figure 2 Process diagram of the calcination of magnesium hydroxide to obtain MgO ( Pilarska. A & Jesionowsky.T, 2011)
Route 3
Table 3 Process information for the pyrohydrolysis of magnesium chorhide
Compound MgCl2
It is used in different
industrial processes such as
the production of textiles,
paper and cement. It is also
Uses used as a catalyst in some
chemical reactions
(Magnesium_chloride, n.d.)
. It is also available in food
products as an electrolyte
MgCl2 anhidrido grado
analítico: 64.95 $USD por
kg. (>99.9% p/p, Sigma
Updated price per kg of compound Aldrich)
Food grade:
9.36 $USD (~12%p/p,
H2 O MgO HCl2
It is a key raw
Active phase and catalyst
material in PVC
support
production and also
Solvent Manufacture of refractory
in pharmaceuticals,
Facilitator of life on earth materials
it is used for water
Raw material to produce Additive in concrete
treatment, pigment
green hydrogen manufacturing (Nobre et
manufacturing and
al., 2020)
food processing
(Hisham et al., 2014)
Grado analítico: 14400
In the city of Medellín the $USD (>99.99% p/p,
Analytical grade:
price per cubic meter of Sigma Aldrich)
175.12 $USD
aqueduct water in industrial
HCl net 37% v/v.
tariff is 526.08 $COP Food grade: 6.25 $USD
Sigma Aldrich
(EPM data, March 2023). (~50%w/w,
PipingRock.Com)
Design of a production reactor: Magnesium oxide 18
 Brymar S.A.S)
It can be obtained of EPM© certifies that the
analytical grade with more water in its aqueducts According to your As a laboratory and
than 99.9% purity, in flakes contains quantities below requirements, up to 99.99% industrial-scale
Purity with which it is obtained in the
market for industrial applications the maximum regulated by purity by weight can be reagent, it is traded
with purity of 98% w/w and the law of: CaCO3, Cl 2, Cl- obtained as a laboratory in concentrations
for human consumption at , nitrates, nitrites, sulfates, reagent. between 31 – 37%.
12% w/w aluminum and iron.
Phases present during the reaction (gas,
liquid and/or solid) Aqueous Liquid and Gas Solid Liquid and Gas
Peso molecular [g/mol] 95.211 g/mol 18.01528 g/mol 40.3044 g/mol 36.46 g/mol
Identification C. A.S 7786-30-3 7732-18-5 1309-48-4 7647-01-0
-85.95°C (pure)
Normal melting point 714 °C 0°C 2850°C 48°C (in water
a38%)
Normal boiling point 1412 °C 100°C 3600°C -85.95°C
Liquid: -285.83
Standard enthalpy of formation
[kJ/mol] -601.58 kJ/mol (NIST) Vapor: -241.83 -601.24 kJ/mol (NIST) 85.4 kJ/mol (NIST)
(NIST)
Liquid: -237.14
Standard formation Gibbs-free
energy [kJ/mol] -591.8 kJ/mol (NIST) Vapor: -228.613 -596.30 kJ/mol (NIST) 69.9 kJ/mol (NIST)
(NIST)
𝐵 𝐵 𝐵 log10 (𝑃𝑣𝑎𝑝 )
log10 (𝑃𝑣𝑎𝑝 ) = 𝐴 − log10 (𝑃𝑣𝑎𝑝 ) = 𝐴 − log10 (𝑃𝑣𝑎𝑝 ) = 𝐴 −
𝑇+𝐶 𝑇+𝐶 𝑇+𝐶 𝐵
= 𝐴−
𝑇+𝐶
With Pvap in bar and T in With Pvap in bar and T in With Pvap in bar and T in
K, the constants are: K, the constants are: K, the constants are: With Pvap in bar
Vapour pressure in terms of A = 7.1380 A = 3. 5596 A = 6.9228 and T in K, the
temperature B = 6697.77 B = 643.748 B = 13826.21 constants are:
C = 161.04 C = -198.043 C = -170.464 A = 4.574
Temperatures between 778 For temperatures between Temperatures between B = 868. 358
and 1412°C (Yaws, 2015) 379 and 573K (NIST) 2832 and 5677°C (Yaws, C = 1.745
2015) Temperatures
between 188.3 and

Design of a production reactor: Magnesium oxide 19

 309.4°C (NIST)
3
2.32 g/cm (solid) 𝑔 3
Density in terms of temperature 1 𝜌: 0.7986 @250°𝐶 3.58 g/cm (solid) 1.49 g/cm3 @ (pure
𝑐𝑚3 liquid)
𝐽 𝐽 𝐽 𝐽
𝐶𝑝 [ ] = 𝐴 + 𝐵𝑇 𝐶𝑝 [ ] = 𝐴 + 𝐵𝑇 𝐶𝑝 [ ] = 𝐴 + 𝐵𝑇 𝐶𝑝 [ ]
𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾
+ 𝐶𝑇 2 + 𝐶𝑇 2 + 𝐶𝑇 2 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2
+ 𝐷𝑇 3 + 𝐷𝑇 3 + 𝐷𝑇 3
+ 𝐷𝑇 3 + 𝐸𝑇 −2
+ 𝐸𝑇 −2 + 𝐸𝑇 −2 + 𝐸𝑇 −2

A = 32. 124
Heat capacity in terms of temperature A = 78.3073 A = -203.606 A = 47.26 B = -13.458
1 B = 2-43588 B = 1529.290 B = 6.682 C = 19.868
C = 6.85887 C = -3196.41 C = -0.87 D = -6.854
D = -1.7289 D = 2474.455 D = 0.104 E = -0.050
E = -0.7299 E = 3.855326 E = -1. Tel. 054
For temperatures
For temperatures between For temperatures between For temperatures between between 298 and
298 and 997K (NIST) 295 and 500K (NIST) 298 and 3105K (NIST) 1200K (NIST)
𝑘𝐽
𝑘𝐽 ∆𝐻𝑣𝑎𝑝 [ ]
∆𝐻𝑣𝑎𝑝 [ ] = 𝐴 (1 𝑚𝑜𝑙
𝑚𝑜𝑙 𝑇 𝑛
𝑇 𝑛 = 𝐴 (1 − )
− ) 𝑇𝑐
𝑇𝑐
Heat of vaporization in terms of A = 30.54
temperature Not reported (solid) A = 50.05 Not reported (solid)
n = 0. 647
n = 0. 321
For temperatures
For temperatures between
between 159 and
273.15 and 647.15 K
324. 5 K (Yaws,
(Yaws, 2009)
2009)
Temperature Not reported (solid) 647.2 K Not reported (solid) 324.7 K
Pressure Not reported (solid) 220.64 bar Not reported (solid) 82.46 bar
Critical properties
Volume Not reported (solid) 3.104 L/kg Not reported (solid) 2.381 L/kg
Density Not reported (solid) 17.9 mol/L Not reported (solid) 15,314 mol/L

Design of a production reactor: Magnesium oxide 20

 𝑊
𝑘𝑙𝑖𝑞 [ ] = 𝐴 + 𝐵𝑇
𝑚𝐾 𝑊
+ 𝐶𝑇 2 𝑘 [ ] = 2.2442
Parameters of (Yaws, 𝑐𝑚 𝐾
∙ 10−5 𝑇
2009) with T in K
+ 7.2095
Thermal conductivity in terms of
temperature 1 ∙ 10−3
A = 0.29875
Adjusted data from
B = 4.70537E-3
(Touloukian et al., 1971)
C = -5.6209E-6
with T in K
Range: 480 – 680K
For temperatures between
273.15 and 633.15 K
𝑠𝑙𝑢𝑔
𝑠𝑙𝑢𝑔 𝜇[ ]
𝑓𝑡 𝑠
𝜇[ ] = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2
𝑓𝑡 𝑠 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2
𝜇 = 0.91215 𝑐𝑃
A = -36.826 A = -9.118
Viscosity in terms of temperature 1 At 25°C with a B = 4.29e-1 Not applicable as it is solid B = 5.55e-1
concentration of g-equiv/L. C = -1. 62e-5 C = -1.11e-4
(Yaws, 2009)
T between 280 and 1073K T between 200 and
(Yaws, 2009) 1000K
(Yaws, 2009)
𝐷 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2

A = -0.0822
𝐷 = 1.19 ∙ 10−9 𝑚2 ⁄𝑠 𝐷 = 2.29 ∙ 10−9 𝑚2 ⁄𝑠 B = 6.54e-4
C = 9.023e-7
Diffusivity in terms of temperature 2 At 25°C with a At 25°C with a Nor reported
concentration of 0.001M concentration of 0.001M D is expressed in
(N/A, s. f.) . (N/A, s. f.) . cm2/s, the
temperature range is
between 200 and
1500K

Design of a production reactor: Magnesium oxide 21


This salt is suitable for
human consumption in low
doses. It can be a
Toxicity contaminant of water so
there are regulations to keep environment
its concentrations in
minimum amounts.
As a pure solid it is
Reactivity thermally stable but highly
reactive with water.
Considering that the process
is done with sea brine as raw
material, aqueous MgCl2
Recommendations for storage and can be stored under normal
transport
conditions in tanks that have
the appropriate corrosion
resistance to store the
electrolyte.
Flash point Not reported (solid)
LFL (Lower
Flammability flamability limit) Non-flammable
UFL (Upper
flamability limit) Non-flammable
Particle size Not applicable
This compound is not toxic It presents low risk of
to humans or the
H2O is thermally and
chemically stable
Store under normal
conditions in tanks, it can
be transported in pipes with
pumps or compressors
depending on the phase in
which it is transported. It is
recommended to ensure the
chemical and mechanical
resistance of the pipe
especially in case it is
transported as steam
Not reported
Non-flammable
Non-flammable
Not applicable
(Yaw’s)
HCl in high
concentrations
causes burns in
biological tissues, is
toxicity for humans since it
highly corrosive and
is easily digested
is considered to
eliminate any type of
organism in water.
It has high thermal and It is highly corrosive
chemical stability in dry and reacts with
conditions, but reacts easily metals generating
with water to form hydrogen and
Mg(OH)2 chlorides.
It can be stored under
normal conditions in silos Store as an aqueous
or containers with humidity solution under
control. Depending on its normal conditions in
particle size, it can be tanks made of highly
transported on mechanical corrosion-resistant
belts or with hydraulic air materials.
transport equipment.
Not reported (solid) Not reported
Non-flammable Non-flammable
Non-flammable Non-flammable
Not applicable Not applicable
Design of a production reactor: Magnesium oxide 22
1
In the state in which it is found in the reaction.
2
For liquid substances with respect to water, for gaseous substances with respect to air.
3
For the catalyst

From Bakker's, J.S.C (2017) the diagram of figure 3 is extracted from figure 1-2 of the
aforementioned document, the process starts from obtaining sea brine to which other metals are
separated apart from magnesium by precipitation with pH adjustment, this precipitation is done in the
presence of MgO to form a soluble complex of MgO and MgCl hexahydrate. The complex is
dehydrated in a fluidized bed reactor at 229°C and then magnesium chloride is calcined to produce
MgO.

Figure 3 Process flowchart for the pyrohydrolysis of MgCl2 into MgO. Bakker's, J.S.C (2017)

0.025

0.02
k [W/cmK]

0.015
y = 2.2442E-05x + 7.2095E-03
0.01
R² = 9.8657E-01

0.005

0
400 450 500 550 600 650 700
T [K]

Figure 4 Y. S. Touloukian, R. W. Powell, C. Y. Ho, y P. G. Klemens, «Thermophysical properties of matter - the TPRC data
series. Volume 2. Thermal conductivity - nonmetallic solids.

Design of a production reactor: Magnesium oxide 23

 18
16
14
12 y = 3.70455E+04x-1.37117E+00
D [mm2/s]
10 R² = 9.96937E-01
8
6
4
2
0
250 450 650 850 1050 1250 1450
T [K]

Figure 5 A. M. Hofmeister, «Thermal diffusivity and thermal conductivity of single-crystal MgO and Al2O3 and related
compounds as a function of temperature»

Figure 6 Values of heat capacity for dolomite in a range of 11-300K (Stout & Robie, 1963)

Design of a production reactor: Magnesium oxide 24

2. Justification of the chemical route to be used to produce the assigned chemical
compound. Use the criteria presented in section 2, complete “Table 1. Process selection matrix”
and justify the weighting assigned to each item and for each route.

Process Selection Matrix

Route (1): Magnesite calcination

Route (2): Calcination of magnesium hydroxide
Route (3): Magnesium Chloride Pyrohydrolysis (Aman Process)

Justification of the assigned weights

Next, the aspects that are taken into account for the selection of the chemical process are described,
their percentage of relevance is justified and the score of each route is analyzed with respect to each
criterion.
2.1. Obsolescence
It refers to the efficiency and useful life of a technology, either due to malfunction or disuse due to
poor or insufficient performance of its functions compared to new technologies.
Route 1: The risk associated with mining exploitation is considered, the Colombian mining
Information System presents a projection of the supply and demand of magnesia in Colombia,
presented as results that approximately in the year 2035, there are very small values for the supply
and demand compared to those currently found. Score: 5. (s. f., Magnesio)

Figure 7 Projection of magnesite production in Colombia (s. f., Magnesio)

Design of a production reactor: Magnesium oxide 25

 Figure 8 Projection of magnesite consume in Colombia (s. f., Magnesio)

Route 2: Recognizing that the main drawback of the production of MgO from Mg(OH)2 is the poor
filterability of the latter due to its colloidal nature. This makes purification of Mg(OH) 2 a very time
consuming affair and demanding in terms of the volume of fresh water required per ton of MgO.
(Process for the Preparation of Magnesia (MgO) from Crude Mg (OH)2, 2006)Score: 3.
Route 3: Producing magnesite from salty seawater is a process that can have low performance
because it depends on the concentration and purity of Mg + 2 in the water so other technologies can
make it obsolete. In addition, although the process could be improved through technologies that
improve the energy efficiency of the process, the chemical reaction as such has no window for
improvement. Score: 4.
2.2. Availability and costs of raw materials
With the information on raw material costs reported in item 1.2, the origin of the raw material and
the price per kg are analyzed. The further away the suppliers are, the lower the score assigned to the
route. The higher the cost of raw materials, the lower the score will also be.
Route 1: In Colombia, magnesite is obtained by exploitation in mines located in Bolviar, Santa Marta
and to a lesser extent in Sogamoso, it is reported that annually the export of the product is greater
than the import, therefore, it is a reagent with a possible scope, the available price is US$0.154/kg.
Score 9 (Veritrade | Importaciones y Exportaciones de CARBONATO DE MAGNESIO NATURAL
(MAGNESITA), s. f.)

Route 2: Magnesium hydroxide occurs in nature in the form of an oxide mineral called brucite,
generally bound to periclase as a product of periclase hydration or as inclusions in deposits of
serpentine, magnesite, and dolomite, so it depends on the exploitation of the mineral as such and the
brucite deposit in Colombia is not very common and the cost of extraction is very high. (EYA
Academy, n.d) Score: 4.
Route 3: If the process is carried out in a coastal city of the country, the acquisition of the raw material
would be highly easy since it would not have a purchase price, but the tax must be paid for the right
to exploit the natural resource. Score: 10.
2.3. Process complexity
We will evaluate this item based on the number of reactions involved, based on the number of unit
operations necessary between the raw material and obtaining the product of interest and the energy
consumption that the reaction conditions in the reactor involved in the process would require. The
more complex the process, the lower the score it will have.

Design of a production reactor: Magnesium oxide 26

Route 1: In the calcination of magnesite, magnesium oxide is obtained as a product, however, in
order to obtain the desired product with high purity, additional processes must be carried out,
including mineral removal, where additional processes are carried out, explained in number 1. In
addition, it is a process where high temperatures are used, ≈>900°C. (Russell Pearce, 1967) Score:
5.
Route 2: Recognizing that the main drawback of MgO production from Mg(OH) 2 is the poor
filterability of the latter due to its colloidal nature. This makes the purification of Mg(OH)2 a time-
consuming and demanding affair in terms of the volume of fresh water required per ton of MgO.
(Process for the preparation of magnesia (MgO) from crude Mg (OH)2. (2006)). Score: 3.
Ruta 3: This process requires 4 stages: it starts with a precipitation, the separation of the precipitate
can be done by filtration or decantation, continues a heating process to dehydrate the salt and finally
pyrohydrolysis is done at high temperature. The unit operations involved are relatively
straightforward and only two of them require complex operating conditions. Score: 7.
2.4. Process efficiency
We will analyze the efficiency of the process based on the time needed to execute each process, their
energy consumption and the product purity achieved with each route.

Route 1: In the patent (Russell Pearce, 1967) it is reported that after the purification process it is
possible to obtain a product with an approximate purity of 98% after purification, but this depends
on the type of purification that is done, and the MgO content in the magnesite, energy consumption
is considered high for the reason mentioned above related to high temperatures, and in terms of the
time required, this directly depends on how CO2 is removed, since removing it increases the
decomposition speed of magnesite. Score 7
Route 2: In the patent "Process for the preparation of magnesia (MgO) from Mg (OH) 2 gross",
(2006) it is indicated that there is no compromise in the quality of MgO achieved in this way, which
reduces the possibility of using this method. Score: 4.
Route 3: In the book "The Chemistry and Technology of Magnesia" by Shand, M. A. (2006) it is
indicated that theprocess of pyrohydrolysis of magnesium chloride can be obtainedmagnesium oxide
with purity >99% and that this process is already carried outon an industrial scale in places such as
the Black Sea. Score: 8.
2.5. Degree of integration with industry
It seeks to use processes that are scalable to produce industrial quantities of the product of interest
since this, being a commodity (Commodity Profile: Magnesium, n.d.) , requires to be produced in
high quantities. Therefore, this criterion is analyzed in terms of the scalability of the process, the
availability of large quantities of raw material and the existence of patents regarding this route.
Route 1: Magnesium oxide is obtained mostly through the calcination of magnesite; therefore it is a
process that is already industrialized (Shand, M. A. ,2006), also as it was mentioned in the item
related to the raw material, magnesite is available In Colombia, the patent for the process is the one
written by R. F., HEUER, in 1967 (Russell Pearce, 1967). During purification, calcium chloride is
obtained, which is a compound used in medicine and in the food industry. (Absortech, 2023) Score:
9.

Design of a production reactor: Magnesium oxide 27

Route 2: According to the patent "Procedure for obtaining Magnesium Hydroxide from saline
effluents".( 2017), currently the production of MgO is carried out mainly by two routes; the first from
the mining extraction that is considered for the present route, of increasingly high costs that make it
necessary to access magnesites whose MgO content exceeds 40%, and the second from water from
high salinity streams, mainly seawater, which has now become the most competitive alternative with
the previous one, which makes this option less suitable. (Bakouri et al., 2017) Score: 4.
Route 3: Pyrohydrolysis of MgCl is already carried out on an industrial scale, the raw material is an
extremely abundant natural resource, and the by-product, which is HCl, is also a commodity with
high demand in the industry. Score: 8.
2.6. Status of development of the process
Chemical processes can be classified according to the scale at which they are carried out and this
accounts for the progress of scientific progress around this process. At laboratory scale, reactions
are executed where scientific research is based on understanding the fundamental phenomena of the
same, when the process is executed at pilot plant scale it indicates that the fundamental phenomena
of the process are understood and it is desired to understand the transport phenomena involved in
industrial production l. Finally, if the process is already carried out on an industrial scale, it indicates
that in addition to the phenomena studied in the two previous stages, an economic feasibility analysis
was carried out for the start-up ofthe process on an industrial scale.
Route 1: Since the process is industrialized and is one of the most used to obtain magnesium oxide,
it is considered a mature process. (Shand, M. A. ,2006) Score: 8.
Route 2: This process is little used (brucite mining is not so used due to the high cost it has), because
there are other methods with which a higher purity can be obtained such as high salinity currents,
which makes it a more competitive and more used process today.(Bakouri.et al, 2017) Score: 5.
Route 3: In the book "The Chemistry and Technology of Magnesia" by Shand, M. A. (2006) it is
reported in table 3.1. that, for the year of publication of the book, between Israel and Jordan 120,000
tons/year of magnesium oxide obtained from brine from the Black Sea were produced between Israel
and Jordan, this being only a small portion of the world MgO market. Therefore, it is a
consolidated process worldwide. Score 7.
2.7. Waste disposal
At present, environmental development is very important, as is the circular economy, where the least
amount of waste possible is expected to be generated, not only from the commercial point of view,
but from social and environmental responsibility, it is expected that the generation of waste is almost
zero, and therefore it is a very important parameter. It is analyzed based on the state of aggregation
in which the by-products of the reaction are found and the possibility that they have of being used or
commercialized.
Route 1: The calcination of magnesite produces two main types of waste: gases and ashes. The gases
resulting from calcination are mainly carbon dioxide (CO2) and water vapor. Ash, on the other hand,
is a solid by-product that forms from calcined magnesite residue and the chemicals used in the
calcination process. These ashes can contain heavy metals and other toxic compounds, so they must
be handled with care. Some of the waste, such as ash, can be recycled and reused in other processes,
such as the production of construction materials. Score: 6.

Design of a production reactor: Magnesium oxide 28

Route 2: In this process, ash and exhaust gases are produced. The ashes are composed mainly of
metallic oxides, while the exhaust gases can contain carbon dioxide or carbon monoxide, some
treatment options include the provision of landfills for the mentioned substances. Score: 6.
Route 3: In this process two wastes are mainly produced: Salts such as sodium chloride, calcium and
iron whose purification can be complex and its sale price is low. If discarded it will be highly
polluting to the water. The other by-product is HCl which is obtained gaseous in high purity and can
be easily marketed. Score: 6.
2.8. Process economy
The costs of a process are vital, since it is perhaps the criterion that is most evaluated in the execution
of a project, to confirm its viability and development, for this reason it is given the highest score. In
this criterion, the production costs of each process are compared and the possible investment costs
that each stage of the process would require are compared.
Route 1: The price of the reagents is specified above, however, to control the process at high
temperatures, the cost of energy must be considered, which directly depends on the location of the
production, in addition the cost of the equipment depends on the defined production capacity and
calcination occurs in a single piece of equipment. Score: 6-
Route 2: The price of the reagent is high because the mineral (Brucite) must be exploited and this
process has a high cost, since it is not so easy to obtain, according to the book "The Chemistry and
technology of Magnesia" (2006), commercial deposits are only found in Russia, China, and the
United States. Score: 4.
Route 3: The process does not require expensive reagents and the investment cost is relative to the
desired production capacity. However, this being a commodity, it is clear that profitability depends
a lot on producing high quantities of product. Equipment maintenance can be straightforward as long
as suitable materials are selected that resist corrosion from the salts and chlorine involved in the
process. Score 9.
2.9. Energy use
Like the previous criterion, it is important to take into account that a high use of energy implies
higher costs in the process, which influences the economy, and in turn, as occurs with waste disposal,
based on sustainability, it is vital to reduce energy consumption in order to also meet the UN's
sustainable development goals, therefore, a high weighting is given.
Route 1: To break down 1.0 kg of magnesite the energy required is 2415 kJ (2289 Btu) or 2.42 x 106
kJ per metric ton (2.3 MBtu) or 2.1 MBtu/short ton. (Shand, M. A. ,2006) Score: 6.
Route 2: The total energy required to break down 0.55 kg of magnesium hydroxide into magnesium
oxide and water vapor is 717 kJ + 318 kJ = 1035 kJ (981 Btu). (Shand, M. A. ,2006) Score: 9.
Route 3: In Bakker's J.S.C. Table 1-1, "The Recovery of Magnesium Oxide and Hydrogen Chloride
from Magnesium Chloride Brines and Molten Salt Hydrates," the process reports that the process
consumes, per ton of product: 650 MJ in drying and 4400 MJ in pyrohydrolysis. (Equivalent to
5050kJ/kg) Score: 3.
2.10. Safety Aspects

Design of a production reactor: Magnesium oxide 29

Reaction conditions with high pressures and temperatures, flammable, corrosive, toxic species, etc.
are aspects that reduce the score of the reaction.
Aunque la seguridad es una clave en una industria, el desarrollo de la ingeniería de los materiales y
otros hace que los procesos industriales sean cada vez más seguros y se puedan prevenir accidentes
aun trabajando a condiciones extremas de presión o temperatura, el valor asignado del 5% está
teniendo en cuenta que sería ideal no manipular sustancias tóxicas, corrosivas o inflamables que
puedan afectar el personal.
Route 1: The temperature at which the calcination occurs ranges between 450-900°C, having a better
performance in its upper limit, therefore, the temperature and pressure of the reactor, would be
aspects to consider when evaluating the safety, in addition, since a by-product of the reaction is CO2,
and this must be constantly eliminated, an adequate gas extraction system must be in place to avoid
the accumulation of this gas. Score 7
Route 2: The calcination of magnesium hydroxide can present some safety risks, such as elevated
temperatures since heat exchange furnaces are used, where dehydrated filter cakes are generally
calcined in clumps at about 950°C, so Workers carrying out the calcination operation must be
protected with appropriate personal protective clothing and equipment. On the other hand, the
calcination of magnesium hydroxide can produce a large amount of heat, which can increase the risk
of fire, also during the process there is emission of gases and handling of hot material. Score: 7.
Route 3: The maximum operating temperature of the process could be rounded up, with a safety
factor, to 600°C. Despite being a high temperature, this and the reactor pressure are the only 2
variables that represent a risk to the operation. Score 7:
2.11. Value added
Value added is the difference between the amount of sales and purchases, that is, the difference
between market prices and production costs. At the business level of cost-benefit analysis, it means
the difference between a company's income and the costs of raw materials, fixed and variable capital.
As a basic approximation, the following expression will be used to calculate the added value.
The added value formula indicated in the project assignment document is used:
(𝑠𝑎𝑙𝑒𝑠 𝑟𝑒𝑣𝑒𝑛𝑢𝑒) − (𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑐𝑜𝑠𝑡)
𝑉𝐴 =
𝑠𝑎𝑙𝑒𝑠 𝑟𝑒𝑣𝑒𝑛𝑢𝑒

Route 1: Taking into account the costs of the reagents associated with the reaction (0.154US$/kg),
and the cost of the product (6.25 $USD), the added value was determined, which has a value of
VA=97.53%. Score: 8.
Route 2: To determine the added value, it was taken into account that the cost of the reagent
associated with the relationship (0.1$USD/kg), and the income from sales that was determined in the
table of properties, considering the stoichiometric relationship 1 to 1, was obtained an added value
of 98.33%. Score: 9.
Route 3: Using an average MgCl 2 concentration in seawater of 1300ppm, and using those molars
of magnesium chloride and magnesium oxide, it can be calculated that 550L of salt water is needed

Design of a production reactor: Magnesium oxide 30

to obtain one kg of MgO. The price per L of seawater cannot be determined, but the price of fresh
water in Medellín will be used as an approximation:
Price per kg of MgO: 30000$ COP (62.5 $USD).
Price of saltwater produce 1 kg of MgO: 290$ COP.
VA = 99.03%.
Score: 10.
2.12. E factor
The E factor is calculated as kg of waste/kg of desired product [5] and is a way of determining the
environmental acceptability of a process, considering as waste any product other than the desired
one.
The added value formula indicated in the project assignment document is used:

𝑘𝑔 𝑜𝑓 𝑤𝑎𝑠𝑡𝑒
𝐹𝐸 =
𝑘𝑔 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

Route 1: CO2 is taken as waste, and after calcination the product contains SiO2 1.16 wt%, Fe2O3
wt% 0.24, Al2O3 wt% 0.14, CaO wt% 7.16, if purification is performed MgCl2 is also obtained.
This would have an approximate FE of 9.5%.
FE = 9.5% Score:9.

Route 2: According to the patent "Process for the preparation of magnesia (MgO) from crude Mg
(OH)2", (2006) The calcined product normally contains ≥99.5 wt% MgO, <1 wt% CaO, ≤0.05wt%
SiO2 , ≤ 0.05 wt% Fe2O3, ≤ 0.005wt% Al2O3 and ≤0.01% B2O3 , so it can be seen that it has a low E
factor.
FE=1.12%
Route 3: The precipitates of sodium, calcium, potassium, bromine and sulfates are taken as wastes
in this process according to the composition taken from Table 3.2 of Shand, M. A. (2006). The
desired product is Mg, Cl is not included because not all chlorine in the water will become usable
HCl(g).

Design of a production reactor: Magnesium oxide 31

 Figure 9 Elemental composition of sea water Shand, M. A. (2006). The chemistry and technology of magnesia

FE = 283%, Score: 1.
Weighting table:
Route (1): Magnesite calcination
Route (2): Calcination of magnesium hydroxide
Route (3): Magnesium Chloride Pyrohydrolysis (Aman Process)

In this process matrix, each process is evaluated and qualified with values from 0 to 10; being
(0) the lowest rating and (10) the highest.
Table 4 Process Selection Matrix

Routes
Criteria %
1 2 3
1 Obsolescence 5 5 3 4
2 Availability and Costs of Raw Materials 5 9 4 10
3 Process complexity 10 5 3 7
4 Process efficiency 6 7 4 8
5 Degree of integration with the industry 5 9 4 8
6 Process development status 7 8 5 7
7 Waste disposal 12 6 6 6
8 Process economy 15 6 4 9
9 Energy use 9 6 9 3
10 Security aspects 5 7 7 7
11 Zone V added 15 8 9 10
12 E-Factor 6 9 10 1
TOTAL 100 6.88 5.87 7.02

Design of a production reactor: Magnesium oxide 32

3. Kinetic model
We are going to work with the experimental methods and results reported at De Bakker, J. S. C.
(2011). The recovery of magnesium oxide and hydrogen chloride from magnesium chloride brines
and molten salt hydrates (Doctoral dissertation, Queen's University).
The reactions are performed in a vertical quartz tube of 42mm of outside diameter. Approximately
1g of sample is heated to temperatures of 450°, 500° or 550°C according to the experiment conditions.
The reactions are performed under an inert atmosphere caused by a flow of nitrogen at 5 L/min, until
complete conversion, the reaction takes between 2 and 3 hours. The authors specify that the inert gas
flow allowed the swept of the gaseous products on the reaction system, with the intention to make
sura that the inversion reaction is not possible because of the lack of water and HCl.

𝑀𝑔𝐶𝑙2 ∙ 6𝐻2 𝑂(𝑠) → 𝑀𝑔𝑂(𝑠) + 5𝐻2 𝑂(𝑔) + 2𝐻𝐶𝑙(𝑔)

Results:
The reaction system emulates the conditions of a batch reactor with reactive distillation because the
gaseous products on the system are removed immediately. Therefore, a global mass balance lets the
calculation of the mass fraction of reactive () that is remaining in the system and in this way, the
results of the experimentation is reported in figure XX.𝑀𝑔𝐶𝑙2 ∙ 6𝐻2 𝑂

Figure 10 From Bakker, J. S. C. (2011).

Therefore, the researchers define the mass balance on the system as under this design equation and
an analytic development of the equations takes to the linearization of both models.
For 1st order kinetics:
𝑑𝑓𝑅
= −𝑘 ∙ 𝑓𝑅
𝑑𝑡

Design of a production reactor: Magnesium oxide 33

Which leads to:

ln(𝑓𝑅 ) = −𝑘𝑡 + 𝐶

For 2nd order kinetics

𝑑𝑓𝑅
= −𝑘 ∙ 𝑓𝑅2
𝑑𝑡
Which leads to:
1
= −𝑘𝑡 + 𝐶
𝑓𝑅
Both models are plotted with the experimental results of the study:

Design of a production reactor: Magnesium oxide 34

We observe that both models (1st and 2nd order reactions) fit to lineal equations with a high
determination coefficient R2. Each one of the 6 curves fitted with the data produce a different value
of specific reaction rate k because it is a temperature dependent parameter. Therefore, for completing
the kinetic model, the three values of k obtained on each model are linearized to compel fit them to
the linearized equation of Arrhenius:
𝐸𝑎 1
ln(𝑘) = ln(𝐴) − ∙
𝑅 𝑇

1st order model:

A = 667.8
Ea = 59,221 J
R2 = 0.615

Design of a production reactor: Magnesium oxide 35

2st order model:
A = 2563797
E2 = 101962 J
R2 = 0.6922
4. Selection and justification
4.1. Annual production capacity
To determine the annual production capacity, the total values of annual imports and exports of
magnesium oxide in Colombia are taken as a reference, which are taken from Trade Map, a database
on international trade statistics. As for exports, the portal reports that, in the year 2021, the total
amount of this indicator was 13 tons, distributed to nearby countries located in Latin America, on
the other hand in terms of imports is reported a total quantity of 27821 tons, among the countries
that contribute the most to this value are China (21853 tons), Brazil (4035 tons), Turkey (761 tons),
among others. From this it can be concluded that in Colombia most of the magnesium oxide consumed
is obtained by imports, therefore, one of the objectives of the proposed process is to reduce the amount
of imported product and strengthen the national industry. (ITC, 2023)
It is proposed to cover 5% of total imports, which is equivalent to 1391.05 tons / year, it is considered
that the accounting working days per year for production are 312 days, as a result 4.45tons/day will
be produced.

Design of a production reactor: Magnesium oxide 36

 Figure 11 Report of total magnesium oxide imports in Colombia

Figure 12 Report of total magnesium oxide exports in Colombia

4.2. Operating conditions

The kinnetic study reported by Bakker has a temperature range between 450° and 550°C, the author
also concludes that “The thermal decomposition kinetics study indicated that the high temperature
decomposition reactor in the conceptual flowsheet should operate at a temperature of 550° - 600°C
” which also consistent with the common temperatures reported by Shand. The operation pressure is
not explicitly reported on the documents, but we consider it as atmospheric since that the common
way in calcinations an pyrolysis processes. According to the table 3.2 form The Chemistry and

Design of a production reactor: Magnesium oxide 37

Technology of Magnesia (Shand, M. A. 2006) the concentration of the reagent in the reaction is
1300ppm.
The kinetic study was made under inert atmosphere conditions which is a requirement for the
pyrolysis occurring. Therefore, oxygen in the reactor must be removed by filling the empty space of
the reactor with nitrogen. The reactions can be performed until total conversion, but an energetic-
economical study of the operation may allow the determination of the time of reaction that optimizes
the energy consumption and guarantees a high amount of product.
Considering the annual production capacity, the amount of total input flow to be used per day is
2447500 L/day. The amount of vapor produced is going to depend on the energetic and economic
analysis of the operation.
5. Selection of reactor type
At present, the Batch reactor together with the semi-batch, are the most used equipment in the
chemical industry due to their great versatility, although their production yield is relatively low and
the quality of the final product usually varies in each batch due to the multitude of elements that affect
chemical reactions such as temperature, pressure, humidity, etc., it is for this reason that for the
selected route, a semi-batch reactor will be used in which the reagents are loaded and unloaded the
products after the reaction is complete. In addition, unlike the traditional batch reactor, the semi-batch
reactor is a kind of batch reactor that allows modifying the dosed addition or extraction of species
throughout the batch, thus having much more complete control of the reaction (allowing to control
the speed of this), which is complemented with an efficient mixing to be able to maintain constant
conditions inside the reactor. (Ibáñez, S.,2019).
One of the main advantages of this system is its flexibility, since due to the need that industries have
to produce a wide variety of products, it is the most used reactor since it offers greater ease to adapt
to different productions without the need to carry out large changes. In addition, they allow a smaller
manufacturing volume, which reduces the economic damage if an incident occurs that affects the
reaction, taking into account that the process produces water vapor and hydrochloric acid, the
equipment will be designed so that the system can have an output of the gases produced by the
reaction, and also that the solids within the system are concentrated. (Noguera, I.B.,2021).

Figure 13 Semi-batch reactor

Design of a production reactor: Magnesium oxide 38

CONCLUSIONS
The routes reported for the industrial production of MgO start, in all cases, from the exploitation of a
natural resource. Either minerals such as magnesite, dolomite, brucite or seawater. It was discovered
that all the routes involve purification processes of the reagents since the raw materials contain
Magnesium in low concentrations. It is also evident that the chemical reactions of each route are
thermal treatments at high temperatures (calcinations or pyrolysis). The process in which seawater is
used as raw material is selected due to its low cost and availability compared to dolomite and brucite,
as well as having the highest added value.
The implementation of the selected process for production in Colombia would be suitable as a large-
scale project, due to the fact that there is currently a great demand, which is evidenced in the amount
of imported product, in addition, in the long term it could be economically favorable for the country.
country, generating employment in the sector and strengthening the national industry by increasing
GDP.
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