ABSTRACT

The contact method, which we will present in this report, is a process based on the use of a
catalyst to convert SO2 to SO3, in which sulfuric acid is obtained by hydration. This is a method
that uses heterogeneous catalysis, that is, the catalyst used is in a different aggregation phase.

Although the method that we will work for the preparation of sulfuric acid (contact method), it
is not a recent method since it was patented in 1831, it is the most frequent method and it
allows to obtain a sulfuric acid of greater purity and concentration.

The contact method has three stages, in the first we will see the production of SO2 from pyrite
(FeS2) which is one of the most used sources in many plants.

In the second stage, we will see the production of sulfur trioxide (SO3) from the purified SO2.

Finally in the third stage we will see the conversion of SO3 into sulfuric acid.

During the process high temperatures will be used, although low temperatures favor the
reaction, for two reasons: one because it increases the speed of the reaction and the other
because it increases the performance of the catalyst, but this will be seen in detail later.

INTRODUCTION

Sulfuric acid is a highly corrosive strong mineral acid . It is viscous liquid which is soluble in
water at all concentrations. Sometimes, it is dyed dark brown during production to alert
people to its hazards. The historical name of this acid is oil of vitriol. Sulfuric acid is a diprotic
acid and shows different properties depending upon its concentration. Its corrosiveness on
other materials, like metals, living tissues (e.g. skin and flesh) or even stones, can be mainly
ascribed to its strong acidic nature and, if concentrated, strong dehydrating and oxidizing
property. Sulfuric acid at a high concentration can cause very serious damage upon
contact,as it burns the cornea and can lead to permanent blindness if splashed onto eyes.
Accordingly, safety precautions should be strictly observed when handling it.

Sulfuric acid has a wide range of applications including domesti acidic drain cleaner,
electrolyte in lead-acid batteries and various cleaning agents. It is also a central substance in
the chemical industry. Principal uses include mineral processing, fertilizer manufacturing, oil
refining, wastewater processing, and chemical synthesis.

It is widely produced with different methods, such as contact process, wet sulfuric acid
process and some other methods.
THEORETICAL FOUNDATION

Sulfuric acid is an extremely corrosive chemical compound whose formula is H2SO4. It is the
chemical compound that is produced the most in the world, that is why it is used as one of the
many meters of the industrial capacity of the countries. A large part is used to obtain
fertilizers. It is also used for the synthesis of other acids and sulfates and in the petrochemical
industry.

a) Raw material used for its production

It refers to the concentrates and sulphide minerals of copper, lead and zinc that are processed
by metallurgical pyro to obtain refined metals. Sulfur is generally present in the form of copper
sulphide (chalcopyrite CuFeS2, calcosin Cu2S), lead sulfide (galena PbS) and zinc sulphide
(blenda ZnS), and may also be present in the form of sulfide. iron (pyrite FeS2), sulfates, etc.

b) Obtaining sulfuric acid

The most common method to fix sulfur from the gases of SO2 is the production of sulfuric acid.
While the gases contain 4% SO2 or more, they can be used to obtain sulfuric acid by the
standard contact process.

The process of obtaining acid consists of four basic stages:

1. Gas purification: The powders are removed by electrostatic precipitation and the moisture is
removed by washing with diluted sulfuric acid (150 ° C).

2. Conversion: SO2 is oxidized with the contact of a catalyst, usually Vanadium pentoxide
(V2O5), to give SO3 by exothermic reaction:
2𝑆𝑂2 + 𝑂2 ↔ 2𝑆𝑂3
To maximize the formation of SO3, thermodynamic considerations and stoichiometry are
taken into account. According to the Principle of Le Chatelier-Braun, the temperature, pressure
or concentration of the reactants can be varied to shift the equilibrium towards the formation
of products.

3. Absorption: SO3 is absorbed in H2SO4 at 99% (the rest is water) to produce H2SO4 of 99.6%

𝑆𝑂3(𝑔) + 𝐻2 𝑂 ↔ 𝐻2 𝑆𝑂4

In a simple contact process, the conversion obtained is approximately 98%, depending on the
catalyst and the design, while in a double contact process a conversion up to 99.5% can be
achieved.

4. Absorption: The H2SO4 of 99.6% concentration is discharged from the absorption system
and diluted with water to a H2SO4 of 98.5%, which is the usual product of the market. Another
commercial product is H2SO4 of 93%.
 1.1. ANNUAL SULFURIC ACID PRODUCTION RATE

Sulfuric acid is one of the largest industrial chemicals produced in the world. For example, in
the early 1970s, the annual production of sulfuric acid in the United States, the largest
producer, exceeded 29 million tons, which corresponded to a daily production of 1/3 kg per
person per year. It is expected that this participation will increase until 2022. About 17% of the
global sulfuric acid is consumed in approximately 20 chemical processes, and the rest is
consumed in a wide variety of industrial and technical applications.

It is projected that the global demand for sulfuric acid will increase at an annual rate of around
2% in the next five years. China is the main market, accounting for more than 37% of
consumption in 2017, followed by North America with around 16%. Africa, Latin America,
Eastern and Western Europe and Southwest Asia are also big users. It is forecast that the
demand for fertilizers for sulfuric acid will grow by about 2.4% per year during the forecast
period, while the demand for chemical use will increase by 2.5% per year. Industrial uses will
decrease slightly until 2022.

Future growth in sulfuric acid consumption will be driven by the increase in population and the
extent to which people in the developing world switch to nutritionally rich food crops that
require significant amounts of fertilizer. It will also be influenced by the rate of increase in the
production of biofuels, especially corn-based fuels.

1.2. SULFURIC ACID PRODUCTION IN INDUSTRIAL PLANTS OF PERU

In Peru there are 3 large mining companies that have production plants of sulfuric acid in their
production process. These are the Ilo Smelter of Southern Copper Corporation, the
Cajamarquilla Zinc Refinery belonging to the company Votorantim Metais Cajamarquilla S.A.
and the La Oroya Metallurgical Complex owned by Doe Run Perú S.A

Zinc Refinery Foundry of La Oroya - Doe Run Perú SRL

of Ilo Smelter -
Cajamarquilla Southern
- Votorantim Copper Corp.
(2 plants) Zinc circuit Lead Circuit Copper Circuit
(under
construction)

Installed
Production
Capacity of 614 752 1 144 000 63 000 115 000 220 000
H2SO4 98.5% /
year

MT of H2SO4
98.5% / year
 499 239 962 984 58 000 115 000 220 000

As can be seen, if operations in La Oroya are resumed and the construction of the acid plant in
the copper circuit is completed, an annual production of 1 855 223 t of 98.5% sulfuric acid is
projected in Peru.

1.3. USES OF SULFURIC ACID

Sulfuric Acid is a fundamental industrial product, its applications are numerous and its
consumption is extraordinary. The uses of sulfuric acid are so varied that the volume of its
production provides an approximate index of the general industrial activity. This acid is a
product that is directly or indirectly present in any industry, and its consumption is the
thermometer of a country's industry.

Due to its corrosive characteristics, sulfuric acid is not used within the environment of the final
consumer, but it is used at the industrial level, although in a very small amount / proportion if
it is found in some household cleaners or in some dishwashers.

1.3.1. Car Batteries: Sulfuric acid is an important component in many types of batteries,
including car batteries and tractors, see battery acid. The battery creates energy from the
reaction between lead and sulfuric acid, which then combine to produce an inert compound,
as well as the electrons that generate the energy. As the reaction happens again and again, the
battery loses its charge. Rechargeable batteries can also contain sulfuric acid, as well as a
component that reverses the reaction and returns the individual compounds to their original
states.

1.3.2. Drain cleaners: Some types of drain cleaners have a sulfuric acid base. These cleaners,
known as sulfuric acid drainage openers, can cause severe burns to anyone who uses them
improperly or is exposed to a spill. For decades, there have been arguments about whether
these drain cleaners should only be used by professionals. In some areas, these types of drain
cleaners have been used as a makeshift weapon, thrown into someone else's face to cause
severe burns and permanent disfigurement.

1.3.3. Fertilizers: Fertilizing the gardens would be more difficult if it were not for the sulfuric
acid. Plants need three main nutrients to grow: nitrogen, phosphorus and potassium. Many
homeowners use various types of fertilizers in their yards and gardens; Inorganic phosphate
fertilizers are usually made with sulfuric acid. When sulfuric acid is combined with phosphate
rock, a chemical reaction produces phosphoric acid. This acid becomes a safe way to handle
and can be easily broken down and absorbed by plants. Ammonium sulfate is another
domestic fertilizer that is created with sulfuric acid.

1.3.4. Chemical manufacturing: As a chemical compound of great importance, sulfuric acid is

used in the manufacturing process of several well-known chemical products, such as
hydrochloric acid, nitric acid, phosphoric acid and many other industrial chemicals.

1.3.5. Oil refining: The refining process of crude oil requires the use of an acid as a catalyst and
sulfuric acid is often used for this purpose. It is used in a SAAU or a sulfuric acid alkylation unit.

1.3.6. Processing of metals: Used in the treatment of metals, to remove impurities, rust or
scale from the surface, as in the manufacture of steel. Nowadays, the use of sulfuric acid for
this purpose has diminished somewhat, since the industry now favors the use of hydrochloric
acid. Although hydrochloric acid is more expensive than sulfuric acid, it produces results more
quickly and minimizes the loss of base metal during the pickling process.

1.3.7. Drug manufacturing: Chemotherapy drugs are used to treat several types of cancer.
Cancer cells are more sensitive to DNA damage than normal cells, so in chemotherapy
treatment cancer cells are destroyed by damaging their DNA. This process is known as DNA
alkylation and a type of medication known as alkylating anti-neoplastic agents is used. Sulfuric
acid is used in the manufacturing process of such drugs.

1.3.8. Other uses: Sulfuric acid is the most commonly used chemical in the world and is used in
almost all industries such as:

• Pharmaceutical products

• Gasoline

• Paper bleaching

• Sugar whitening

• Water treatment

• Sulphonating agents

• Cellulose fibers

• Steel fabrication

• Coloreantes

• Amino acid intermediates

• Regeneration of ion exchange resins

1.4. ENVIRONMENTAL IMPACTS OF THE PRODUCTION OF SULFURIC ACID

The main environmental impacts that can be given in a general way in any sulfuric acid
production plant are those detailed below.

1.4.1. Energy consumption

This impact is positive. The processes of oxidation of sulfur, from SO2 to SO3, and the
absorption process, are exothermic, so the recovery of heat in sulfuric acid production plants is
key both economically and environmentally. It is estimated that between 57% and 64% of the
energy produced will generate steam that will be used in other points of the plant.

The production of energy from these processes also has the advantage that it does not form
CO2 as when using oil or natural gas.

1.4.2. Water consumption

This impact is negative. Water is used in two ways:

Cooling water: Most plants have systems installed in closed circuit to control the consumption
of cooling water.
Dilution water: to adjust the concentration of the acid by adding water to the absorption
system. The control of the addition of water is important to ensure the correct concentration
in the absorption tower and to prevent acid mists in the chimney.

1.4.3. Gaseous emissions

This impact is negative. In the manufacturing process of sulfuric acid, emissions to the
atmosphere of SO2, SO3 and H2SO4 may occur.

These emissions have different origins in the process and there are several techniques to
minimize their emission, which are detailed below:

Issue Causes Minimization techniques

𝑆𝑂2
Low efficiency in the In relation to the gases: Composition, speed through the
conversion from SO2 to catalyst and distribution, quality of the refrigeration,
SO3 operating pressure.

Converter design, number of beds.

In relation to the catalyst: quality and quantity.

𝑆𝑂3 Poor absorption Improvements in absorption: Design of the absorption

efficiency. tower (speed), acid distribution, acid temperature
(vapor pressure).
Steam pressure of
sulfuric acid and Oleum

𝐻2 𝑆𝑂4 Collection of the drained in the tower itself.

Design of the tower.
Design of the absorption tower.
Formation of mists.
Droplet separators, or mist filters (internal).
Vapor pressure.
Process control: efficiency of the drying tower, gas inlet
temperature in the absorption, NO content in the gases,
acid vapor pressure

1.4.4. Water discharges

This impact is negative. You can have the following water discharges in a sulfuric acid
production plant:

• Drainage of weak acid solutions

• Accidental spills.
To control this impact, water treatment plants must be operated, whose discharges must
comply with the Maximum Permissible Limits of Liquid Mining-Metallic Effluents established in
Peruvian environmental regulations.

1.4.5. Solid waste

During the manufacture of sulfuric acid, the following solid waste can be produced:

• Exhausted catalysts. These wastes could be recycled to recover the vanadium content
(generally made by the manufacturer itself) or they should be disposed "in a safe, sanitary and
environmentally appropriate manner" because it is a hazardous waste.

• Waste packaging and packaging. According to their content, these wastes are considered
dangerous and should be handled as such.

1.4.6. Accidental contamination

There is always a risk of accidental contamination when handling chemicals. In a sulfuric acid
production plant, the stage of greatest risk is the transport of the product. Due to this risk, the
transport of these materials is subject to specific regulations. There is also a risk of accidental
contamination in the storage of sulfuric acid, but each plant has different systems to control
spills. It also has guidelines / regulations that apply to the storage of sulfuric acid.

2. METHOD OF CONTACT

The contact method starts from the sulfur dioxide obtained by different methods

2.1. FIRST STAGE: PRODUCTION OF SO2

The required so2 can be obtained by means of elemental sulfur, but we will consider as the
raw material pyrite, iron disulfide mineral, FeS2, which by roasting with excess air produces
iron (III) oxide and sulfur dioxide in a reaction Redox:

4𝐹𝑒𝑆2(𝑆) + 11𝑂2(𝑔) → 2𝐹𝑒2 𝑂3(𝑆) + 8𝑆𝑂2(𝑔)

Once the sulfur dioxide is obtained and before entering the reactor, it must be purified, since it
can be mixed with residues of other compounds. Various methods can be used for this, such as
passing through dust separators, mechanical or electrostatic, and washing with water and
concentrated sulfuric acid. Already purified it will pass to the reactor for the production of
SO3.

2.2. SECOND STAGE: PRODUCTION OF SULFUR TRIOXIDE FROM SULFIDE DIOXIDE

The production of sulfur trioxide from the reaction of sulfur dioxide with oxygen is an
exothermic and reversible reaction (it does not occur completely but reaches a chemical
equilibrium, in which there is still presence of both reagents and We can write your
thermochemical equation as:
 𝐾𝐽
2𝑆𝑂2(𝑔) + 𝑂2(𝑔) ↔ 2𝑆𝑂3(𝑔) ∆𝐻 = −196
𝑚𝑜𝑙

The reaction is carried out in the presence of a solid catalyst, for this process we will consider
the vanadium pentoxide, V2O5. The catalytic reactions that are produced are the following:

𝑆𝑂42− + 𝑆𝑂3 → 𝑆2 𝑂72−

2𝑉 5+ + 𝑂2− + 𝑆𝑂2 → 𝑆𝑂3 + 2𝑉 4+

1
2𝑉 4+ + 𝑂2 → 2𝑉 5+ + 𝑂2−
2

1
𝑆𝑂2 + 𝑂2 ↔ 2𝑆𝑂3
2

2.3. THIRD STAGE: CONVERSION OF SO3 IN SULFURIC ACID

The gases from the catalysis are cooled to approximately 100 ° C and pass through an oleum

tower, to achieve partial absorption of SO3. The waste gases pass through a second tower,

where the remaining SO3 is washed with 98% sulfuric acid.

𝐻2 𝑆𝑂4(𝑙) + 𝑆𝑂3(𝑔) → 𝐻2 𝑆2 𝑂7(𝑙)

The unabsorbed gases are discharged into the atmosphere through a chimney.

A stream of water that reacts with the disulfuric acid is added and we obtain 98% sulfuric acid

𝐻2 𝑆2 𝑂7(𝑙) + 𝐻2 𝑂(𝑙) → 2𝐻2 𝑆𝑂4(𝑙)

8. APPENDIX

8.1. PYRITE

Pyrite, also called the gold of the poor, falls into the category of sulfide minerals. It is
commonly related to gold, because of its metallic yellow color. However, it can be
distinguished from this one thanks to its diverse and particular characteristics.

8.1.1. Characteristics of pyrite

It is composed of sulfur and iron (almost equal parts), is fine and solid grain, with little or no
light input. It is usually found in cubic pieces, although it can also occur in octahedra or
pyritohedra (12 pentagonal faces). Rarely in spheroidal form. The presence of crystals that
cross each other, gives a unique appearance.

It is insoluble in water, but soluble in nitric acid. Its chemical formula is FeS2.

There are different types of pyrite: iron pyrite (pyrite); Copper pyrite (Chalcopyrite); Arsenic
pyrite (Arsenopyrite); and Magnetic pyrite (Pirrotine).

8.1.2. Pyrite deposits

The most known pyrite deposits are located in locations in Italy, Peru, Spain, the United States,
China, Australia and Bulgaria. In Huanuco, Castrovirreyna, Huaron and Quiruvilca, the most
beautiful crystals have been found. While the largest mines (Riotinto and Tharsis), are in
Huelva, Spain. Collection crystals have been extracted in Falun, Sweden and Colorado (United
States).

8.2. EQUIPOS USADOS

8.2.1. Horno de lecho fluidizado.

El principio de funcionamiento estriba en la gran transferencia de calor que se lleva a cabo

desde las partículas de refractario que constituyen el lecho que se mantiene en constante
agitación, gracias al caudal de fluidificación.

A una determinada velocidad de ascensión del aire (1.5 a 2m/s) el lecho se fluidiza y adquiere
las características de un fluido (régimen de burbujeo). En este momento el lecho se expande
proporcionando unas condiciones químicas optimas de superficie específica, mezcla solido/gas
y homogeneidad térmica.

8.2.2. Drying tower

The drying tower has been specifically designed to allow the processing of small quantities of
product. Despite the small scale of the equipment, the powders produced are comparable to
those produced by large-scale production dryers. This system offers unparalleled flexibility,
with independent individually controlled inlet and outlet fans, along with the possibility of
varying the nozzle position and selecting flow configurations of parallel or countercurrent
currents. This flexibility is enhanced by an unrivaled range of options, designed especially for
use in laboratories and research.
8.2.3. Heat exchanger.

Heat exchangers are basic equipment for the operation of any energy facility, but also a key
system to improve energy efficiency and reduce energy consumption.

A heat exchanger is one of the most used equipment at the level of thermal installations, both
at the building, tertiary and industrial levels. A heat exchanger is a device designed to transfer
heat between two fluids. These two fluids (liquids, gases) can be in contact or separated by a
solid barrier. Its use is basic in all types of air conditioning or refrigeration systems, air
conditioning, energy transfer or chemical processes. The transmission of heat occurs by
convection and conduction.

8.2.4. Catalytic converter.

The purpose or purpose of a catalytic converter is to reduce the harmful emissions emitted by
the exhaust of a properly tuned internal combustion engine. This activity is achieved through
the combination of heat and a precious metal catalyst which generates the oxidation of
harmful emissions or manages to reduce them in harmless elements in the exhaust outlet, if
the engine of a vehicle is not tuned and has not been calibrated According to the specifications
of the Original Equipment Manufacturer, it reduces the efficiency of the catalytic converter
notably and generates faults.