Chapter III.

Industrial Production of Sulfuric Acid H₂SO₄ 2024/2025

Introduction

Sulfuric acid with the chemical formula H₂SO₄ is a highly important industrial product,
widely used in numerous applications in the chemical industries. Its production can be
considered the foundational industry of mineral chemistry. The production of sulfuric acid
already exceeded 10 million tons (Mt) at the beginning of the 20th century, reached 38 Mt in
1955, 160 Mt in 1990, and has now reached 180 Mt.

1. Properties of Sulfuric acid

Anhydrous sulfuric acid is a colorless, odorless liquid, more or less viscous depending on
its concentration, with a specific gravity of 1.83 at +15°C. It solidifies at +10.35°C and forms
several hydrates with the general formula H₂SO₄, nH₂O (where n = 1, 2, 3, 4, 6). The
solidification temperature varies significantly with the degree of hydration. It boils at 320°C,
containing about 98% pure acid. Commercial solutions are commonly used: one is 66°Baumé
acid, containing approximately 98% acid, and the other is 26°Baumé acid, which contains about
30% acid.

2. Production of Sulfuric Acid

Sulfuric acid is primarily produced from sulfur dioxide (SO₂), which is one of the main
gases produced by the combustion of fossil fuels or mineral processing. There are mainly two
industrial processes for producing this acid:

2.1. Lead Chamber Process

This is an older method that involves passing gases containing sulfur dioxide through lead
chambers, where sulfur dioxide is oxidized into sulfur trioxide by the air. The sulfur trioxide is
then absorbed into water to produce sulfuric acid. This method is less common today.

2.2. Contact Process

This is the most commonly used method for large-scale sulfuric acid production. It relies
on the oxidation of sulfur dioxide (SO₂) into sulfur trioxide (SO₃) using a vanadium-based
catalyst. This process occurs at high temperatures and produces a gas that is then absorbed into
a water solution to form sulfuric acid.

3. Raw Materials for Sulfuric Acid Production

The production of sulfuric acid requires several essential raw materials for its manufacturing
process. The main raw materials used in sulfuric acid production are:

1. Sulfur (S)

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 Chapter III. Industrial Production of Sulfuric Acid H₂SO₄ 2024/2025

o Sulfur is the primary raw material used in sulfuric acid production. It is often
extracted from natural deposits or industrial by-products (such as petroleum and
natural gas).
o Sulfur is burned to produce SO₂ (sulfur dioxide), which is the first step in the
production process.
2. Oxygen (O₂)
o Oxygen is essential for the oxidation of SO₂ into SO₃ (sulfur trioxide) in the
second step of the process. It is usually obtained from ambient air, and in the
contact process, oxygen is used to enhance the efficiency of the SO₂ oxidation
reaction.
3. Water (H₂O)
o Water is used in the final step of the process, where SO₃ is absorbed in water to
form sulfuric acid (H₂SO₄). The absorption of SO₃ in water is an exothermic
reaction that releases heat.
4. Vanadium-based Catalyst (V₂O₅)
o In the contact process, a vanadium-based catalyst is used to accelerate the
oxidation reaction of SO₂ to SO₃. Vanadium pentoxide (V₂O₅) is used as the
catalyst to increase the efficiency of the reaction without being consumed in the
process.

4. The Contact Method

The sulfuric acid productio process primarily consists of three phases: combustion,
oxidation, and absorption.

First Step : Production of Sulfur Dioxide (SO₂)

Sulfur dioxide (SO₂) is a colorless gas with a pungent odor. It is primarily produced industrially
by the combustion of sulfur or sulfur-containing minerals. Here are the main methods of
production :

[Link] by Sulfur Combustion

In this stage, sulfur dioxide (SO₂) is produced through the combustion of elemental sulfur is in
the presence of oxygen at. This process occurs at temperatures ranging from 900 to 1100°C.
The liquid sulfur is sprayed into fine droplets inside excess dry air to ensure complete
combustion and prevent any unburned sulfur. This means that sulfur fully reacts with oxygen,
leaving no unreacted sulfur. This reaction is highly exothermic (releases heat).

S(l) + O₂(g) → SO₂(g) ΔH°r, 298K = - 297 kJ/mole

After the reaction is complete in the furnaces, the composition of the exiting gases is as follows
12% SO₂: The percentage of sulfur dioxide produced.
10% O₂: The percentage of remaining oxygen.

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 Chapter III. Industrial Production of Sulfuric Acid H₂SO₄ 2024/2025

78% N₂: The percentage of nitrogen that does not react.

1. Production from Sulfur-containing Minerals

Sulfur dioxide can be produced by roasting sulfur-containing ores, mainly pyrite (FeS₂),
sphalerite (ZnS), and chalcopyrite (CuFeS₂).

Oxidation of pyrite : 4FeS2 + 11O2 → 2Fe2O3 + 8SO2

Oxidation of zinc sulfide : 2ZnS + 3O2 → 2ZnO + 2SO2

Oxidation of chalcopyrite : CuFeS2 + 4O2 → Cu+ 2FeO + 2SO2

2. Production by Sulfate Reduction

Some processes allow the production of SO₂ by reducing metallic sulfates with carbon :

Na2SO4+C→Na2S+2CO2+SO2

This method is less common and is mainly used in some chemical industries.

3. Production by Recovery from Industrial Gases

SO₂ is also a by-product of various industrial processes, including :

 Non-ferrous metallurgy (extraction of copper, lead, zinc).

 Combustion of sulfur-containing fossil fuels (coal, oil).
 Oil refining.

In these cases, SO₂ is often recovered and converted into sulfuric acid via the contact process.

Second Step : Conversion of SO₂ to SO₃ (Thermodynamics, Kinetics, and Converter

Calculations)

The conversion of SO₂ to SO₃ is an oxidation reaction that occurs in the sulfuric acid production
process using the contact process. This reaction requires a catalyst, usually vanadium oxide
(V₂O₅), and takes place at high temperatures.

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1. Thermodynamics

The reaction between SO₂ and O₂ to form SO₃ is exothermic, meaning it releases heat during
the reaction. The ΔH°r for this chemical equation is negative, indicating that the reaction
generates heat as it proceeds.

SO₂ + 1/2 O₂ ⇌ SO₃ ΔH°r, 298K = -99 kJ/mole

Equilibrium is achieved at high temperatures, which helps maximize the production of SO₃.

2. Kinetics

Kinetics depends on several factors, such as concentration, temperature, and the presence of the
catalyst. The rate of the reaction is highly dependent on temperature and the available oxygen.
At high temperatures and with the presence of vanadium oxide as a catalyst, the reaction occurs
much faster.

3. Calculations in Converters

In contact process converters, the conversion rate of the reaction is measured, which is the ratio
of the number of SO₃ molecules formed to the number of SO₂ molecules available in the
incoming gas. The conversion rate can be calculated using the following equation :

Conversion Rate = X = (SO₂ (inlet) - SO₂ (outlet)) / (SO₂ (inlet)) × 100 (%)

Where :

 SO₂ (inlet) : The concentration of sulfur dioxide in the incoming gas to the converter.
 SO₂ (outlet) : The concentration of sulfur dioxide in the gas exiting the converter after
the reaction.
 The conversion rate represents the ratio of SO₃ molecules formed to SO₂ molecules in
the incoming gas.

These calculations are used to determine the efficiency of the converter and to adjust operating
conditions such as temperature and gas pressure to achieve the optimal conversion rate. For
example, temperature can be adjusted to accelerate the reaction, or pressure can be increased to
improve the conversion rate and increase the production of SO₃.

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Third Step : Absorption of SO₃

After sulfur trioxide (SO₃) is formed in the contact process converters, it is absorbed in
water or an aqueous solution to produce sulfuric acid. This process involves absorbing the gas
containing SO₃ into cold water or an aqueous solution containing sulfuric acid, where SO₃
reacts with water to form sulfuric acid (H₂SO₄) according to the following chemical equation :

SO₃ + H₂O → H₂SO₄

At this stage, the gas containing SO₃ is cooled after being absorbed by water or the aqueous
solution. The heat generated from the previous reaction is used to accelerate the absorption
process.

The process is typically carried out in absorption towers or special reactors equipped with
systems to effectively distribute the gas and liquid, ensuring complete absorption of SO₃ and
its conversion into sulfuric acid. Production units can have capacities of up to 2500 tons per
day.

5. Manufacturing and Environmental Aspects

The manufacturing of sulfuric acid, particularly through the contact process, involves
significant chemical reactions that impact the environment. These reactions, which produce
SO₂ and SO₃, generate heat and contribute to emissions if not properly managed.

5.1. Environmental Aspects of Sulfuric Acid Production

1. Air Pollution
o SO₂ emissions : If the process is not properly controlled, sulfur dioxide (SO₂),
a significant air pollutant, can be released into the atmosphere. SO₂ is a precursor
to acid rain, which harms ecosystems, soil, water bodies, and infrastructure.
o Nitrogen oxides (NOx) : The use of high-temperature processes can lead to the
formation of NOx, which contributes to air pollution, acid rain, and smog.
2. Water Usage and Contamination
o Water consumption : The absorption of SO₃ into water to form sulfuric acid
requires substantial amounts of water. This can lead to water scarcity concerns
in areas with limited freshwater resources.
o Water contamination : If sulfuric acid production waste or gases like SO₂ are
not treated properly, there is a risk of water contamination, impacting local water
quality.
3. Energy Consumption
o The process requires high temperatures (around 430-600°C), making energy
consumption a significant environmental concern. The use of fossil fuels to
generate this heat can contribute to carbon emissions and climate change.
4. Waste Management

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o Solid waste : The spent catalysts and other residues from the process must be
properly managed to prevent contamination. Disposal of hazardous materials
can pose environmental risks.

5.2. Mitigating Environmental Impact

1. Emission Control : Scrubbers and filters are often used to capture SO₂ and NOx before
they are released into the atmosphere, reducing harmful emissions.
2. Sustainable Practices : Sulfuric acid production can benefit from improved recycling
of sulfur compound and better management of waste products to minimize
environmental impact.
3. Energy Efficiency : Improving energy efficiency in the production process by using
cleaner sources of energy or waste heat recovery systems can help reduce overall
environmental impact.

By improving these practices, sulfuric acid production can be made more environmentally
sustainable while reducing its impact on the atmosphere, water, and energy consumption.

6. Flow-Sheets

Flow-sheets are graphical representations used to describe industrial processes or chemical

reactions in various systems. These diagrams show the sequence of operations and their
relationships, using symbols and lines to represent equipment, components, and materials
entering and exiting the system.

6.1. Types of Flow-Sheets

1. Simple Flow Diagram : Used for processes that require a simple sequence of stages. It
shows the incoming and outgoing materials and basic processes like combustion,
oxidation, or absorption.
2. Complex Flow Diagram : Used in large industrial systems or multi-stage processes,
where detailed stages such as chemical reactions, catalysts, and temperature are
represented. It often includes multiple reactors, absorption towers, or chemical plants.
3. Process Flow Diagram (PFD) : Commonly used in chemical engineering, it shows the
flow of materials and energy through the system using standard symbols such as vessels,
pipes, reactors, and heat exchangers.
4. Piping and Instrumentation Diagram (P&ID) : Used in mechanical and chemical
engineering to represent processes in more detail, including pipes, valves, pumps, and
industrial equipment. This diagram provides in-depth information about the control
systems and instrumentation involved in the process.

6.2. Importance of Flow-Sheets

 Simplifies Understanding : They help in understanding complex processes easily.

 Process Improvement : Used to identify bottlenecks or weak points in operations.

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 Documentation : Serve as a method for documenting industrial and chemical systems.

 Communication : Facilitate communication between engineers, technicians, and
process supervisors.

6.3. Example of a Flow-Sheet for Sulfuric Acid Production

In the sulfuric acid production process, a flow-sheet can represent stages such as :

1. Combustion to produce SO₂.

2. Oxidation using a vanadium catalyst to produce SO₃.
3. Absorption in water or an aqueous solution to produce sulfuric acid.

These flow-sheets show the flow of chemical materials through reactors or towers, as well as
operational variables such as temperature and pressure.