Faculty of Engineering and Technology

Department of Chemical Engineering

Title: Manufacture of Sulfuric Acid from Pyrite

Surname and Initials : Thusini M

Student Number : 22017332

Subject : Chemical Process Industries

Examiner : Prof. John Kabuba Tshilenge

Report Type : Short report

Submission Date : 17 May 2023

Table of content

1. Cover page……………………………………………………………. (i)

2. Table of content………………………………………………………. (ii)

3. Introduction……………………………………………………………. (1)

3.1 Sulfuric acid background……………………………………………… (1)

Table 1.1 Background information on Sulfuric Acid………………… (2)

4. Capacity limitations……………………………………………………. (3)

4.1 Availability of raw materials……………………………………………... (3)

Availability of raw materials………………………………………….……. (4)

5 Flow diagram and Process Description …………..……………………… (5)

5.1 Method………………………………………….……….………………… (5)

5.2 First stage of roasting …………………………….……….…………….... (5)

First stage of roasting ……………………………………….………..…… (6)

Figure 1-Pyrrhotizing roasting Plant………………………………………. (7)

5.3 The second stage of roasting……………………………………………… (7)
The second stage of roasting……………………………………………….. (8)
6. Conclusion and Recommendations……………………………………….. (9)
7. References……………………….………………………………………… (10)
3 Introduction

3.1 Sulfuric Acid background

Sulfuric acid commonly known in antiquity as oil of vitriol which is an ancient

name by Medieval European alchemist because it was prepared by roasting iron

sulphate or green vitriol in an iron retort, it is a mineral acid made up of hydrogen,

sulphur and oxygen in a molecular form H2SO4. The concentration of sulfuric acid

is a leading factor that determine its properties, with that being said a strong

concentration of sulfuric acid can damage almost anything it comes into contact

with this ranges from rock matter, metals and tissues (e.g. skin tissue or flesh),

100% concentrated sulfuric acid (degrading concentration) corrodes matter. This is

due to it being a strong dehydrating and oxidizing agent. It forms a homogeneous

mixture when it is mixed with water. Although special caution should be taken

when adding sulfuric acid to water as it is an exothermic reaction (heat is released).

Water should not be added to sulfuric acid as the heat released will boil the

solution and spray spheroid of hot acid which can cause severe acid burns, to

explain this phenomenon more in detail, partial decomposition of the pure acid into

water and sulphur trioxide forms and escapes as a vapour causing a decrease in the

concentration of acid by 1.7% (Encyclopaedia Britannica).

3.2 Table 1.1 Background information on Sulfuric Acid (Sulfuric Acid)

Names

IUPAC name
Sulfuric acid
Other names
Oil of vitriol
Hydrogen sulfate
Properties

Chemical formula H2SO4

Molar mass 98.079 g/mol

Appearance Colorless viscous liquid

Colorless viscous liquid Odorless

Density 1.8302 g/cm3, liquid

Melting point 10.31 °C (50.56 °F; 283.46 K)

Boiling point 337°C (639 °F; 610 K) When sulfuric acid is

above 300 °C (572 °F; 573 K), it gradually

decomposes to SO3 + H2O

Solubility in water miscible, exothermic

Vapor pressure 0.001 mmHg (20 °C)

Related compounds

Related strong acids Sulfurous acid

Peroxymonosulfuric acid
Sulfur trioxide
Oleum
Except where otherwise noted, data are given for materials in their standard state (at 25 °C

[77 °F], 100 kPa)

4 Capacity Limitations

4.1 Availability of raw materials

The sourcing of raw materials is a core attribute that limits the plant’s capacity.

Historically, pyrite was used commercially as a source of sulphur, specifically for

the manufacturing of sulfuric acid, but in today’s chemical industry sulphur is

gathered on a large scale as a by-product of petroleum processing, due to the fact

that it is an abundant source of iron, pyrite is not generally used as an iron ore.

Sulphur and iron(sulfuric) pyrite are traditionally the basic sources of raw material

for the manufacture of sulfuric acid. About 50% of the sulfuric acid is produced

from sulphur and one third is from pyrite.

Pyrite is widely dispersed and forms under extremely varied conditions. For

instance, it can be produced by magnetic (molten rock) segregation, by

hydrothermal solution, and as stalactitic thickening. It occurs as an accessory

mineral in igneous rocks, in vein deposits with quartz and sulphide minerals, and in

sedimentary rocks, such as shale, coal, and limestone.

Pyrite occurs in large deposits in contact metamorphic rocks. Deposits of copper

bearing pyrite are widely distributed and often of great size. They usually occur in

or near the contact of eruptive rocks with schists or slates.

Sulfuric acid is formed naturally by the oxidation of sulphide minerals, such as

iron sulphide. The water derived from it is highly acidic and is called acid mine

drainage or acid rock drainage. It has the ability to dissolve sulphide ores’ metals,

which progress in brightly coloured solutions of toxicity. The oxidation of pyrite

by molecular oxygen produces iron (II)

2FeS2(s) + 7O2 + 2H2O → 2Fe2+ + 4SO-2 + 4H+

Oxidation of Fe2+ into Fe3+

4Fe2+ + O2 + 4H+ → 4Fe3+ + 2H2O

The precipitation of Fe3+ produced into hydroxide or hydrous iron oxide:

Fe3+ + 3H2O → Fe(OH)3 + 3H+

Oxidation of pyrite by the iron ion:

FeS2(s) + 14Fe3+ + 8H2O → 15Fe2+ + 2SO42- + 16H+

Pyrite (iron disulphide, FeS2) yields iron (II) sulphate FeSO4 when heated in air,

when it is oxidized for the second time to form iron sulphate, Fe2(SO4)3, which

decomposes to iron oxide and sulphur trioxide when heated to 480֯C and yields

sulfuric acid in any concentration when immersed in water. This is however an

expensive process which the large-scale use of concentrated sulfuric acid.

5 Flow diagram and Process Description

At the beginning we have a moisture content of 1.2%, a 49.8% content of sulphur,

a range between 43% to 86% of iron, 0.72% CaO), 0.5% Al2O3, 2.4% SiO2, 0.13%

Cobalt contained in the concentrate of pyrite and 89% of the constituents had a size

range of less than 0.1mm.

5.1 Method

In figure 2 we can see a see a semi industrial pyrrhotite roasting in autogenous

system at 22% blowing oxygen(O2) content and 20-25% lattice temperature were

controlled in this device, which encompasses the furnace fluidized bed (operation

area 0.33 m2) with the mobile heating chamber, handling system and dust trapping

apparatus.

5.2 First stage of roasting

The centre of method is in following: the autogenous roasting production of

sulphide materials of the ash(cinder) and unalloyed production of gas appropriate

for driest processing to produce sulfuric acid excluding anhydride and oxygen is

accomplished by alteration or modification of 60% to 65% of sulphur ‘pyrite’ into

SO2 in the initial stage. Multiple reactions take place in this process and after this,

the SO2 which comes in with the gas is completely demolished and the overall

oxygen used for blowing is consumed completely.

In the procedure of test, velocity of concentrate feeding air-consumption and mazut

were regulated, the eject under the arch, resistance of layers, temperature under

lattice, the layer (location 3), under the grid, the final burning chamber, cyclone

and coolers of accumulation, the concentration of CO2 and SO2 in gases was

controlled.

Autogenous pyrrhotizing roasting at specific capacity of 26 to 29tons/m2.day with

60-65% of desulphurization was achieved. Iron oxide of 20 to25% with pyrrhotite

are the product produced from solid roasting. An excess of 95% oxygen is used.

Average into extraction into gas: 40.1%dust and 49.3% is from the ash(cinder).

Sulphur and iron proportionate to expanse of pyrite separation 90% to 95% and in

cyclone grime, 74% to 75%. In the layer created from different time there

concentrate of different sizes and they have different extent of pyrite dissociation.

Whilst coming through the assembly hall fine dirt trapped in the electrical filter of

final sculpture burning are partly oxidized. An average of 0.1% to 0.5% oxygen

and 16.7% to 17% SO2 is produced in the gas. This proportionate to the expense of

oxygen use in the layer exceeding 95%.

 Figure 1-Pyrrhotizing roasting Plant
1. Fluidized bed furnace, 2. Fire hall, 3. Bunker, 4. Feeder, 5. Unloading, 6.
Accumulator cooler, 7. Container, 8. Cyclone.

5.3 The second stage of roasting

A two stags roasting operation is shown in Figure 2. The gasification of the
remainder of the Sulphur takes place in the second stage. With the utilizing of the
cold air blowing on the layer at the temperature of 685-700֯C Fe3O4 cinder(ash) is
produced. The expenditure is 900-1000 Nms/m2h. The oxygen usage in the blowing
was 0.14-0.175Nm3/kg of the concentrate.
The second stage roasting is done in furnaces of KC, where by product gases are
produced with 9 to 10% O2, 8 to 10% SO2, and almost 0.5% SO3 using the standard
of cold air blowing gases. Gases are produced with 16 to 17% SO2, 0.1 to 0.15 SO3
and 0.1 to 0.5 O2. As a result of blending of by-product gases of the two stages
synthesizing of gases with a reduced amount of SO3 result in less quantity washing
water acid, reduced the corrosion effect on the dirt trapping and gas piping regimes
and increase the sulfuric acid output in the end product.

Fig.2 Principle scheme of two-stage roasting of pyrite concentrate

The reduced usage of the fanning air in contrast with studied technologies give rise
to more concentrate gases and this is followed with less energy consumption for
lower fanning volume, less operating costs for the decontamination of produced
gases, and the plant becomes more profitable.
6 Conclusion and Recommendations
To conclude the industrial experimental scale for technology of the two-stage
roasting of pyrite concentrates for producing rich sulphurous gas with 0.5 to 1.5%
sulphur trioxide:
• we can increase the roasting gas from 50 to 70%, which enhances the
equipment’s resistance to corrosion and improve productivity of roasting.
• Decrease the fanning usage by 30% at the disbursement of increasing the
stretch of the oxygen utilization and similarly increase the content of SO2 in the
roasting gases.
• Decrease the needed roasting region of the furnace for 30 to 40%
• Stream line the regime of dust-gas decontamination at the disbursement of
reduce the volume of roasting gases, decrease the content of sulphur trioxide
• Make the technology more environmentally friendly for the processing of raw
material with non-ferrous metals
• Decrease the capital and operational costs for roasting.
Thus, enabling the production of sulphuric acid to become more economical by
reducing the concentration of SO3 from 0.5 to 0.1 to 0.15, which enhances the work
of the cooling equipment and decontamination of roasting gas.
For the manufacturing of sulfuric acid, we can recommend:
• Using high quality catalyst and raw feed to decrease contaminants and increase
conversion rate
• Applying improved control and monitoring systems to recognize or pick up any
variation(deviation) or system crash and maximize the process requirements
• Obtaining the best available techniques and emission limits to reduce
environmental of sulfuric acid production and adhere to the carbon emission
regulatory standards
• Reducing energy and chemical depletion by retrieving waste heat and acid
vapours from this process which also increase productivity
• Sulfuric acid production such as pyrite roasting or bioleaching are alternative
methods which lower costs or benefit the environment.
7 References
1. Vanyukov, A.V., Zaitsev, V.Ya., 1993, Theory of pyrometallurgical processes:
Metallurgy,Moscow.
2. Method of processing of cobalt containing pyrite concentrates: Patent 1990.
3. Method of processing of sulfide raw materials. Preliminary patent. Almaty: 2005.
4. Luganov, V.A., Shabalin, V.I., Vasilevskiyi, O.V., 1982, “Autogenous
pyrrhotizing roasting of pyrite concentrate”. J. Chemistry and technology of
chalcogenes and chalcogenides.
5. Tarasov, A.V., 2001, Production of non-ferrous metals and alloys: Metallurgy,
Moscow.
6. Habashi, F. “Clean Technology in the Metallurgical Industry”. International
conference: Metallurgical high technology and new materials of heavy
nonferrous metals. April 3-5, 2002
7. Merichem Gas Technologies. (n.d.). Safe Handling of Molten Sulfur.
(VertMarkets, Inc.) Retrieved June 16, 2013, from Oil and Gas online:
http://www.oilandgasonline.com/doc/Safe-Handling-Of-Molten-Sulfur-0001
Chemical Safety Handbook. (2002).
8. Retrieved June 16, 2013, from Southern States Chemical:
http://www.sschemical.com/wp-content/uploads/SAFETY1.pdf
9. www.bitannoca.com/science/pyrite
10.https://en.wikipedia.org/wiki/Sulfuric_acid