Natural occurrence, Sulfur Production, Frasch process, Surface Sulfur Mining, Underground Sulfur Mining, Reserves, World Sulfur Production, Sulfur USAGE

1. Topic 7: Sulfur Ore Deposits
Prof. Dr. H.Z. Harraz Presentation
Sulfur Ore Deposits
2015- 2016
Hassan Z. Harraz
hharraz2006@yahoo.com

2. Outline of Topic 7:
Natural occurrence
Production
Frasch process
Surface Sulfur Mining
Underground Sulfur Mining
Reserves
World Production
USAGE
21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits

3. Introduction
 Sulfur (S) composes 0.06% of Earth’s crust
 Sulfur (S) is an important constituent of volcanic gases, magmatic emanations, and is
common in hot springs.
 Sulfur (S) is distributed in the earth's crust in the form of sulfates (SO4), sulfides, and
native sulfur.
 The largest physical reservoir is the Earth's crust where sulfur is found in gypsum
(CaSO4.2H2O) and pyrite (FeS2).
 The largest reservoir of biologically useful sulfur is found in the ocean as sulfate anions
(2.6 g/L), dissolved hydrogen sulfide (H2S) gas, and elemental sulfur.
 Sulfur is deposited from sulfates (SO4) and hydrogen sulfide (H2S) in bodies of water
where reducing conditions.
 Sulfates (SO4) are also reduced by anaerobic bacterial (e.g., Clostridium nigrificans) to
hydrogen sulfide (H2S), which, in turn oxidises to sulfur (S) and water (H2O).
 Sulfur is a vital element for all forms of life, and is widely used in biochemical processes. It
is one of the major plant nutrient after nitrogen, phosphorus, and potassium. Sulfur
provides a direct nutritive value to the plants hence contributing to an increase in the crop
yields.
7) Sulfur Ore Deposits
21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 3

4. Natural occurrence
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 On Earth, elemental sulfur can be found near hot springs and volcanic regions in many
parts of the world, especially along the Pacific Ring of Fire; such volcanic deposits are
currently mined in Indonesia, Chile, and Japan. Such deposits are polycrystalline, with the
largest documented single crystal measuring 22×16×11 cm. Historically, Sicily was a large
source of sulfur in the Industrial Revolution.
 Native sulfur is synthesized by anaerobic bacteria acting on sulfate minerals such as
gypsum in salt domes. Significant deposits in salt domes occur along the coast of the Gulf
of Mexico, and in evaporites in eastern Europe and western Asia.
 Native sulfur may be produced by geological processes alone. Fossil-based sulfur
deposits from salt domes have until recently been the basis for commercial production in
the United States, Russia, Turkmenistan, and Ukraine.
 Currently, commercial production is still carried out in the Osiek mine in Poland. Such
sources are now of secondary commercial importance, and most are no longer worked.
 Common naturally occurring sulfur compounds include the sulfide minerals {such as pyrite
(FeS2), cinnabar (HgS), galena (PbS), sphalerite (ZnS) and stibnite (SbS)} and the
sulfates {such as gypsum (CaSO4.2H2O), anhydrite (CaSO4), Celestite (SrSO4), alunite
(KAl3(SO4)2(OH)6), and barite (BaSO4)}.
 On Earth, just as upon Jupiter's moon Io, elemental sulfur occurs naturally in volcanic
emissions, including emissions from hydrothermal vents.

5. Natural surface Sulfur Deposit
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6. Production
 Any of the natural mineral formations containing native sulfur in concentrations that
make extraction technically feasible and economically profitable.
 Sulfur ores are classified according to the composition of the enclosing rock and include
limestone-calcite (more than 90% of world production), calcitic dolomite, clay, gypsum,
opalite, and quartzite ores.
 Deposits of sulfur ores can occur as sheet-like, lenticular, or pocket formations and can
be simple or complex (with rock intercalated).
 Deposits can vary in extent from tens of centimeters to tens of meters.
 Common naturally occurring sulfur compounds include the sulfide minerals {such as
pyrite (FeS2), cinnabar (HgS), galena (PbS), sphalerite (ZnS) and stibnite (SbS)} and
the sulfates {such as gypsum (CaSO4.2H2O), anhydrite (CaSO4), Celestite (SrSO4),
alunite (KAl3(SO4)2(OH)6), and barite (BaSO4)}.
 Depending on the structure and texture of the ores, which determine the ores technical
properties, distinctions are made between, for example, ores containing crystal
aggregates and those with finely disseminated sulfur particles.
 Sulfur ores containing : i) >25% sulfur are considered rich, ii) <25 to 10% are
classified as intermediate, and iii) those with < 10 to 5% are considered lean.
 Useful by-products of the ores include limestones (flotation wastes, used for liming
soils), celestite, pyrite, and alunite. Harmful substances in the ores include organic
matter (bitumens), As, and Se.
21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 6

7. Production
 Elemental Sulfur is found on the Earth in:
 Volcanic deposits or volcanic emanations (i.e.,
Fumaroles)
 Underground deposits
 The largest physical reservoir is the Earth's crust where
sulfur is found in gypsum (CaSO4.2H2O) and pyrite (FeS2).
• Elemental sulfur was once extracted from salt domes where
it sometimes occurs in nearly pure form, but this method has
been obsolete since the late 20th century.
 Today's sulfur production is as a side product of other
industrial processes such as oil refining; in these processes,
sulfur often occurs as undesired or detrimental compounds
that are extracted and converted to elemental sulfur.
• Today, almost all elemental sulfur is produced as a by-
product of removing sulfur-containing contaminants from
natural gas and petroleum.
• Today, sulfur is produced from petroleum, natural gas, and
related fossil resources, from which it is obtained mainly as
hydrogen sulfide (H2S(g)). Organosulfur compounds, undesirable
impurities in petroleum, may be upgraded by subjecting them to
hydrodesulfurization, which cleaves the C–S bonds:
R-S-R + 2 H2 → 2 RH + H2S
• The resulting hydrogen sulfide from this process, and also as it
occurs in natural gas, is converted into elemental sulfur by the
Claus process. This process entails oxidation of some hydrogen
sulfide to sulfur dioxide and then the comproportionation of the
two:
3 O2 + 2 H2S → 2 SO2 + 2 H2O
SO2 + 2 H2S → 3 S + 2 H2O
Sulfur powder
Roll Sulfur
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Sulfur occurs in fumaroles
such as this one in Vulcano, Italy

8. Production
Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 8
 The major genetic and industrial type of deposit is that formed by infiltration and
metasomatism in the sulfates of sedimentary strata and cap-rock formations
over salt domes. Aside from ores, sulfur and sulfur compounds can also be
obtained from pyrites, from the hydrogen sulfide in natural gas, and from the
wastes (tailings) from the concentration of chalcopyrite and other sulfide ores.
Other sources include bituminous sandstones, anhydrite and gypsum, the sulfur
gases of furnaces used in metallurgy and in the coking of heavy residual
bottoms of crude oil, and petroleum containing sulfur. All sources exclusive of
ores are known collectively as sulfur-bearing raw materials.
 Sulfur is extracted from sulfur ores by a mining process (10–20% of world
production) and a geotechnological process (90–80%). In the former, sulfur
ores are mined in quarries or, much less frequently, in underground shafts. The
ores are then concentrated by flotation with the production of a sulfur
concentrate, from which crude, or lump, sulfur is obtained using special
furnaces, kettles, and autoclaves. The crude sulfur is then purified to yield
refined sulfur.
 In the geotechnological process, the sulfur is melted from sulfur ores at the
deposit site using superheated water (Frasch process). A hole is boredfrom the
ground surface to the deposit. Three pipes are then lowered: one for the water at
165°–170°C, one for air, and one for conveying the molten sulfur to the surface.
21 November 2015

9. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 9
Sulfur and algae turn hot springs into pools of living color.
The water is condensation from hot gases rising from
magma chambers. As the water evaporates, salts and
minerals form a vivid crust.
In Africa's Afar depression, pastoral tribes and salt traders
survive amid a surreal landscape of fissures, faults, and a
boiling lake of lava.
Sulfur and Algae Hot Springs

10. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 10
Sicilian kiln used to obtain sulfur from
volcanic rock.
Negative Impact Sulfur
Sulfur Lumps

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 As a mineral, native sulfur under salt domes is produced by the action of
ancient bacteria on sulfate deposits.
 It was removed from such salt-dome mines mainly by the Frasch process.
 In this method, superheated water was pumped into a native sulfur deposit to
melt the sulfur, and then compressed air returned the 99.5% pure melted
product to the surface.
 Throughout the 20th century this procedure produced elemental sulfur that
required no further purification. However, due to a limited number of such
sulfur deposits and the high cost of working them, this process for mining
sulfur has not been employed in a major way anywhere in the world since
2002.
Production

12. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 12
Production

13. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Salt Deposits
13
Jashak salt dome is one of the largest and the most
beautiful and typical salt domes in Iran and the
Middle East

14. • Subsurface sulfur recovered
by the Frasch Process:
 superheated water pumped
down into deposit, melting the
sulfur and forcing it up the
recovery pipe with the water
Frasch Process
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15. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 15
Sulfur recovered from hydrocarbons in Alberta,
stockpiled for shipment in North Vancouver, B.C.
 Owing to the high sulfur content of the Athabasca Oil Sands, stockpiles of
elemental sulfur from this process now exist throughout Alberta, Canada.
 Another way of storing sulfur is as a binder for concrete, the resulting product
having many desirable properties (see sulfur concrete). Sulfur is still mined
from surface deposits in poorer nations with volcanos, such as Indonesia.
Production

16. Surface Sulfur
Mining
Sulphur Mine, Kawah Ijen Volcano, Java, Indonesia
On Earth, elemental sulfur can be found near
hot springs and volcanic regions in many
parts of the world, especially along the Pacific
Ring of Fire; such volcanic deposits are
currently mined in Indonesia, Chile, and
Japan.
A man carrying sulfur blocks from Kawah Ijen, a volcano in East Java,

17. A Sulfur Deposit
Melted sulfur obtained from surface
deposits by the Frasch process.
Fig. 2: The Frasch Process for Recovering Sulfur from surface deposits
Important sedimentary sulfur deposits occur near Knibyshev, Sukeievo, and
Chekur in Russia. The occurrences consist of thin gypsum beds with layers of
pure sulfur, laminations of sulfur and calcite, or sulfur nodules in bituminous
limestone. Celestite (SrSO4) is an unusual associate.
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18. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 18
Underground Sulfur Mining

19. Reserves
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World reserves of native sulfur at the beginning of
1973 were estimated at 871.5 million tons, not
including reserves of the socialist countries.
Most sulfur ores (approximately 76%) are
concentrated in Iraq (335 million tons), the United
States(150 million tons of extractive reserves),
Chile (100 million tons), and Mexico (80
milliontons). Large deposits of sulfur ores are
known to exist in Poland (Tarnobrzeg and
Grzybów deposits).

20. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 20
Production and price (US
market) of elemental sulfur
 The world production of sulfur in 2011 amounted to 69 million tonnes (Mt),
with more than 15 countries contributing more than 1 Mt each. Countries
producing more than 5 Mt are China (9.6), US (8.8), Canada (7.1) and Russia
(7.1).
 Approximately 27% came from native sulfur, 38% from natural gas and
petroleum, 19% from pyrites, and 16% from other types of sulfur-containing
raw materials.
 While the production has been slowly increasing from 1900 to 2010, the price
was much less stable, especially in the 1980s and around 2010.
World Production

21. 21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 21
MAJOR SULFUR PRODUCERS OF THE WORLD-2010
COUNTRY
PRODUCTION IN
(THOUSAND METRIC
TONNES)
China 9600
Russia 7100
Canada 7100
Germany 3800
Japan 3400
Saudi Arabia 3200
Kazakhstan 2000
United Arab Emirates 2000
Mexico 1700
Iran 1600
Chile 1600
South Korea 1600
France 1300
India 1200
Australia 930
Venezuela 800
Kuwait 700
Poland 750
Italy 740
Spain 640
Finland 615
South Africa 540
Netherlands 530
Uzbekistan 520
Other Countries 4800

22. USAGE
• Sulfur had been known and used since a long time in
ancient Greece, China, and Egypt.
• The fumes of the element were used as fumigants.
Sulfur was used in medicinal mixtures mostly as balms
and anti-parasitics. It was also used to make the best
quality of black gunpowder.
• Elemental sulfur is used in Black gunpowder, Matches
and Fireworks in the vulcanization of rubber; as a
fungicide, insecticide, and fumigant; in the
manufacture of phosphate fertilizers; and in the
treatment of certain skin diseases.
• The principal use of sulfur, is in the preparation of its
compounds, such as:
 Sulfuric acid.
 in fertilizers
 is also used in matches, insecticides and
fungicides.
 Sulfur dioxide, used as a bleaching agent,
disinfectant, and refrigerant;
 Sodium bisulfite, used in paper
manufacture; carbon disulfide, an
important organic solvent;
 Hydrogen sulfide, sulfur trioxide, used as
reagents in chemistry;
 Epsom salts (magnesium sulfate), used as a
laxative, bath additive, exfoliant, and
magnesium supplement in plant nutrition; the
21 November 2015 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 22
Sulfuric acid production in 2000