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Sulfur Ore Deposits

Presentation · October 2015

DOI: 10.13140/RG.2.1.4410.9685

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Topic 7: Sulfur Ore Deposits

Hassan Z. Harraz
hharraz2006@yahoo.com

2015- 2016

Prof. Dr. H.Z. Harraz Presentation

Sulfur Ore Deposits
 Outline of Topic 7:
 Sulfur Ore Deposits
 The Cycle of Sulphur
 Natural occurrence
 Production
Frasch process
Surface Sulfur Mining
Underground Sulfur Mining
 Reserves
 World Production
 USAGE

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits

 7) Sulfur Ore Deposits
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.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 3

SULFUR ORE DEPOSITS
The Cycle of Sulfur
 Sulphur is distributed in the earth's crust in the form of sulfates, sulfides,
and native sulphur.
 It is copious and important constituent of volcanic gases and magmatic
emanations and is common in hot springs.
 The sulfur of sedimentary deposits is derived from sulfates in rocks, from
partial oxidation of hydrogen sulfide obtained from volcanic emanations and
anaerobic bacterial reduction of sulfates in solution.
 Sulphur is deposited from sulfates and hydrogen sulfide in bodies of water
where reducing conditions and anaerobic bacteria of the Desulfovibric
desulfurican prevail. Sulfates are also reduced by Clostridium nigrificans to
hydrogen sulfide, which, in turn oxidises to sulfur and water.
 Hydrogen sulfide becomes so highly concentrated in some waters lacking in
oxygen that it inhibits marine life.
 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 is an unusual associate.
 Sulfur compounds
• Organic sulfur compounds such as proteins in living organisms cycle with inorganic sulfate ions in soil or water. Most sulfur is bound
up in rocks and salts or buried in deep ocean sediments.
• Decomposers break down organic sulfur compounds to gases such as hydrogen sulfide which enter the atmosphere and are
oxidised to sulfur dioxide.
• Sulfur dioxide dissolves in water droplets in the atmosphere to give solutions of sulfurous acid, H2SO3.
SO2(g) + H2O(l) H2SO3(aq)
• Sulfurous acid is a weak acid and only partially ionises in water
H2SO3(aq)  H+(aq) + HSO3-(aq)
• This is oxidised in water droplets in clouds to form sulfuric acid, H2SO4.
• Sulfuric acid is washed into the soil by rain. Sulfate ions form which can be absorbed and utilised by plants.
• Sulfuric acid can also be formed from DMSP (dimethyl sulfonioproprionate) which is formed by plankton species and gives the
seaside it characteristic smell.
• Photosynthetic sulfur bacteria are able to form free sulfur from hydrogen sulfide gas. Industrial processes, including burning fossil
fuels and volcanoes liberate hydrogen sulfide and sulfur dioxide gases.
• Sulfate ions are easily leached out of the soil.

Figure 1 The sulfur cycle

 The Sulfur Cycle

 The essential steps of the sulfur cycle are:

 Mineralization of organic sulfur to the inorganic form, hydrogen sulfide, H 2S.
 Oxidation of sulfide and elemental sulfur (S) and related compounds to sulfate, SO 4 2–.
 Reduction of sulfate to sulfide.
 Microbial immobilization of the sulfur compounds and subsequent incorporation into
the organic form of sulfur.

 These are often termed as follows:

 Assimilative sulfate reduction assimilation) in which sulfate (SO4 2–) is reduced to
organic sulfhydryl groups (R–SH) by plants, fungi and prokaryotes. The oxidation
states of sulfur are +6 in sulfate and –2 in R–SH.
 Desulfuration and Dissimilative sulfur reduction in which organic molecules containing
sulfur can be desulfurated, producing H2S. Note the similarity to deamination.
 Oxidation of hydrogen sulfide produces elemental sulfur (So), oxidation state = 0. This
reaction is done by the photosynthetic green and purple sulfur bacteria and some
chemolithotrophs. Further oxidation of elemental sulfur produces sulfate.
 Natural occurrence
 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.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 7

 Sulfur Reservoirs in Nature
 Reservoirs of sulfur atoms:
 The largest physical reservoir is the Earth's crust where
sulfur is found in gypsum (CaSO4) 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 gas, and elemental sulfur.
 Other reservoirs include:
 Freshwater - contains sulfate, hydrogen sulfide and
elemental sulfur
 Land - contains sulfate
 Atmosphere - contains sulfur oxide (SO2) and methane
sulfonic acid (CH3SO3-); volcanic activity releases some
hydrogen sulfide into the air.
 Natural surface Sulfur Deposit

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 9

 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.
4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 10
 Production
 Elemental Sulfur is found on the Earth in:
 Volcanic deposits or volcanic emanations (i.e.,
Fumaroles).
 The largest physical reservoir is the Earth's crust where
sulfur is found in gypsum (CaSO4.2H2O) and pyrite (FeS2). Sulfur occurs in fumaroles
• Elemental sulfur was once extracted from salt domes where such as this one in Vulcano, Italy
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 Sulfur powder
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 Roll Sulfur
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

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 11

 The discretionary extraction of sulfur has declined as more
and more production is based on nondiscretionary by-product
sulfur extracted to comply with environmental regulations at
nonferrous smelters and roasters, natural gas and crude
petroleum processing plants, coking plants, and the like.
i) Volcanic deposits or volcanic emanations (i.e.,
Fumaroles)
ii) Native sulfur associated with the cap rock of salt
domes
iii) Native sulfur in sedimentary deposits is still mined by
the Frasch hot-water method (mainly in Poland but no
longer in the United States), and
iv) The Mining of pyrite as a source of sulfur is restricted
to China.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation 12

Chert & Phosphate Deposits
Production
 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.
4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 13
 Sulfur and Algae Hot Springs

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.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 14

 Sicilian kiln used to obtain sulfur from Negative Impact Sulfur
volcanic rock.

Sulfur Lumps

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 15

 Production
 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.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 16

 Production

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 17

Jashak salt dome is one of the largest and the most
beautiful and typical salt domes in Iran and the
Middle East 18
4 May 2016 Prof. Dr. H.Z. Harraz Presentation Salt Deposits
 Frasch Process
• 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

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 19

 Production
 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.

Sulfur recovered from hydrocarbons in Alberta,

stockpiled for shipment in North Vancouver, B.C.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 20

 Surface Sulfur
Mining
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.

Sulphur Mine, Kawah Ijen Volcano, Java, Indonesia

A man carrying sulfur blocks from Kawah Ijen, a volcano in East Java,
 Melted sulfur obtained from surface
A Sulfur Deposit
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.

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 22

 Underground Sulfur Mining

Example: Mining of pyrite as a source of

sulfur is restricted to China.
4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 23
 Reserves
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).

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 24

 World Production
 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.

Production and price (US

market) of elemental sulfur

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 25

 MAJOR SULFUR PRODUCERS OF THE WORLD-2010
PRODUCTION IN
COUNTRY (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

4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 26

 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 production in 2000
 Sulfuric acid.
 in fertilizers
 is also used in matches, insecticides and fungicides.
 Sulfur dioxide, used as a bleaching agent, • The pyrite processed by the Chinese is a
disinfectant, and refrigerant; source of sulphur for manufacturing
 Sodium bisulfite, used in paper manufacture; sulphuric acid & byproduct a source of iron.
carbon disulfide, an important organic solvent; The pyrite to be free of deleterious
 Hydrogen sulfide, sulfur trioxide, used as elements such as arsenic and fluorine.
reagents in chemistry; • The recovery of pyrite in the Mt Morgan
 Epsom salts (magnesium sulfate), used as a laxative, (Qld Aust) waste is currently being
bath additive, exfoliant, and magnesium supplement in
investigated to clean up an environmental
plant nutrition; the numerous other sulfate compounds;
and sulfa drugs. legacy.
• In the current depressed market for iron ore
pyrite is unlikely to be considered as a
primary source of iron ore unless there are
special circumstances that reduce overall
costs.
4 May 2016 Prof. Dr. H.Z. Harraz Presentation Sulfur Deposits 27
• Are mining methods,
including
“beneficiation”/concentra
tion described?
• Yes (2). The Frasch
process is presented in
some detail, both in the
text (Section 5.3) and in
Figure 3.
• Figure 2a) is a schematic diagram of an environmental disaster—a calcaroni, or
sulfur kiln (from Partington, 1937). The kiln is loaded with lumps of the sulfur/rock
mixture and covered with a layer of powdered sulfur. When the latter is ignited, a
fraction of the sulfur is melted and collected in a reservoir at the bottom. The
vertical channels are air vents.
• Figure 2b) shows a sulfur refinery (from Partington, 1937). Sulfur is boiled in an
iron retort and the sulfur vapors are condensed in a brickwork chamber. Note the
similarity between this process and that described by Agricola in 1556 (Figure 1b).

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