Sulfur

sulfur is essential to life. It is a minor

constituent of fats, body fluids, and
skeletal minerals.
 Fast facts
Name: sulfur
Symbol: S
Atomic number: 16
Atomic weight: 32.065 (5) g r
 spelling
The spelling of sulphur is "sulfur" in the
USA and now that IUPAC has decided it
has jurisdiction over the British English
language (as distinct from American
English) as well as nomenclature, so
people in the UK are expected to use the
Sulfur word.
 Where Sulfur is Found
Sulfur is found in meteorites, volcanoes,
hot springs, and as galena, gypsum,
Epsom salts, and pyrite ores. It is
recovered commercially from "salt
domes" along the Gulf Coast of the USA.
Jupiter's moon Io owes its colors to
various forms of sulfur. A dark area near
the crater Aristarchus on the moon may
be a sulfur deposit.
 Caution: Sulfur
Carbon disulphide, It is insidious in that it
hydrogen sulfide, and quickly deadens the
sulfur dioxide should be sense of smell.
handled extremely
Sulfur dioxide is a
carefully.
dangerous component
Hydrogen sulfide in very
in atmospheric air
small concentrations can
be metabolized, but in pollution and is one of
higher concentrations it the factors responsible
can cause death quickly for acid rain
by respiratory paralysis.
 Sulfur Forms
Lumps Sulfur
The majority of sulfur that is
transported around the world is done
as a bulk solid. The sulfur is often
stored in the open in huge stockpiles
at terminals ready to be loaded onto
ships, railcars or truck or at plant sites
to be melted and used in the
production of sulfuric acid. Most
sulfur stockpiles are located outdoors
in open where it is exposed to wind,
rain, dust, salt air, etc. In some cases
sulfur is stored indoors where some
protection from the elements is
available.
 Sulfur Forms
Lumps Sulfur
Bulk sulfur produced from
sulfur that has been crushed
from larger pieces will be
irregular in shape and posses
many sharp edges and points
which will be easily broken
producing smaller particles
and dust.
 Sulfur Forms
Lumps Sulfur
The properties of solid elemental
sulfur leave a lot to be desired from
the point of view of handling and
transport. Since it is by no means
always Practical to move sulfur
around in the molten form, the sulfur
industry has expended a considerable
amount of effort over the years on
developing methods of forming
sulfur into regularly-sized particles
which can be handled without giving
rise to excessive amounts of dust.
 Sulfur Forms
Molten sulfur
Molten sulfur is present in an ever
widening presence in many
industries. Besides the traditional
sources of sulfur, such as
refineries and natural gas plants,
and the well known users of
sulfur, such as sulfuric acid plants
and fertilizer production, sulfur
has become a common feedstock
in more conventional chemical
production such as tire and rubber
additives, polymer production,
and even food products.
 Sulfur Forms
Molten sulfur
Sulfur is transported both as
a solid in bulk and as a liquid
in the molten form. Each
form has its own special
requirements in order to
transport sulfur safely, with
minimal environmental
impact and minimal
contamination of the sulfur.
 Sulfur Forms
Molten sulfur
The key to transporting sulfur in molten form is
maintaining its temperature at approximately
140oC. Transport over short distances can be done
in well insulated containers. The low thermal
conductivity of sulfur minimizes heat loss and
helps it to retain heat so it does not solidify. Over
longer distances, a heating system is required to
maintain the sulfur in the liquid state.
The capacity of the tank is approximately 3,800
USGal and is constructed of stainless steel and is
insulated.
 Sulfur Forms
Molten sulfur
The amount of sulfur transported per trip
can be increased by going to a B-train
arrangement. The equipment shown below
is a B-train arrangement manufactured by
Bedard Tankers and has a capacity of 5,500
Imp. Gal.
.
 Sulfur Forms
Molten sulfur
Tank trailers designed for molten sulfur are generally dedicated to
hauling molten sulfur. A tank that has just carried molten sulfur
cannot be easily cleaned so that the trailer can carry a different
commodity on the return trip or to another destination. The result
is that the tank is full on the delivery trip but is empty on the
return trip. To maximize what is known as "loaded miles", a
specially designed tank trailer combines a tank for molten sulfur
and a bulk carrier. On one trip, the trailer carries molten sulfur
and on the return trip carries a bulk commodity such as
fertilizers. This type of trailer is called a backhaul double and is
used in the Florida region by fertilizer manufacturers to improve
the trucking economics. Backhaul doubles are also used in
western Canada but instead of a sulfur/bulk carrier, a sulfur/fuel
carrier is used.
 Sulfur Forms
Molten sulfur
Sulfur can be shipped in either solid or
liquid form over long distances by ocean
going ships. Solid sulfur can be shipped
in virtually any bulk carrier provided care
has been taken to thoroughly cleanout the
hold. Molten sulfur is transported in
specially designed ships equipped with
heating systems.
 Sulfur Forms
Slate Sulfur
Slate sulfur is formed by pouring molten
sulfur on a moving belt where it is
solidified into a continuous slab with a
thickness of 3 to 5 mm. The sulfur begins
to break into smaller pieces when it is
separated from the belt and when sulfur is
discharged from the belt at the head
pulley. This process produces irregular
shaped pieces with sharp edges. Fines
(less than 50 Tyler Mesh) amount to
about 3.5% by weight. Additional fines
are produced through further handling of
the product.
 Sulfur Forms
Slate Sulfur
Slating Process was developed to meet the need
for a low cost, high volume method of converting
molten sulfur into a solid form that can be
stockpiled and handled using conventional bulk
handling techniques.
The slating technology uses a liquid sulfur spread
pan to apply molten sulfur evenly to a slow
moving slating belt, on which the molten sulfur is
cooled and subsequently solidifies to a solid sheet.
Cooling is accomplished through both air-cooling
and immersion in water as the belt transports the
sulfur to the discharge point at the head pulley of
the slating unit.
 Sulfur Forms
Molded Sulfur

A refined sulfur molded into half

cylinder shaped bricks averaging 0.75 to
1.5 pounds each. This product is
primarily used in oil refining, steel
production, and secondary smelting.
 Sulfur Forms
Prilling Sulfur

In the wet sulfur prilling process, molten sulfur is pumped on to

perforated trays that direct the sulfur in narrow streams into an
agitated water bath. Pellets form as the sulfur comes in contact with
the water. The low thermal conductivity, high specific heat, and long
transformation time of sulfur make it necessary to maintain the
pellets in suspension for as long as possible, allowing them to
harden. This process produces spherical, uniformly sized, low
moisture pellets.
 Sulfur Forms
Prilling Sulfur
The wet process forms prills by pumping liquid sulfur onto
perforated trays through which the sulfur streams into an agitated
water bath. As the molten sulfur streams contact the cool water, the
pellets form and are maintained in suspension to allow enough time
to solidify.
The solid prills settle to the bottom of the prill tank and flow by
gravity to high frequency dewatering screens. The cooling water and
undersized prills recovered from the dewatering screens flow by
gravity to a settling tank where undersize prills are removed from the
settling tank using a screw conveyor. The undersize prills can then
be remelted or blended with the final product on the collector
conveyor.
 Sulfur Forms
Prilling Sulfur
The process water is pumped back to the prill tank by
water pumps mounted on the settling tank, passing
through a water cooled heat exchanger that removes
the heat delivered to the process by the liquid sulfur.
As the process water is contained in a closed loop
system, makeup water to compensate for losses due to
evaporation and product water is minimal.
Sulfur prills of product quality are discharged to a belt
conveyor for transport to storage and/or further
handling.
 Sulfur Forms
Pastillated Sulfur
Pastillated process is a drop-forming technology,
solidifying liquid sulfur into uniform
hemispherical pastilles. The technology uses a
rotary depositor mounted above, and transversely
to, a metal cooling belt. The depositor consists of
a perforated rotating shell with an internal
distribution and metering bar, which produces
closely spaced rows of precisely metered drops.
Molten sulfur product at approximately 125oC is continuously fed
through heated pipes at the specified pressure to the dropforming
depositor. The rotational speed of the shell is synchronized with
speed of the cooling belt to ensure that the droplets assume a
hemispherical shape upon contact with the belt.
 Sulfur Forms
Pastillated Sulfur
Owing to conductive and convection cooling processes,
solidification of the droplets begins at the surface, thereby preserving
the hemispherical shape, and progresses into the center. A small
dimple forms at the top of the pastille during the solidification
process to accommodate volumetric shrinkage.
The temperature of the cooling belt is controlled by regulating the
flow and temperature of the cooling water sprayed onto the
underside of the belt. The cooling water is collected and re-circulated
through a cooling system. Control of the heat transfer rate from the
molten sulfur droplets to the metal belt and from the metal belt to the
cooling water not only optimizes production capacity, but also
ensures the production of a high quality product.
 Sulfur Production
Sulfur is currently produced from four major
sources:

1. As elemental sulfur (brimstone) from

mined deposits by the Frasch process
2. As elemental sulfur recovered from oil and
gas production
 Sulfur Production
3. As sulfuric acid from smelting of non
ferrous metals (sulfur in other forms or
SOF).

4. As sulfuric acid from pyrites "Crude"

sulfur is produced from the Frasch
process or recovered from "sour"
natural gas or petroleum. Although
termed "crude", this sulfur possesses a
minimum purity of 99.5% and is
suitable for a majority of uses. The
impurities consist primarily of trapped
organic matter.
 Sulfur Production
In some regions of the world the sulfur
occurs at depths of 500 to 3,000 feet in
domes subterraneously up-thrust by
columns of salt. This native sulfur
associated with the cap rock of salt
domes and in sedimentary deposits was
mined by the Frasch hot-water method, in
which the native sulfur was melted
underground and brought to the surface
by compressed air.
 Frasch process
1) Elemental Sulfur Production
In 1900, Herman Frasch was trying to perfect his
hot water melting process for producing sulfur.
Domestic production was about 3,200 metric tons
of sulfur valued at $88,100. Native sulfur deposits
in Louisiana, Nevada, Texas, and Utah were mined
with conventional mining methods. Domestic
sulfur production, including mined elemental sulfur
and pyrites, supplied about one-quarter of the U.S.
sulfur demand of about 415,000 tons. Most sulfur
and pyrites, domestic and imported, were used to
produce sulfuric acid that was consumed in many
different industries.
 Frasch process
1) Elemental Sulfur Production
Virtually all elemental sulfur imports came from the
Italian island of Sicily, and pyrite imports were from
unspecified locations. Pyrites remained a significant raw
material for sulfuric acid until 1982. When the Frasch
process was successfully commercialized in 1903, the
U.S. sulfur industry took a turn for the better. By about
1915, the United States surpassed Italy as the worlds
leading producer of sulfur, a situation that continued
throughout the century, during which eight companies
produced nearly 340 million tons of sulfur from 36
mines in Louisiana and Texas. Frasch sulfur production
hit its peak in 1974 when 12 mines produced 8 million
tons.
 Frasch process
Sulfur is extracted through the following
process known as the Frasch Process.
underground deposits of sulfur are
forced to the surface using superheated
steam and water (160C, 16 atmospheres,
to melt the sulfur) and compressed air
(25 atmospheres). This gives molten
sulfur which is allowed to cool in large
basins. Purity can reach 99.5%.
 Frasch process
The Frasch process utilizes
a steel tube made up of three
concentric pipes that are
driven underground to reach
the sulfur deposit.
a) Superheated water is then
pumped down under great
pressure in the outermost
pipe to melt the sulfur.
b) Air pressure from the
innermost pipe forces the
sulfur up the third pipe to the
surface where it cools and
solidifies.
2. Elemental sulfur recovered from oil
and gas production
Pyrites is the term given to a variety of
sulfide ores. In the United States, iron
pyrites are used in the production of only
a limited amount of sulfur. The salt dome
deposits and sulfur recovered from
petroleum and natural gas are much more
economical sources. On a worldwide
basis, however, sulfur tonnages from
pyrite ore are substantial.
2. Elemental sulfur recovered from oil
and gas production
Pyrites are obtained either as run-of-mine
or beneficiated ore from straight pyrite
deposits or recovered, as it usually is in the
United States, as by-product flotation
concentrates during the refining of iron
ore. Depending upon the process used,
pyrites can be made to yield elemental
sulfur or sulfuric acid.
2. Elemental sulfur recovered from oil
and gas production
Recovered elemental sulfur, a
nondiscretionary byproduct from petroleum
refining, natural gas processing, and coking
plants, was produced primarily to comply
with environmental regulations that were
applicable directly to emissions from the
processing facility or indirectly by restricting
the sulfur content of the fuels sold or used by
the facility.
2. Elemental sulfur recovered from oil
and gas production
Recovered sulfur from petroleum refining
and from "sour" natural gas has surpassed
Frasch process sulfur as the world's most
important source of supply. Recovered
sulfur tonnages are expected to increase
as the demand for clean-emission fuel
continues.
2. Elemental sulfur recovered from oil
and gas production
Sulfur recovery refers to the conversion

Claus process
of hydrogen sulfide (H2S) to elemental
sulfur. Hydrogen sulfide is a byproduct
of processing natural gas and refining
high-sulfur crude oils.

H2S(g) +3/2 O2(g) SO2(g) +H2O(g)

SO2(g) + 2H2S(g) 3S(l) +H2O(g)

 Claus process
The multi-step Claus
process recovers
sulfur from the
gaseous hydrogen
sulfide found in raw
natural gas and from
the by-product gases
containing hydrogen
sulfide derived from
refining crude oil and
other industrial
processes.
 Claus process

The by-product gases mainly originate from physical and chemical

gas treatment units (Selexol, Rectisol, Purisol and amine scrubbers)
in refineries, natural gas processing plants and gasification or
synthesis gas plants. These by-product gases may also contain
hydrogen cyanide, hydrocarbons, sulfur dioxide or ammonia.
 Claus process
The Claus process is the most widely used
process for treatment of the off gas and is
used to reduce hydrogen sulphide and the
other sulfur compounds to elemental sulfur.
The first step in treatment of the amine
scrubber tail gas consists of
a) Thermal reaction furnace (or Claus
Furnace) where the acid gas is reduced to
elemental sulfur at high temperature under
controlled combustion conditions.
Claus Thermal Reaction Furnace
 Claus process
b) The reaction furnace gases are cooled in
a waste heat boiler and gaseous sulfur is
condensed.
c) The gases then pass to the Claus reactor
where residual sulfur compounds are
catalytically converted to sulfur in one or
more stages.
d) To improve the efficiency of the process,
the gases are reheated in the in-line heaters
upstream of the Claus reactors.
Claus Catalytic Convertor
Scot Catalytic Convertor
 Claus process
e) Tail gas treatment is used to further
increase the sulfur removal efficiency before
the tail gases pass to the incinerator.
f) The basic Claus unit comprises a thermal
stage and two or three catalytic stages.
Typical sulfur recoveries efficiencies are in
the range 95-98% depending upon the feed
gas composition and plant configuration.
 Claus process
The most common conversion
method used is the Claus process.
Approximately 90 to 95% of
recovered sulfur is produced by the
Claus process. The Claus process
typically recovers 95 to 97 % of the
hydrogen sulfide feed stream.
 Claus process
Sulfur removal facilities are located at the
majority of oil and gas processing facilities
throughout the world. The sulfur recovery
unit does not make a profit for the operator
but it is an essential processing step to allow
the overall facility to operate as the
discharge of sulfur compounds to the
atmosphere is severely restricted by
environmental regulations.
Oil and gas producers are attempting to maximize
production at minimum cost. This often means
debottlenecking existing upstream facilities and may
result in extra sulfur recovery capacity being required.
Oil refiners are also increasingly being forced to comply
with legislation reducing the levels of sulfur in products.
Combine this with the ability or need to process sourer
crude oils and many refiners find that their existing sulfur
recovery units do not have sufficient capacity.
Furthermore, in many countries environmental legislation
is demanding higher recoveries from sulfur recovery
units.
 Claus process
Several technologies exist for removal of sulfur
compounds from acid or sour gases which arise in
the oil refining, gas processing and other process
industries. The sour feed gas is treated in an amine
scrubber in which the acid gases are absorbed in a
basic amine solution to produce sweet (sulfur free)
sales gas and an off gas stream (tail gas) rich in
hydrogen sulfide and carbon dioxide.
The sulfur compounds present in acid gas include
hydrogen sulphide which is highly toxic and has a
strong odour at low concentrations.
Claus process
SULFUR
RULES!