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Introduction 1

Sulfur is a valuable commodity that is used to manufacture fertilizers, chemicals, and is a vital nutrient. It occurs naturally in the earth's crust and can be mined or extracted from oil and gas production. The Frasch process was historically used to extract underground sulfur deposits but has been replaced by extraction from petroleum and gas sources. The Claus process is commonly used to convert hydrogen sulfide into elemental sulfur, using catalytic reactions. It typically recovers 95-97% of hydrogen sulfide and involves burning it with air to form sulfur dioxide and then reacting the remaining hydrogen sulfide with sulfur dioxide to form elemental sulfur.

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0% found this document useful (0 votes)
30 views9 pages

Introduction 1

Sulfur is a valuable commodity that is used to manufacture fertilizers, chemicals, and is a vital nutrient. It occurs naturally in the earth's crust and can be mined or extracted from oil and gas production. The Frasch process was historically used to extract underground sulfur deposits but has been replaced by extraction from petroleum and gas sources. The Claus process is commonly used to convert hydrogen sulfide into elemental sulfur, using catalytic reactions. It typically recovers 95-97% of hydrogen sulfide and involves burning it with air to form sulfur dioxide and then reacting the remaining hydrogen sulfide with sulfur dioxide to form elemental sulfur.

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m6drrr
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Introduction 1.

Sulphur is a valuable commodity and integral component of the world


economy used to manufacture numerous products including fertilizers and
other chemicals. sulphur also is a vital nutrient for crops, animals and people.

Sulphur occurs naturally in the environment and is the thirteenth most


abundant element in the earth's crust. It can be mined in its elemental form,
though this production has reduced significantly in recent years. Since early
in the 20th Century, the Frasch process has been used as a method to extract
sulphur from underground deposits, when it displaced traditional mining
principally in Sicily. Most of the world's sulphur was obtained this way until
the late 20th century, when sulphur's recovery from petroleum and gas
sources (recovered sulphur) became more commonplace. As of 2011, the
only operating Frasch mines worldwide are in Poland and since 2010 in
Mexico. The last mine operating in the United States closed in 2000. A Frasch
mine in Iraq closed in 2003.

Sulphur that is mined or recovered from oil and gas production is known as
elemental sulphur, or brimstone. Sulphur can be combined with other
elements to form various compounds. Sulphur compounds, such as sulphuric
acid, also are produced as a by-product of ferrous and non-ferrous metal
smelting. Other compounds, such as sulphur dioxide, may be emitted from
petroleum products used in cars and coal generating electricity. Plants
absorb sulphur from the soil as sulphate.

Elemental sulphur is produced all over the world. Largest production occurs
where sour (meaning sulphur-rich) gas and oil is processed and refined:
United States, Canada, the Former Soviet Union, and West Asia.
Sulfur hazards:

1. Sulfur content seriously spoils the equipment. During petroleum


processing, many sulfur-containing compounds decompose under the
influence of high temperature to produce hydrogen sulfide. When
hydrogen sulfide is present with water, it can cause severe corrosion to
metal equipment. For example, in atmosphere and vacuum units, high-
temperature heavy oil corrosion is mainly concentrated at the bottom
of the atmosphere tower. If the oil contains sulfur and salt, the
corrosion of metal equipment will be more serious.
2. Sulfur content affects product quality. The presence of sulfur-
containing compounds seriously affects the storage stability of oil,
accelerates the oxidative deterioration of refined oil, and produces
sticky deposits; Sulfides can also poison and deactivate catalysts in
reformers and automobile exhaust gas purification units in the refining
process.
3. The sulfur content pollutes the environment. In the process of
petroleum processing, hydrogen sulfide and low molecular mercaptans
are toxic gases with a strong odor, which can cause environmental
pollution and hinder human health.

Sulfur extraction unit from H2S


History 1.2

The process was invented by Karl Friedrich Krauss, a German


chemist working in England. A British patent was issued to him in
1883. This process was later extensively modified by IG Farben.
Klaus was born in Kassel, Hesse, Germany in 1827, studied
chemistry in Marburg, and moved to England in 1852 , In
nineteenth century, there were many alkali manufacturing plants in
England producing sodium carbonate (Na2CO3) by the Leblanc
process. The original Claus process was developed by Carl Friedrich
Claus, a chemist working in England, for the purpose of recovering
sulfur from the waste calcium sulfide (CaS) generated by the
Leblanc process. As a catalyst, he chose a bog iron ore and later
bauxite (a mineral with a high alumina content).[9] In 1883, Claus
was granted a British patent for the process.
During the next 53 years, the Claus process underwent several
minor modifications. In 1936, I.G. Farbenindustrie a (German
conglomerate of chemical companies) introduced a modification of
the process that utilized a thermal conversion step followed by
catalytic conversion steps, which is the basically the concept
currently used in modern Claus sulfur recovery units
Properties 1.3

Physics:
1. This raw ingredient has no taste or smell, and is a yellowish-white
compound.

2. It is a poor conductor of electricity and insoluble in water.

3. Its melting point is 115.21 degrees Celsius, and its boiling point is
444.60 degrees Celsius, with density is 2.067.

4. With heat, the viscosity of sulfur gradually decreases until it reaches


its lowest viscosity at 157°C, but it quickly rises again to reach its
maximum viscosity at 187°C.

5. Its color also changes from yellow when heated to dark red, until it
reaches black at a temperature of 250 degrees Celsius.

Atomic number 16
3
Density )g/cm ) 2.07
Melting point (oc) 112.8 oc
boiling point (oc) 444.6 oc
Atomic weight )g) 32.066
Electronegativity 2.58
Electrical conductivity 2.5
Ionic energy 999
Chemical:
1. Reaction between Sulphur and Oxygen

2. Reaction between Sulphur and Acids

3. Reaction between Sulphur and bases

4. Reaction between Sulphur and non-metals

5. Molten sulfur combines with hydrogen gas to form hydrogen sulfide


gas
Sulfur Recovery 1.4
Sulfur recovery refers to the conversion of hydrogen sulfide (H2S) to
elemental sulfur. Hydrogen sulfide is a byproduct of processing natural gas
and refining high-sulfur crude oils. The most common conversion method
used is the Claus process. Approximately 90 to 95 percent of recovered sulfur
is produced by the Claus process. The Claus process typically recovers 95 to
97 percent of the hydrogen sulfide feedstream.

Over 5.9 million megagrams (Mg) (6.5 million tons) of sulfur were recovered
in 1989, representing about 63 percent of the total elemental sulfur market
in the U. S. The remainder was mined or imported. The average production
rate of a sulfur recovery plant in the U. S. varies from 51 to 203 Mg (56 to 224
tons) per day.

Process Description
Hydrogen sulfide, a byproduct of crude oil and natural gas processing, is
recovered and converted to elemental sulfur by the Claus process. Figure (1)
shows a typical Claus sulfur recovery unit.

Figure (1) a typical Claus sulfur recovery unit


The process consists of multistage catalytic oxidation of hydrogen sulfide
according to the following overall reaction:

Each catalytic stage consists of a gas reheater, a catalyst chamber, and a


condenser.

The Claus process involves burning one-third of the H2S with air in a reactor
furnace to form sulfur dioxide (SO2) according to the following reaction:

The furnace normally operates at combustion chamber temperatures


ranging from 980 to 1540°C (1800 to 2800°F) with pressures rarely higher
than 70 kilopascals (kPa) (10 pounds per square inch absolute). Before
entering a sulfur condenser, hot gas from the combustion chamber is
quenched in a waste heat boiler that generates high to medium pressure
steam. About 80 percent of the heat released could be recovered as useful
energy. Liquid sulfur from the condenser runs through a seal leg into a
covered pit from which it is pumped to trucks or railcars for shipment to end
users. Approximately 65 to 70 percent of the sulfur is recovered. The cooled
gases exiting the condenser are then sent to the catalyst beds.

The remaining uncombusted two-thirds of the hydrogen sulfide undergoes


Claus reaction (reacts with SO2) to form elemental sulfur as follows:

The catalytic reactors operate at lower temperatures, ranging from 200 to


315°C (400 to 600°F). Alumina or bauxite is sometimes used as a catalyst.
Because this reaction represents an equilibrium chemical reaction, it is not
possible for a Claus plant to convert all the incoming sulfur compounds to
elemental sulfur. Therefore, 2 or more stages are used in series to recover
the sulfur. Each catalytic stage can recover half to two-thirds of the incoming
sulfur. The number of catalytic stages depends upon the level of conversion
desired. It is estimated that (95 to 97 percent) overall recovery can be
achieved depending on the number of catalytic reaction stages and the type
of reheating method used.

If the sulfur recovery unit is located in a natural gas processing plant, the type
of reheat employed is typically either auxiliary burners or heat exchangers,
with steam reheat being used occasionally. If the sulfur recovery unit is
located in a crude oil refinery, the typical reheat scheme uses 3536 to 4223
kPa (500 to 600 pounds per square inch guage [psig]) steam for reheating
purposes. Most plants are now built with 2 catalytic stages, although some
air quality jurisdictions require 3. From the condenser of the final catalytic
stage, the process stream passes to some form of tailgas treatment process.
The tailgas, containing H2S, SO2, sulfur vapor, and traces of other sulfur
compounds formed in the combustion section, escapes with the inert gases
from the tail end of the plant. Thus, it is frequently necessary to follow the
Claus unit with a tailgas cleanup unit to achieve higher recovery.

In addition to the oxidation of H2S to SO2 and the reaction of SO2 with H2S
in the reaction furnace, many other side reactions can and do occur in the
furnace. Several of these possible side reactions are:

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