Report

--Submitted by:
Stuti Jain (2018uch1632)
Shivam Mishra (2018uch1633)

Sulfur-bearing compounds are very detrimental to the environment and to

industrial process equipment. They are often obtained or formed as a by-
product of separation and thermal processing of fuels containing sulfur,
such as coal, crude oil and natural gas. The two sulfur compounds, which
need special attention, are: hydrogen sulfide (H2S) and sulfur dioxide
(SO2). H2S is a highly corrosive gas with a foul smell. SO2 is a toxic gas
responsible for acid rain formation and equipment corrosion. Various
methods of reducing pollutants containing sulfur are described in this
paper, with a focus on the modified Claus process, enhanced by the use of
High Temperature Air Combustion technology in the Claus furnace. The
Claus process has been known and used in the industry for over 100 years.
It involves thermal oxidation of hydrogen sulfide and its reaction with
sulfur dioxide to form sulfur and water vapor. This process is equilibrium-
limited and usually achieves efficiencies in the range of 94-97%, which
have been regarded as acceptable in the past years. Nowadays strict air
pollution regulations regarding hydrogen sulfide and sulfur dioxide
emissions call for nearly 100% efficiency, which can only be achieved
with process modifications. High temperature air combustion technology
or otherwise called flameless (or colorless) combustion is proposed here
for application in Claus furnaces, especially those employing lean acid
gas streams, which cannot be burned without the use of auxiliary fuel or
oxygen enrichment under standard conditions. With the use of, it has been
shown, however, that fuel-lean, Low Calorific Value (LCV) fuels can be
burned with very uniform thermal fields without the need for fuel
enrichment or oxygen addition. The uniform temperature distribution
favors clean and efficient burning with an additional advantage of
significant reduction of NOx, CO and hydrocarbon emission.

Sulfur compounds in refinery HDS feedstock’s

The refinery HDS feedstocks (naphtha, kerosene, diesel oil and heavier
oils) contain a wide range of organic sulfur compounds, including thiols,
thiophenes, organic sulfides and disulfides, and many others. These
organic sulfur compounds are products of the degradation of sulfur during
the natural formation of the petroleum crude oil. When the HDS process
is used to desulfurize a refinery naphtha, it is necessary to remove the the
total sulfur down to the parts per million range or lower in order to prevent
poisoning the noble metal catalysts in the subsequent catalytic reforming
of the naphthas. When the process is used for desulfurizing diesel oils, the
latest environmental regulations in the United States, Europe and
elsewhere mandate what is referred to as ultra-low sulfur diesel (ULSD)
which requires very deep hydrodesulfurization. In the early 2000's, the
governmental regulatory limits for highway vehicle diesel was within the
range of 300 to 500 ppm by weight of total sulfur. As of 2006, the total
sulfur limit for highway diesel was in the range of 15 to 30 ppm by weight.

Hydrodesulfurisation
Hydrodesulfurization (HDS) or Hydrotreating is a catalytic chemical
process widely used to remove sulfur compounds from refined petroleum
products such as gasoline or petrol, jet fuel, diesel fuel, and fuel oils. One
purpose for removing the sulfur is to reduce the sulfur dioxide emissions
resulting from using those fuels in automotive vehicles, aircraft, railroad
locomotives, ships, or oil burning power plants, residential and industrial
furnaces, and other forms of fuel combustion. Another important reason
for removing sulfur from the intermediate product naphtha streams within
a petroleum refinery is that sulfur, even in extremely low concentrations,
poisons the noble metal catalysts platinum and rhenium in the catalytic
reforming units that are subsequently used to upgrade the of the naphtha
streams. Hydrogenation of the sulfur compounds results in the formation
of undesirable, toxic gaseous hydrogen sulfide. The industrial
hydrodesulfurization processes include facilities for the capture and
removal of the hydrogen sulfide gas. In petroleum refineries, the hydrogen
sulfide gas is then subsequently converted into byproduct elemental
sulfur. In fact, the vast majority of the 68,000,000 metric tons of sulfur
produced worldwide in 2010 was byproduct sulfur from petroleum
refining and natural gas processing plants.

The process chemistry

Hydrogenation is a class of chemical reactions that results in the addition
of hydrogen. Hydrogenolysis is a type of hydrogenation that results in the
cleavage of the C-X chemical bond, where C is a carbon atom and X is a
sulfur, nitrogen or oxygen atom. The net result of a hydrogenolysis
reaction is the formation of C-H and H-X chemical bonds. Thus,
hydrodesulfurization is a hydrogenolysis reaction. Using ethanethiol
(C2H5SH), a sulfur compound present in some petroleum refining
streams, as an example, the hydrodesulfurization reaction can be
expressed as:

Ethanethiol + Hydrogen ⇒ Ethane + Hydrogen Sulfide

C2H5SH + H2 ⇒ C2H6 + H2S
Catalysts
Many metals catalyze the HDS reaction, but it is those at the middle of
the transition metal series that are most active. Ruthenium disulfide
(RuS2) appears to be the single most active catalyst, but binary
combinations of cobalt and molybdenum are also highly active. In
practice, most HDS units in petroleum refineries use catalysts based on
cobalt-modified molybdenum disulfide (MoS2) together with smaller
amounts of other metals. Aside from the MoS2 catalysts, nickel
andtungsten are also used, depending on the nature of the feed. For
example, nickel-wolfram (Ni-W) catalysts are more effective for the
hydrodenitrification (HDN) which is also desired in many HDS units.
Metal sulfides are supported on materials with high surface areas. A
typical support for HDS catalyst is alumina. The support allows the more
expensive catalyst to be more widely distributed, giving rise to a larger
fraction of the MoS2 that is catalytically active.

Claus Process
Sulfur recovery refers to the conversion of hydrogen sulfide (H2S) to
elemental sulfur.The claus process is the most significant gas
desulfurizing process whose main objective is to recover elemental
Sulphur from gaseous hydrogen sufide. First introduced in 1883 by the
chemist Carl Friedrich Claus thus named claus process. It was further
modified by I.G. Farben.
Since the Sulphur recovered from hydro desulfurisation is in the form of
hydrogen sulfide (H2S) , further treatment is needed in order to obtain
elemental Sulphur, that is where Claus process comes into picture. The
process consists of multistage catalytic oxidation of hydrogen sulfide.
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.
There are Various type of Flow Patterns available for Claus Process
depending on the concentration of Hydrogen disulfide in the feed gas:
Straight through process scheme–
• Best for higher H2S feed concentrations (> 50 mole % of H2S
in acid gas feed)
• Combustion air and acid gas pass through the reaction furnace
, like a typical Claus process.
• Recovery efficiency is about 96 to 97 %.
Split flow process scheme–
• Best for low H2S feed concentrations (30-50 mole % of H2S
in acid gas feed)
• Used with or without preheating.
• Combustion air and atleast one-third of the acid gas pass
through the reaction furnace and the remaining acid gas is
mixed with the exit gases from the waste heat reboiler.

Direct oxidation –
• Used in case of concentration less than 30 mole % of H2S in
acid gas feed.
• Hi- activity catalyst based unit is used.
• For acid gas with less than 30 % H2S, a stable flame in the
reaction furnace is difficult to maintain, so we use oxygen
based Claus processes.
• The process is similar to a modified Claus unit, except that the
last catalytic stage is replaced with Hi Activity Catalyst.

Hydrogen sulfide, a byproduct of crude oil and natural gas processing, is

recovered and converted to elemental sulfur by the Claus process. The
process consists of multistage catalytic oxidation of hydrogen sulfide
according to the following overall reaction:
2H2S+ O2  2S+ 2H2O
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:
2H2S+ 3O2  2SO2 +2H2O+ heat
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:
2H2S+ SO2 3S +2H2O +heat
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.

Utilities required:
Acid gas.
Combustion air.
Cooling water for condensation.
Steam for reheating or preheating.
Boiler feed water.
Fuel for incineration.

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 gauge [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. Claus reaction represents a reversible
chemical reaction, hence 100% conversion is not possible. Practically, 95
to 97 percent overall recovery can be achieved. Tail gas units are used to
provide improved conversion.
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:
CO2+ H2S  COS+ H2O
COS+ H2S  CS2 +H2O
2COS  CO2 +CS2
Following is the typical schematic diagram of modified Claus process
with definite stages and recovery efficiency of Sulphur after every unit.
Working of Claus process is summarized here:
The process involves burning of H2S gas with just sufficient combustion
air in a reactor furnace to form sulfur dioxide (SO2). The furnace normally
operates at 1200°C. Hot gas from the combustion chamber is quenched in
a waste heat boiler that generates high to medium pressure steam. The
reaction gases are then sent to condenser where cooling to 150-190°C
takes place, and about 60 % of the sulfur is recovered here. The remaining
uncombusted H2S undergoes Claus reaction. The catalytic reactors
operate at lower temperatures(200 to 315°C) which can be obtained by
reheating reaction gases and then passed to a bed of bauxite catalyst,
where further conversion takes place. Then it is passed through a sulphur
condenser, heater and reactor. From the condenser of the final catalytic
stage, the process stream passes to some form of tail gas treatment process
or it is incinerated to oxidize last traces of H2S and elemental sulphur and
then vented to atmosphere via stack.
THE RECYCLE SELECTOX PROCESS
The recycle selectox process, developed by Prasons and Unacol, treats
lean acid gas containing 5 to 30 mole % H2S. The Selectox catalyst
directly catalyzes the oxidation of H2S to SO2 eliminating the reaction
furnaces of the Claus process. It also catalyzes the Claus reaction for the
production of elemental sulfur. The exothermic Claus reaction results in
a temperature rise of about 30 degee Celsius in the first reactor stage and
about 15 degree Celsius across the second stage. It usually consists of one
Selectox Stage, followed by two Claus stages. A recycle blower dilutes
the incoming acid gas with Selectox condenser off-gas to an H2S
concentration of less than 5%. Diluted acid gas is mixed with air before
the mixture passes to the catalyst bed. A typical H2S conversion to
sulphur is more than 80 percent. Total sulphur recovery with two
subsequent Claus stages ranges from 94 to 96 percent. If the lean acid gas
contains less than 5% H2S, the once-through Selectox process can be
used, in which recycle loop is not required. Except for the recycle loop
,the equipment arrangement is same.