FINISHING

HRPROCESSINTRODUCTION,HYDR
OGEN SULPHIDE
REMOVAL &SULPHUR
NAME:SHANTHINI
CONVERSION
ID NO:1000173
COURSE
NAME:PETROLEUM
PROCESS
REFINERY

Refining end-products

The primary end-products produced in petroleum refining may be grouped

into four categories:light distillates, middle distillates, heavy distillates and
others.

Light distillates
Liquid petroleum gas (LPG) Gasoline (also known as petrol) Kerosene
Jet fuel and other aircraft fuel.

Middle distillates
Automotive and rail-road diesel fuels
Residential heating fuel
Other light fuel oils

Heavy distillates
Heavy fuel oils
Bunker fuel oil and other residual fuel oils

Others:Many of these are not produced in all petroleum

refineries.
Speciality petroleum naphthas
Speciality solvents
Elemental sulphur, and sometimes sulphuric acid
Petrochemical feed-stocks
Asphalt and tar
Petroleum coke
Lubricating oils

FINISHING PROCESSES
Secondary refining processes referred to as finishing or
treating processes are necessary to make the petroleum
products suitable for use with respect to performance ,
corrosivity ,suitability on storage , odour and etc
The undesirable constituents of the products produced by
primary refining processes are hydrogen sulphide ,
mercaptants , nitrogen bases,compounds causing colour and
discolourisation ,gum forming compounds,napthenic acid.
The effect of this contaminants have a significant effect on the
fuel performance and customer acceptance.
Some of these can be eliminated by proper use of additives
(antioxidants and metal oxides ).
Various finishing processes employed in petroleum refining
industry include hydrogen sulphide removal processes
,sulphur recovery processes, sweetening procceses ,solvent
extraction processes and hydrotreating processes .

HYDROGEN
SULPHIDE
REMOVAL
PROCESS

AMINE GAS TREATING

 The condensed water is separated in the refux accumulator and returned to the still.
Hot, regenerated, lean amine is cooled in a solvent aerial cooler and circulated to the
contactor tower, completing the cycle.
Rich amine is then further heated in the regeneration still column by heat supplied
from the reboiler. The steam rising through the still liberates H2S and CO2,
regenerating the amine.
Steam and acid gases separated from the rich amine are condensed and cooled.
The amine solution is now considered Rich and is carrying absorbed acid gases.
The Lean amine and Rich amine fow through the heat exchanger, heating the Rich
amine.

Sour gas enters the contactor tower and rises through the descending amine.
Purified gas fows from the top of the tower.

SULPHUR
CONVERSION
PROCESS

CLAUS PROCESS

 In order to avoid sulphur condensing in the downstream catalyst

bed, the gas leaving the sulphur condenser must be heated before
entering the reactor.

The combustion products are further cooled in the first sulphur

condenser, usually by generating LP steam at 3 5 bar g. This
cools the gas enough to condense the sulphur formed in the
furnace, which is then separated from the gas and drained to a
collection pit.

The hot combustion products from the furnace at 1000- 1300C

enter the waste heat boiler and are partially cooled by generating
steam. Any steam level from 3 to 45 bar g can be generated.

 The sulphur plant tail gas is routed either to a Tail Gas treatment Unit
for further processing, or to a Thermal Oxidiser to incinerate all of the
sulphur compounds in the tail gas to SO2 before dispersing the
efuent to the atmosphere.
A further one or two more heating, reaction, and condensing stages
follow to react most of the remaining H2S and SO2.

The hot gas leaving the first reactor is cooled in the second sulphur
condenser, where LP steam is again produced and the sulphur formed
in the reactor is condensed.
The heated stream enters the first reactor, containing a bed of
sulphur conversion catalyst. About 70% of the remaining H2S and
SO2 in the gas will react to form sulphur, which leaves the reactor
with the gas as sulphur vapour.

THE RECYCLE SELECTOX

 The Recycle Selectox process developed by

Parsons and Unocal treats lean acid gas
containing 5 to 30 mole percent H2S
The Selectox catalyst directly catalysed the
oxidation H2S to SO2,eliminating the reaction
furnace the Claus process .It also catalyzes the
Claus reaction for the production of elemental
sulphur .
The Recycle Selectox Process consists of one
Selectox stage,followed by two Claus stages.

 A recycle Blower dilutes the incoming gas with

Selectox condenser off gas to H2S concentration of 5
% or less .
Diluted acid gas is mixed with a stoichiometric
amount of air before the mixture passes to the
catalyst bed.
A typical H2s conversion to sulphur is more than 80
% .Total sulphur recovery with two Claus stages
ranges about 94 to 96 %.
If the lean acid gas contain less than 5 % H2S,then
once through Selectox process can be used.

SELECTIVE OXIDATION
PROCESSES

In a Claus type unit,complete

conversion of H2S and SO2 to elemental
sulphur is not possible due to the
limitations of thermodynamic
chemical equilibrium of the Claus
reaction.
Selective oxidation of H2S to can be
thermodynamically complete as
indicated by the following reaction:

PARSONS HI-ACTIVITY
PROCESS
Parsons Hi-Activity process utilises a
series of proprietary catalysts for direct
oxidation of H2S to elemental sulphur.
The Hi-Activity catalysts,which are prepared
with different mixtures of iron-based metal
oxides without a use of a carrier.
The process scheme is very similar to a
conventional modified Claus unit,except
the last catalytic stage is replaced with HiActivity catalyst.

 Air is introduced to the unit at two

different locations with major portion
of the process air directed to the
thermal section and the first two
Claus catalytic reactors.
The remaining portion of the process
air is then mixed with the reaction
gases entering the last catalytic
reactor , which contains the Hi-Activity
catalyst for selectively oxidizing the
residual H2S to elemental sulphur.
The Hi-Activity process can achieve
sulphur recovery of more than 99%.

WET OXIDATION
BASED ON AQUEOUS
Aqueous-phase oxidation-reduction(redox)
reactions absorb
H2S in a solution that contains
SOLUTION
oxidizing agents.
When the H2S is absorbed by contact with the lean
solution and oxidized to sulphur,the lean solution
is reduced and regenerated in the oxidizer.
Sulphur slurry is separated from the solution ,
either upstream or downstream from the oxidizer
and then concentrated by filtration or
centrifugation into moist sulphur cake.
The regenerated lean solution is returned to the
absorber for reuse.

HERMAL CRACKING OF H2
In this process, a portion of the incoming
rich H2S acid-gas stream is fed to thermal
cracker to form hydrogen and sulphur.
The energy required for thermal cracker
is provided by sending the remaining
portion of feed H2S stream to the
conventional Claus furnance for the
thermal heat generation.
Valuable hydrogen is separated from
sulphur and uncracked H2S and can be
reused in hydrosulphurization unit.

 The separated sulphur and

uncracked H2S are recycled back
to the Claus furnance for further
sulphur recovery.
As much as 25 % of the total
hydrogen sulphide being fed to the
system can be cracked to
hydrogen without dropping the
Claus furnace temperature below
1000 Celsius for destablizing the
flame.

YDRODESULPHURIZATIO

 Hydrodesulphurization(HDS) is acatalytic
chemical
process widely used to removesulfur(S)
fromnatural gas and fromrefined petroleum
products, such as gasoline or petrol,jet
fuel ,kerosene,diesel fuel, andfuel oils.
The purpose of removing the sulfur is to reduce
thesulfur dioxide (SO2) emissions that result from
using those fuels in automotivevehicles,aircraft,
railroadlocomotives,ships, gas or oil
burningpower plants, residential and
industrialfurnaces, and other forms of
fuelcombustion.
An HDS unit in the petroleum refining industry is also
often referred to as ahydrotreater.

 The hydrodesulfurization reaction takes place in a

fixed-bedreactorat elevatedtemperaturesranging
from 300 to 400 C and elevated pressures ranging
from 30 to 130atmospheresof absolute pressure,
typically in the presence of acatalystconsisting of
analuminabase impregnated
withcobaltandmolybdenum(usually called a CoMo
catalyst). Occasionally, a combination
ofnickelandmolybdenum(called NiMo) is used, in
addition to the CoMo catalyst, for specific difficult-totreat feed stocks, such as those containing a high
level of chemically bound nitrogen.

 The liquid feed is pumped up to the required elevated pressure

and is joined by a stream of hydrogen-rich recycle gas. The
resulting liquid-gas mixture is preheated by fowing through
aheat exchanger.
The preheated feed then fows through afired heaterwhere the
feed mixture is totallyvaporized and heated to the required
elevated temperature before entering the reactor and fowing
through a fixed-bed of catalyst where the hydrodesulfurization
reaction takes place.
The hot reaction products are partially cooled by fowing through
the heat exchanger where the reactor feed was preheated and
then fows through a water-cooled heat exchanger before it fows
through the pressure controller (PC) and undergoes a pressure
reduction down to about 3 to 5 atmospheres. The resulting
mixture of liquid and gas enters the gas separatorvesselat
about 35 C and 3 to 5 atmospheres of absolute pressure.

 Most of the hydrogen-rich gas from the gas separator

vessel is recycle gas, which is routed through anamine
contactor for removal of the reaction productH2Sthat it
contains.
TheH2S-free hydrogen-rich gas is then recycled back
for reuse in the reactor section. Any excess gas from
the gas separator vessel joins thesour gas from the
stripping of the reaction product liquid.
The liquid from the gas separator vessel is routed
through areboiled stripperdistillation tower. The
bottoms product from the stripper is the final
desulfurized liquid product from
hydrodesulfurization unit.

 The overhead sour gas from the stripper contains

hydrogen,methane,ethane,hydrogen
sulfide,propane, and, perhaps, somebutaneand
heavier components.
That sour gas is sent to the refinery's central gas
processing plant for removal of the hydrogen sulfide in
the refinery's mainamine gas treating unit and
through a series of distillation towers for recovery of
propane, butane andpentane or heavier components.
The residual hydrogen, methane, ethane, and some propane
is used as refinery fuel gas.
The hydrogen sulfide removed and recovered by the
amine gas treating unit is subsequently converted to
elemental sulfur in aClaus processunit or to sulfuric
acid in awet sulfuric acid processor in the
conventionalContact Process.