FINISHING PROCESSES

PRESENTATION
 Clause processes
This process is used to treat gas streams containing high concentrations of
H₂S. It is a key method in the petroleum industry for recovering sulfur from
hydrogen sulfide (H₂S) gas, which is a by-product of refining high-sulfur
crude oils and processing natural gas. This process is responsible for the
conversion of hydrogen sulfide (H₂S) into elemental sulfur, thereby
reducing sulfur emissions. The chemistry of the units involves the partial
oxidation of hydrogen sulfide to sulfur dioxide, followed by a catalytically
promoted reaction of H₂S and SO₂ to produce elemental sulfur.The
reactions are staged and are as follows:
 Stages of the Clause
process
Stage 1
Conversion of Hydrogen Sulphide to Sulphur dioxide
In this is where one-third of the H2S is burnt with air in a reactor
furnace to form sulfur dioxide (SO2) according to the following
reaction:
2H2S + 3O2 → 2SO2 + 2H2O + heat
This reaction takes place at high temperature within the range of 980 to
1540 degrees celcius and pressure higher than 70kPa
 Stage 1 continue

• 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 or sulfur trap (sulfur
traps operate similar to an inverted bucket condensate trap) 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 from the reactor
furnace condenser. The cooled gases exiting the condenser are reheated
then sent to the catalyst beds.
 Stage 2
• Claus reaction (reacts with SO2)
The remaining uncombusted two-thirds of the hydrogen sulfide undergoes Claus
reaction 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).
• Activated alumina or titanium dioxide 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.
 Stage 2 Continue
• However, with the condensation and removal of sulfur after each reactor,
high sulfur removal efficiencies can be achieved using 2 or more reactors
(or stages) in series with sulfur condensed and recovered after each
stage.
• Each catalytic stage can recover about 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 used and the
reactor temperatures used.
• Higher recoveries are achieved at lower temperatures, but the traditional
Claus reactors must be operated above the dew point of sulfur to prevent
sulfur from condensing within the reactor and deactivating the catalyst.
CLAUS PROCESS
DIAGRAM
• 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 (4)
COS + H2S → CS2 + H2O (5)
2COS → CO2 + CS2 (6)
• The uncondensed vapor leaving the condenser of the final catalytic stage is
commonly referred to as “tailgas.” The tailgas contains nitrogen, H2S, SO2, sulfur
vapor, and traces of other sulfur compounds formed as a result of these side
reactions. It is frequently necessary to follow the Claus unit with a tailgas
treatment unit to achieve higher sulfur recovery efficiencies and/or a thermal
incinerator to convert remaining hydrogen sulfide and other sulfur compounds
in the tailgas to sulfur dioxide.
 Emissions And Controls for SO2
• Emissions of sulfur compounds from the Claus process are directly related to the
recovery efficiency. Higher recovery efficiencies mean less sulfur emitted in the tailgas.
• Claus plants without tailgas treatment have sulfur recovery efficiencies ranging from 92 to
97 percent; Claus plants with tailgas treatment have sulfur recovery efficiencies ranging
from 99 to 99.9 percent.
• The efficiency depends upon several factors, including the number of catalytic stages, the
concentrations of H2S and contaminants in the feedstream, stoichiometric balance of
gaseous components of the inlet, operating temperature, catalyst maintenance, and the
type of tailgas treatment process used.
• Regardless of whether or not a tailgas treatment process is used to increase recovery
efficiency, most sulfur recovery plants use a thermal oxidizer or incinerator to convert H2S
and other sulfur compounds SO2 prior to atmospheric release.
 Doctor Process
• Removes mercaptans (sulfur compounds) from petroleum products
like gasoline, kerosene and diesel fuel.

• Mercaptans give petroleum products an offensive (bad) odor and

increase toxic sulfur dioxide engine emissions.

• The process employs doctor solution (a mixture of lead oxide and

sodium hydroxide) to remove mercaptans.

• Petroleum product is mixed with doctor( sodium plumbite) solution to

convert mercaptans to mercaptides which are removed by filtration or
settling
 Steps of Doctor
Process
 Pros and cons of doctor process
Pros
• Relatively simple process
• Reduces sulfur dioxides emissions from fuels
• Improves the product colour
• Effective for odor reduction
 Cons of doctor process

• Generates hazardous lead containing sludge which is an environment

concern
• The treated product often requires additional refining steps to meet
product specifications
• Its less efficient than modern processes in mercaptans removal
• Handling lead compounds requires strict safety measures to protect
workers
• Due to use of lead compoundsbcan lead to corrosion in refinery
equipment
 HYDROTREATING
• Hydrotreating is an established refinery process for reducing sulfur,
nitrogen and aromatics while enhancing cetane number , density and
smoke point .
• Cetane number is the percentage of pure cetane in a blend of cetane
and alpha-methyl-naphthalene. It measures how quickly diesel fuel
ignites after being injected into the engines combustion chamber. A
higher cetane number indicates a faster ignition.
• Smoke point is a measure of the quality of a kerosene – type fuel .It is
defined as the maximum height (mm) to which the flame can be
raised without producing a contious trail of smoke when a standard
kerosene sample is burned under specific conditions.
 Objectives of hydrotreating

• Removing impurities such as sulphur , nitrogen and oxygen for the

control of a final product specification or for the preparation of feed
for further processing
• Removal of metals , usually in a separate guard catalytic reactor when
the organo-metallic compounds are hydrogenated and decomposed ,
resulting in metal deposition on the catalyst pores.
• Saturation of olefins and their unstable compounds
 Main role of hydrotreating
1. Meeting finished product specification 2. Feed preparation for downstream units

 kerosene , gas oil and lube oil • Naphtha is hydrotreated for removal of
desulphurization metal and sulphur.
 Olefin saturation for stability
• Sulphur , metal , polyaromatics and
improvement
Conradson carbon removal from vacuum
 Nitrogen removal
gas oil (VGO) to be used as FCC feed.
 De-aromatization for kerosene to improve
• Pretreatment of hydrocracking feed to
cetane number
reduce sulphur , nitrogen and aromatics
 Hydrotreating reactions
1.Desulphurization 2.Denitrogenation
 Hydrotreating reactions cont..
3.Deoxydation
Hydrotreating reactions
 1. Naphtha hydrotreating

 To remove the impurities so that the hydrotreated naphtha can be

introduced to the catalytic reformer.
 The expensive platinum based catalyst is used in the reformer is
sensitive to poisoning by such impurities
 2.Middle Distillates Hydrotreating
• Middle distillate is mainly composed of saturated paraffins and also
some aromatics which include simple compounds with up to three
aromatic rings .

• Kerosene , jet fuel oil and diesel fuel are all derived from middle
distillate fractions.
3. Atmospheric Residue Desulphurization

• Atmospheric residue has a sulphur content and (Ni +V)

• The purpose of this process is to remove most of the metals and

reduce sulphur content in the product to less than 0.5 wt%
Reactor
Hydrogen requirements for hydrotreating
are classified into :
1.Chemical requirement
 This is the amount of hydrogen required to remove impurities such as
sulphur , oxygen , nitrogen , olefins and organometallic compunds ,
according to the stoichiometry of these reactions.
 Sometimes , it might be required to convert aromatics and
naphthenes to corresponding paraffins.
Hydrogen requirements for hydrotreating
are classified into :
2). Hydrogen lost due to the dissolution of hydrogen in the
hydrocarbons treated.
3)Amount of hydrogen lost with the purging of light hydrocarbonds
( C1_C4) and hydrogen sulphide ( if not removed by amine treatment)
 Storage of hydrocarbon
It refers to methods and facilities used to store crude oil, refined
petroleum products and other hydrocarbon based fluids.

Classification of storage
• Underground Storage
• Aboveground Storage
 Uderground Storage
Underground storage involves storing hydrocarbons in geological
formations beneath the earth's surface. This method is often used for
large-scale storage due to the natural containment provided by the
surrounding rock.

Examples of uderground storage

1. Porous Media(Depleted Oil and Gas Reservoirs)
2. Salt Caverns
3. Mined Caverns
Depleted Oil and Gas Reservoirs
• These are former oil or gas fields
that have been emptied of their
original hydrocarbons. They are
repurposed for storing natural gas,
LPG, or other hydrocarbons due to
their proven containment
capabilities.
• These reservoirs have a long
history of use, primarily for natural
gas storage. They offer large
storage capacities and are cost-
effective since the infrastructure is
already in place.
 Salt Caverns
• Created by dissolving salt deposits,
these caverns are used for storing
LPG, natural gas, and other
hydrocarbons.
• The process of creating salt caverns
involves injecting water to dissolve
the salt, then removing the brine.
These caverns are ideal for storing
hydrocarbons due to their structural
integrity and low permeability.
Mined Caverns
• These are excavated spaces in rock formations, used for
storing crude oil and other liquid hydrocarbons.
• They are specifically excavated for storage purposes. They are
lined to prevent leaks and can store large volumes of
hydrocarbons safely.
 Aboveground Storage
Aboveground storage involves storing hydrocarbons in tanks or
containers located on the earth's surface. This method is often used
for easier access and monitoring.

Examples of aboveground storage

1. Fixed Roof Tanks
2. Floating Roof Tanks
3. Spherical Tanks:
 Fixed roof tank
• Commonly used for storing
low vapor pressure
hydrocarbons like diesel and
fuel oil.
• These tanks have a
permanent roof and are
simple in design.
• They are cost-effective but
can have higher vapor
losses compared to floating
roof tanks.
Floating roof tank
• Used for storing volatile hydrocarbons like gasoline and crude oil.
• These tanks have a roof that floats on the liquid surface, reducing
the space for vapor to accumulate and thus minimizing emissions.
• They are commonly used for storing large volumes of volatile
hydrocarbons.
 Spherical tank

• Typically used for storing

liquefied gases such as
Liquefied Petroleum Gas (LPG)
and Liquefied Natural Gas
(LNG).
• The spherical shape evenly
distributes stress, making these
tanks suitable for storing gases
under high pressure. They are
often used for LPG and LNG
storage.
Safety and Environmental Considerations

1. Leak Detection Systems

• Essential for preventing environmental contamination. Early detection
allows for prompt action to mitigate damage.

2. Fire Protection
• Implementing fire suppression systems and maintaining safe distances
between tanks is critical to prevent and control fires.

3. Ventilation and Gas Blanketing

• Proper ventilation prevents the buildup of explosive gases, while gas blanketing
systems maintain an inert atmosphere to reduce the risk of ignition
 Operational Procedures
Filling and Pumping Operations
• Ensuring safe and efficient transfer of hydrocarbons is vital.
• This includes using appropriate pumps and maintaining proper flow
rates to avoid overfilling and spills.
Maintenance and Inspection

• Regular checks are necessary to prevent leaks and ensure the

structural integrity of storage tanks.
• This includes inspecting for corrosion, cracks, and other potential
issues
 Operational Procedures
Filling and Pumping Operations
• Ensuring safe and efficient transfer of hydrocarbons is vital.
• This includes using appropriate pumps and maintaining proper flow
rates to avoid overfilling and spills.
Maintenance and Inspection

• Regular checks are necessary to prevent leaks and ensure the

structural integrity of storage tanks.
• This includes inspecting for corrosion, cracks, and other potential
issues
• A pressure vs temperature phase diagram is used to conditions at
which various phases exist.