19-04-2021

Chapter

Finishing Processes

Introduction
• Different contaminants found in most refinery products before their finishing (See
table)
Table: Major contaminants of distillates and their effects

• Finishing processes: Secondary refining processes which are necessary to make the
petroleum products suitable for use with respect to performance, corrosivity,
suitability on storage, odour, etc.

1
 19-04-2021

• Some of these effects can also be eliminated by proper use of additives (e.g.
antioxidants, metal deactivators, etc.)

• Types of finishing processes

• Sulphur conversion processes
• Sweetening process
• Solvent extraction processes
• Hydro treating processes, etc.

Sulphur Conversion Processes

• Processes used for conversion of sulphur impurities into their useful forms (e.g. elemental S)

Classified in three different categories as:

1. Dry oxidation of H2S to sulphur and water: Claus process is one of the basic type of dry
oxidation process to convert H2S to elemental sulphur. This is most widely used in
refineries.

2. Wet oxidation to sulphur and water: Primarily used for H2S removal in sulphur recovery
and tail gas treating applications when both concentration of H2S in gas stream and sulphur
production tonnage are low.

3. Thermal cracking of H2S to sulphur and hydrogen

2
 19-04-2021

Claus Process • Consisting thermal stage

followed by two or three
reactor stages

• Thermal stage: Includes

reaction furnace, waste heat
re-boiler and condenser

• Reaction involved
3H2S + 3/2 O2 →
2H2S + SO2 + H2O
Exothermic reaction and
temperature reach up to
Figure: Process flow diagram for Claus process 1200ºC in the stage.

• Catalytic stage: Consisting

feed heater, catalyst bed and
condenser

• In this stage gases reheated

to 200-260ºC before
passing to reactor
containing bed of bauxite
catalyst.

• Reaction involved
2H2S + SO2 →
3/n Sn + H2O
Figure: Process flow diagram for Claus process

3
 19-04-2021

• For maximum sulphur

recovery, H2S to SO2 mole
ratio of 2:1

• Sulphur recovery efficiency

for three catalytic reactor
stages with rich acid-gas
feed is about 96-97%.

Figure: Process flow diagram for Claus process

Thermal Cracking of H2S

• Can be integrated with existing Claus sulphur plants

• A portion of H2S acid-gas stream (As much as 25% of total H2S) is fed to cracker to
form H2 and S.

• Energy required for cracker is supplied by sending remaining portion of feed H2S to
conventional Claus furnace and recovered energy from that.

• H2 is separated and can be reused in hydrodesulphurization.

• Separated S and uncracked H2S are recycled to Claus process.

4
 19-04-2021

Sweetening Processes
• Organic S contaminants mostly found in petroleum products: Alkyl and aromatic
mercaptans (R-SH)

• Cause foul odour, corrosion to metals, oxidative deterioration of various additives

(e.g. TEL)

• Sweetening processes are used to reduce S contents (mostly mercaptans) from

different naphtha products (e.g. gasoline).

Types of sweetening processes

1. Process which removes mercaptans but do not affect materially other sulphur
compounds (e.g. Caustic scrubbing, merox extraction, solutizer process and unisol
process, etc.).

2. Processes which convert mercaptans to disulphides (e.g. Doctor sweetening, PbS

sweetening, merox sweetening and copper chloride sweetening, etc.).

3. Processes which remove some or all of different types of S compounds (e.g. Acid
treating, clay treating, catalytic processes and sodafining, etc.).

5
 19-04-2021

Caustic Treatment
• Caustic treating of petroleum products is as old as the industry itself.

• This uses non-regenerative caustic wash.

• Used for removal of hydrogen sulphide in low concentration, naphthenic acids, aryl
mercaptans, alkyl phenol from C4, C5 and naphtha feed

• Calcium, ammonium and sodium hydroxides (being by far the most widely) are used.

• Has no competition in C4, C5 treating but not too satisfactory on heavier stocks

Merox Processes
• Efficient and economical catalytic process to remove mercaptans (Merox extraction)
or to convert them into di-suphides (Merox sweetening)

• Used for liquid phase treating of LPG, Natural gas liquids, naphtha, kerosene, jet
fuels and heating oils

• Extraction and sweetening can be used singly or in combination depending upon the
type and content of mercaptans in the feed and finished product specification.

• Based on ability of a catalyst to catalyse the oxidation of mercaptans to disulphides in

alkaline medium at ambient temperature using air

• Merox catalyst: Sulphonated derivate of Cobalt phthalocynine complex

6
 19-04-2021

• Mild caustic wash of feed before Merox processes, to remove H2S, lower mercaptans
and acidic catalyst toxins

• Overall reaction
2RSH + ½ O2 → RSSR + H2O

Merox Extraction
• Used to extract lower mercaptans from
gases, LPG and light naphtha fractions

• Low molecular weight mercaptans are

soluble in caustic solution.

• Mercaptans are extracted by

countercurrent caustic stream.
RSH + NaOH ↔ RSNa + H2O

Figure: Process flow diagram

7
 19-04-2021

• Forward reaction is favoured by low

temperature, low molecular weight of
mercaptans and high caustic
concentration.

• Treated product passes overhead.

• Regeneration of caustic
RSNa + ¼ O2 + ½ H2O →
NaOH + ½ RSSR

Figure: Process flow diagram