MICAL TREATMENTS

NEED OF CHEMICAL TREATMENTS

 Fractions of napthanic crudes contains impurities
1. Sulfur, oxygen and nitrogen compounds
2. Gum like substances
3. Asphalts like materials

Thiols / mercaptans – organosulphur compound

Have a strong odors resembling that of rotten eggs
Used in detection of natural gas
MERCAPTAN’S DISADVANTAGES
 Sulfur compounds darken gasoline
 Impart foul smell.
 Reduce Octane Number
 Elementary Sulfur and Presence of Mercaptans
Cause Corrosion
 Pollute Environment (toxic emissions)
 Dangerous to Human Health.
TYPES OF CHEMICAL TREATMENTS
 Sulphuric acid treatment
 Sweetening processes
 Catalytic desulfurization
SULFURIC ACID TREATMENT
 It is one of the oldest process

 It partly removes sulfur, precipitate asphalts, and gum like

material

 Improves color and stability

 To some extent improves odor

 Products Strength of sulfuric acid Temperature C

Natural gas 75 <30

Straight run gasoline 75 <30

Kerosene 93 <40

Lube oil 98 75-80

Ttransformer oil 80-90

Paraffin and Napthene HCs ----- 93% acid

Olefins and Diolefins and acetylenes ----- 75% of acid

93 % OR MORE ACID IS REQUIRED TO REMOVE SULPHUR

DISADVANTAGES
 With the increasing acid strength and temperature, acid
sludge also increases

 Disposal of these sludge forms a major obstacle

So sulfuric acid treatment is replaced by other processes.

SWEETENING PROCESS:
 Presence of sulphur compounds like H 2 S and mercaptans makes the
oil sour

 Sour stocks have bad odour

 The processes by which the foul smelling sour petroleum products

are converted into sweet smelling or odourless products are called
sweetening processes
SWEETENING PROCESSES
1. Caustic treatment
2. Solutizer process
3. Doctor treating process
4. Copper chloride sweetening process
5. Hypochlorite sweetening
6. Air and inhibitor treating process
7. Merox processes
8. Clay treatment
DOCTOR’S SWEETENING PROCESS
 Mercaptans in sour gasoline is converted into disulphides
 Doctor’s solution (Sodium plumbite solution) and sulphur
 This process reduces only odor

 A gasoline is called as doctor sweet if after shaking with sodium

plumbite solutions, the addition of powered sulfur fails to produce a
dark precipitate of lead sulfide
 Sour gasoline Lead Mercaptide

Powered Sulfur Disulphide

Lead oxide solution causes oxidation of the mercaptans to the corresponding organic sulphides,
which are comparatively odorless
DOCTOR’S SWEETENING PROCESS
DISADVANTAGES
 The process does not remove sulfur from the oil, but even
may increase the sulfur content if too much powered sulfur
is added

 Some of the lead may remain in the petroleum

COPPER CHLORIDE SWEETENING PROCESS
Involves in the oxidation of mercaptans to disulphides and reduction of
cupric chloride to cuprous state.

Then the cuprous chloride is then oxidized with air or oxygen

Both the reaction takes place simultaneously in the presence of Cupric

chloride and fuller’s earth.
 Involves contacting gasoline with sodium, calcium, aluminium, magnesium hydroxide

 Caustic solution ranging from 5-15 % is employed.

 One stage wash in a mixer or settler unit

Advantages
1. Removal of
 Lighter mercaptans

 hydrogen sulfide in low concentration

 Napthenic acids

 Aryl mercaptans

 Alkyl phenol

2. Saving in chemicals in subsequent treatments.

Disadvantages:
 Only lower molecular weight mercaptans are dissolved in caustic solution
 An organic agent is used to increase the solubility of mercaptans in caustic solution
 Solutizer is added to remove heavier mercaptans

 Unisol Process
 Mercapsol Process