Fuel Additives

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 Fuel Additives
 Fuel additives are chemical substances added in small quantities as a rapid,
economic and easy mean for:
 Improving fuel performance properties.
 Control fuel quality during production, distribution and storage.
 Control emissions.
 FUEL ADDITIVES CLASSIFICATION
1. Additives providing oxidation stability
 Antioxidants: minimize oxidation and gum formation during storage
 Metal Deactivators: deactivate trace metals that can accelerate oxidation
2. Additives influencing fuel combustion
 Octane Boosters
 Cetane Improvers
3. Additives used in distribution
 Corrosion/Rust inhibitors: minimize rust throughout the gasoline supply chain
 Dyes & Markers: as per the legal requirements and distinguish brands
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 Demulsifies & Dehazares: minimize haze/emulsion formation
 Fuel Additives (Cont.)
 FUEL ADDITIVES CLASSIFICATION (Cont.)
4. Additives to protect vehicle fuel system
 Detergents and dispersants: controls the deposition of carbon in engine
 Lubricity improvers: improves lubricity and reduces wear
 Corrosion /Rust inhibitors: prevents corrosion/rust on ferrous and non-ferrous
surfaces
 Need for additive
 Primarily due to
 lower fuel quality
 Greater engine demand
 Benefits of Additive use
 Utilization of lower grade crude
 Enhanced fuel stability
 Fuel economy
 Drivability ease
 Longer engine life
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 Lower exhaust emission
 Fuel Additives (Cont.)

 Additives and their functions

 Detergent and dispersant: Keep the engine clean, keep the sludge
in suspension.

 Antioxidant: Prevents the formation of sludge and deposits; slows

down the rate of oxidation of the hydrocarbons.

 Corrosion/Rust inhibitor: Prevents corrosion/rust on ferrous and

non-ferrous surfaces.

 Foam inhibitors: Minimizes foam formation.

 Lubricity additive: Improves lubricity and reduces wear.

 Octane boosters: Improves the octane number of the gasoline.

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 Fuel Additives (Cont.)

 OXIDATION AND ANTIOXIDANT ADDITIVES:

 Hydrocarbon degradation process induced by:
 Oxygen
 Heat
 Metal surface, metal ions
 Irradiation (ultraviolet, daylight)
 Impurities (e.g. free radicals from fuel combustion)
 May lead to:
 Viscosity increase
 Sludge formation
 Formation of organic acids leads to corrosion
 Foam
 Color darkening
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 Fuel Additives (Cont.)
 Hydrocarbon Oxidation Products:
 Oxidation during storage and in use in an engine
 Olefins and diolefins are more susceptible to oxidation
 Organic acids
 Organic esters
 Alcohols
 Alkyl nitrites
 Nitroalkanes
 Aldehydes
 Ketones

 Antioxidant Chemistry:
 Antioxidants extend storage life but can’t destroy gum already formed.
 Essential to add at refinery end to control initiation of oxidation.
 Examples: Hindered aryl phenols, Alkyl-aryl phenylene diamines, substituted
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amino phenols, imidazolines, tetra alkyl primary amines.
 Fuel Additives (Cont.)
 Metal Deactivators:
 Trace levels of metal compounds, e.g., Cu, catalyze the oxidation.
 Lead to the formation of gums.
 Metal deactivators make the metal inactive.
 N.N’–disalicylidene -1,2-propanediamine
 Dosage: 4-12 ppm
 ADDITIVES IN FUEL DISTRIBUTION:
 Dyes and Markers:
 As per legal requirements.
 To distinguish brands.
 To check adulteration/theft.
 Low treat rates: 2-100 ppm
 Markers may not give color to fuel, but are detected by reaction with another
chemical /other means. 7
 Fuel Additives (Cont.)
 ADDITIVES IN FUEL DISTRIBUTION (Cont.):
 Corrosion and Rust Inhibitors:
 To protect storage tanks, pipelines, and tanks from corrosion and rust.
 Chemicals Used:
o Dimeric acids and carboxylic acid derivatives
o Alkylphosporic acids amine salts
o Mannich amines (diethylene triamine, poly (oxypropylene) diamine)
o Sulphonic acid salts

 Demulsifiers and Dehazers:

 Free /dissolved water in fuel during processing and distribution.
 Dissolved water can be separated by a sudden drop in temperature and
appear as haze.
 Antihaze additives having surfactant properties minimize haze/emulsion
formation.

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 Fuel Additives (Cont.)
 ADDITIVES TO PREVENT VEHICLE FUEL SYSTEM:
 Deposit Formation:
 Fuel contains cracked compounds.
 High temperature leads to free radicals.
 Sticky mass & deposit precursors.
 Affect drivability and fuel consumption.
 Detergents prevent these deposits and can also clean up existing deposits,
e.g., Alkanol amines, imidazolines.
 Dispersants improve behavior in fuel injectors; suspend soot (carbon
residue), e.g., polyisobutylene connected to an amine group (maleic
anhydride).
 Anti-icing Additive: Minimize ice formation in carburetors during cold weather.

 ANTIKNOCK ADDITIVES:
 Oxygenates/ Octane Boosters (discussed earlier)
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 Fuel Additives (Cont.)

 Biocide Additives: To be used to inhibit bacterial growth during storage

in contact with water. Eg.: cyclic imines (pyrrolidine hexamethyleneimine),
imidazolines.

 Antistatic additives:
 Generally, hydrocarbons have very low electrical conductivities.

 Manipulation of these fluids creates electrostatic charges that can

result in fire or explosions.

 Cetylvinylether-vinylpyrrolidone copolymer used as an antistatic

additive.

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 Fuel Additives (Cont.)
 LOW TEMPERATURE FLOW PROBLEM:
 Diesel from paraffinic crudes has poor low-temperature flow performance.
 Higher cloud/ pour points result in
 filter plugging
 inability to start
 In India, diesel of 18 oC, 6 oC and 0 oC pour points are being used.
 The extent of the flow problem depends upon
 Fuel hydrocarbon type
 Wax molecular weight/distribution
 Storage temperature/time.
 Flow Improvers:
 Ash less polymers (Ethylene-vinyl acetate copolymer, alkyl methacrylate
polymers/copolymers, alkyl fumerate-maleate polymers)
 Function by interacting with wax crystals and modifying their growth pattern.
 Additives also inhibit the growth of wax crystals.
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 Make the crystal smaller and less prone to agglomeration.
 Fuel Additives (Cont.)

 DIESEL LUBRICITY ADDITIVE:

 The need:

 The sulfur level in diesel is being brought down due to environmental

reasons.

 Lowering of sulfur by hydroprocessing/hydrotreating leads to the removal

of certain polar components from diesel, which are associated with the
deterioration of the lubricity of diesel.

 Lower fuel lubricity can cause failure in injection pumps.

 No effect on the lubricity of diesel when landed with S compounds.

 Lubricity is enhanced on formulating diesel at different dosages of

aromatics.

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 Fuel Additives (Cont.)

 Additives used in Diesel Fuels:

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