1. ADDITIVES FOR FUELS & LUBRICANTS

2. OBJECT OF PETROLEUM INDUSTRY
To Provide Energy As Heat or Power
Modern Engines are Designed to give maximum Power with Fuel Economy
Improved Engine Design And Transmission require Matching Efforts by Petroleum Industry to provide Fuel and Lube of Desired Performance Level
Fuel and Lube have to meet Stringent SPECIFICATIONS

3. WHY ADDITIVES ???
Additives have Unique Role to Play in Meeting Product Quality and Performance Level
Additives Provide Economic and Easy Means a) of Improving Performance
b) Controlling Quality during , Production, Distribution, and in Use
Additives Play Key Roles in Formulations of Fuels And Lubes

4. WHAT IS ADDITIVE ?
Additive is a Fine Chemical which Modifies the Characteristic of Refined Petroleum Fractions, thus
Improve Performance
Extend the Area of Application

5. FUNCTION OF AN ADDITIVE
Prevent Finished Product from Detoriation
Protect Equipment
Improve Performance
Impart Property Not Already Present

6. ESSENTIAL CHARACTERISTICS OF ADDITIVES
Solubility in Base Stocks
Low Volatility
High Chemical Stability
Compatibility-Synergistic /Antagonistic
Acceptable Color and Odor
Low Toxicity
Should be Cheap
Derived from Easily Available Raw Material
Preferably Multifunctional

7. TYPES OF FUEL ADDITIVES (FUNCTIONAL POINT OF VIEW)
Ignition Control Additives
- Antiknock Agents
- Cetane Number Improver
- Pre-ignition Additives
Oxidation Inhibitor
Metal Deactivator
Enable To Meet the Specifications

8. TYPES OF FUEL ADDITIVES (FUNCTIONAL POINT OF VIEW)
Corrosion Inhibitor
Anti - Icing Agents
Anti - Static agents
Detergent Additives
Improve Performance
Improve Vehicle Operation
Reduce Fuel Consumption
Reduce Exhaust Emission

9. ANTI-KNOCK AGENTS

10. Engine Knocking Leads To
What is Knocking
Engine Knocking Leads To
- Loss of Fuel Efficiency
- Engine Over Heating
- Damage to Piston Ring and Bearing
ON/1

11. OCTANE NUMBER. Indication of Anti-knock Quality of
OCTANE NUMBER Indication of Anti-knock Quality of FUEL for Spark Ignition Engine Developed by Grahm Edger REFERENCE FUELS iso-Octane n- Heptane Proportion of iso-Octane (vol..%) in Standard Mixture Which Matches in Knocking Behavior with Test Fuel in CFR Engine ON /2

12. - Knocking is a Function of Both the. Engine and the Fuel
- Knocking is a Function of Both the Engine and the Fuel - For a Given Set of Engine Conditions Knocking is a MOLECULAR PROPERTY of the Fuel Quality - Anti-Knock Agents are Required to Improve the Octane Number of Gasoline in Spark Ignition Engine ON /3

13. ADDITIVE TYPES Most Popular and Most Effective are TEL and TML UNIQUE FEATURE OF LEAD ALKYLS - Effective in Minute Dosages - Good Response to All Types of Gasoline - Very Large Cost Effectiveness PROBLEMS WITH LEAD ALKYLS - Non Volatile Deposits (Mainly Oxides) on a) Combustion Chamber b) Spark Plug and c) Exhaust Line - LEAD POLUTION ON /4

14. OCTANE NUMBER OF HYDROCARBONS
N- Paraffin upto C4 Very Good
n-Paraffin Beyond C4 Very Poor
Iso-Paraffins High
Cyclo-Paraffins Lower than iso- Paraffins
Aromatics / Olefins High
Higher proportions of olefins not tolerated because of storage stability and gum forming problems
ON /4

15. METHYL TERT BUTYL ETHER (MTBE)
CH3
CH3- C O CH3
Gained Interest as High Octane Blending Component
Advantages of MTBE
Clean Fuel
Provide Principal Fuel Outlet of Methanol
ON /5

16. LEAD PHASE DOWN
In Absence of Alternate Anti-Knock to Lead Alkyls Octane Number Will be Met by Refinery Processes and Not by Additive Use

17. CETANE NUMBER IMPROVER

18. CETANE NUMBER REFERENCE FUEL CN n- Hexadecane 100
Performance Index of Diesel Fuel
REFERENCE FUEL CN
n- Hexadecane
-Methyl Naphthalene 0 2,2,4,4,6,8,8-Hepta
Methyl Nonane (HMN) 15
CETANE No. = % Cetane ( % HMN)

19. HIGH CETANE VALUE REFLECTS DEPENDS ON Easy Start Smooth Burning
Low Piston Varnish
DEPENDS ON
Ignition Delay

20. IGNITION DELAY
The Time Lag Between the Beginning of Fuel Injection and Beginning of Explosion.
DEPENDS ON
Hydrocarbon Type Present in the Fuel
Paraffinic < Olefinic / Cyclo- Paraffinic < Aromatic Fuel

21. LARGE IGNITION DELAY CAUSE
Engine Roughness / Knocking
Decrease in Efficiency
Smokey Exhaust
Carbonous Deposits in Piston Rings

22. ADDITIVES TYPE Chemicals Having Thermally Sensitive Groups
Alkyl Nitrates
Ether Nitrates
Ethylene Glycol Nitrates
More Complex Nitrates
Thio - Nitrates
Chloro Picrines
Peroxides
Acetyl Peroxide

23. MECHANISM OF ACTION Precise Mechanism Not Known
They Lower Autoignition Temperature
Cetane Improver Readily Decompose to Free Radicals
Thus Enhance the Rate of Chain Initiation for Hydrocarbon Oxidation
CN / 6

24. PRE IGNITION CONTROLE ADDITIVES
These are Phosphorous Containing Additives and are no more Require Due to Lead Phase Down

25. OXIDATION INHIBITOR

26. WHY ANTIOXIDENTS ARE NEEDED ???
On Prolong Storage Petroleum Fuels Undergo a Slow But Progressive Oxidative Degradation
It Result in the Formation of Non-Volatile Gummy Residues
Gum Formation is the End Product of Oxidation and Polymerization Reactions Involving Mainly Olefinic Constituents

27. EFFECT OF OXIDATION PRODUCTS
In IC Engines
Choking of Intake System
Plugging of Fuel Filters
Operational Problems
Engine Stalling
Upsetting Air : Fuel Ratio Resulting in Power Loss And Poor Fuel Economy

28. EFFECT OF OXIDATION PRODUCTS
In Diesel Engines
Increase Emissions
Increase Noise
Increase Engine Wear

29. ANTIOXIDDANTS INDUCTION PERIOD
- Successful in Controlling Potential - Gum Efficiency is Measured by Ability to Increase the INDUCTION PERIOD
INDUCTION PERIOD
- Initial Stage of Oxidation
- Very Little Absorption of Oxygen

30. i ) Heat, ii) Light, iii) Metals
MECHANISM OF ACTION
AUTO - OXIDATION
RH R· + H·
RH + O2 R· + ROO·
ROOH RO· + ·OH
2ROOH RO· + ROO· +H2O
2ROO· 2RO· + O2
ROO + HA ROOH + A·
i ) Heat, ii) Light, iii) Metals
INITATION

31. TYPES OF ADDITIVE Two Types of Additives are in Use Hindered Phenols
Amines

32. METAL DEACTIVATORS

33. WHY REQUIRED Trace Amount of Metal may Find its Way in Fuel
It has Pronounced Adverse Effect on the Storage Quality of Fuel
Metals have Variable Valences Typified by Cu2+ Ions
These Metals are Active Catalysts for Oxidative Degradation of Fuel at Very Low Concentration (1.0 ppm)
MD / 1

34. TYPES OF CATALYST
Metal Deactivators are Organic Compounds Soluble in Fuel
MECHANISM OF ACTION
They Form Strong Co-ordinate Complexes with Metals
By Chelate Formation ,Catalytic Activity of the Metal is Completely Suppressed

35. METAL DEACTIVATORS ROOH + Cu+ RO. + OH- + Cu+(n+1)
R + M+n R. + H+ + M+(n-1)
O2 + M+n M+(n+1) + O2.- CH 3 CH 2
- CH
C=N
N=C CH 2
- CH 2
C=N
N=C OH HO
CuCL 2 OH HO CH 3
NN' - DISALICYLIDIENE - 1,2- CH 2
- CH
ETHYLENE DIAMINE
C=N
N=C Cu O O
DOSAGE
4ppm

36. CORROSION INHIBITOR

37. WHY REQUIRED Corrosion is not a Serious Problem with HYDROCARBON Alone
Mainly Due To
Entry of Water by Condensation or Accident
Additional Corrosion Problem Arise with
- Alcohol or Oxygenates as they Give Rise to
a) Corrosive By- products (Organic Acids or
Alcoxides)
b) Dissolve Increased Amount of Water
Water Can Precipitate Resulting in Area of Localized Corrosion
CI / 1

38. TYPES OF ADDITIVES
High molecular weight Carboxylic Acids and their Derivatives
Alkyl Phosphoric Acid and their Amine Salts
Aryl Sulphonic Acids and Amine Salts
Mannich Amines
CI / 2

39. MECHANISM OF ACTION
Forms Hydrophobic Film by Physical Adsorption on Metal Surface
Water
Oil soluble group
Polar group
Metal surface * * * * * *
Dosage 250ppm
Mandatory in some Military Fuels
CI / 3

40. ANTI-ICING AGENTS

41. WHY NEEDED ??
Water Present in the Fuel or in In-coming Air Freezes in Carburetor due to Heat of Evaporation of Fuel
EFFECT OF ICE FORMATION
Stalling of Engine
Clogging of Filters

42. TYPES OF ADDITIVES Freezing Point Depressants
- (a)Low Molecular Weight Alcohols e.g.
Methanol, iso-Propanol etc
- (b) Other Compounds e.g.
DMF, Propylene glycol, Hexylene glycols
Surface Active Agents e.g.
- Amine Neutralized Alkyl Phosphates
- Ethoxylated, Propoxylated Alcohols,Phenols etc AI / 2

43. MECHANISM OF ACTION For Alcohols type :- Lower the Freezing Point
Mechanism is similar to Corrosion Inhibitors
Water

44. DOSAGES Dosages Type - I (a) 0.5 - 2.0 % Type - I (b) 0.05 - 0.2 %
Type - II %
AI / 4

45. ANTI STATIC AGENTS

46. WHY REQUIRED
Hydrocarbon Fuels Specially Highly Refined are Bad Conductor of Electricity
Can Develop Considerable Static Charge During Mechanized Filling Operation in
a) Refinery Storage Tanks
b) Fuel Loading Vehicles etc
Spark due to Static Charge can Ignite Fuel if Spark Energy Exceed  0.2 millijoules
ASA / 1

47. ADDITIVE TYPE One such Additive ASA-3 (Shell) Three Component System
a) Cr - Salt of Alkylated ( C14-C18 ) Salicylic Acid
b) Ca- Di (2-Ethyl Hexyl ) Sulfo-
succinate
c) Polymer as Stabilizer
ASA / 2

48. MECHANISM OF ACTION Increases Electric Conductivity from
picomho / meter to 1000
picomho / meter
Allow Rapid Dissipation of Charge
Dosage
< 1.0 ppm
increase Conductivity to > 50 picomho
ASA / 3

49. DETERGENT ADDITIVE

50. WHY REQUIRED ?? Change of Carburetor to Fuel Injection Systems
Wide Use of Cracked Components in Gasoline (Deposit in Injection Nozzles)
Engine Modification to Reduce Exhaust Emissions eg
Positive Crankcase Ventilation (PVC)
Exhaust Gas Recycle (EGR)
DA / 2

51. ADVANTAGES OFFERED Reduce Exhaust Emission
Improve Vehicle Derivability
Reduce Maintenance Cost
Reduce Starting Problems
Reduce ORI
Det A / 2

52. ADDITIVE TYPES: FATTY AMINES FATTY AMIDES IMIDAZOLINES SUCCINIMIDE
POLY ETHER AMINES
Det A / 3

53. OTHER ADVANTAGES ANTI – ICING PROTECTION CORROSION PROBLEMS Dosages
PPM.

54. EFFECT OF DETERGENTS ON DEESEL EXHAUST EMISSION AFTER 1000 KM.

55. DEMULSIFIERS

56. WHY NEEDED ?? Water can Come in Contact During Distribution or Storage
Presence of Detergents in Fuel Leads to Emulsions Specially During Pipeline Dynamic Transportation
Emulsions Have a Tendency to Pick-up Particulates Present in Fuel
Dem. / 1

57. Water Emulsions in Fuels Leads to. - Corrosion. - Carburetor Icing
Water Emulsions in Fuels Leads to - Corrosion - Carburetor Icing - Filter Plug Blockage
Demul / 2

58. ADDITIVES TYPES
Surface Active Chemicals of Limited Solubility in Fuels
- Long Chain Alcohols
- Long Chain Amines
- Alkyl Phenols
- Carboxylic Acids
- Ethoxylated Alkyl Phenols are Popular and are Extensively Used
Dosages:- <10ppm
Used in Both Gasoline and Diesel Demul / 3

59. BIOCIDES

60. WHY NEEDED
Growth of Bacteria at WATER / FUEL Interface Effect Fuel Quality
- Bacteria may Produce Slime which Blocks Fuel Filters
- Problem more Sever with Paraffinic
Fuels (ATF) as Bacteria Live in Water
/ Survive on Paraffin
Bio / 1

61. ADDITIVE TYPES - Borate Ester - Glycol Ethers - MFA with Barium
Dosages
Very Low <10 ppm
One Time Dosage of ppm recommended for Quick - Kill of Existing Bacteria
Bio / 2

62. MULTIFUNCTIONAL ADDITIVES

63. Multifunctional Additives
These Additives Provide More than One Benefits
Gained Popularity Recently
One Lubrizol Additive Based on Barium Metal Provides Following Benefits
- Dispersancy
- Combustion Improvement
- Exhaust Smoke Control
- Anti-Wear
- Fuel Economy
MFA / 1

64. BENEFITS OF MFA Reduction of Exhaust Smoke
Use of MFA (0.25 %) Increase Power up-to 7 % with Smoke Reduction by 50 %
Increase Fuel Injector Life Many Folds
Reduce Engine Wear
Alkaline MFA Neutralize Acidic Diesel Combustion Products there by Reducing their Attack on Metal Surface. Reduction in Wear Implies:
- Extended Operational Period
- Leading to Profitability
MFA Incorporation in Fuel Allow High Sulfur Fuels by Controlling Acidic Corrosion
MFA / 2

65. ADDITIVE TYPES
Mainly Highly Alkaline Organo-metallic Compounds Containing Metals Like Ba, Ca, Mg, or Mn having %by weight of Metal
Dosage
ppm Depending on the Extent of Desired Benefit
MFA / 3

66. MISCLANEOUS ADDITIVES

67. DYES
g/100 gallon

68. Upper Cylinder Lubricants:
To counter effect of Gum Deposits (soluble in these oils)
Light lube oils.
Stable Poly olefins.
Ester Lubricants.
Spark Aids:
Strengthen Spark in IC Engine
Reduce Misfiring During Acceleration or Hesitation
Improve Fuel Economy
Polymeric Pot. Compounds Mis / 2

69. Exhaust smoke controlling additive:
Effective in reducing diesel exhaust
Similar to metallic detergents dispersant containing metal, like Ba.
Cold Flow Improver
Ethylene Vinyl acetate polymers
Chlorinated hydrocarbons.
Poly olefins
Not effective universally.
Mis. / 3

70. Residual Fuel Additive:
LPG Additives
Low mol. wt. Thiols
15 lb/10,000 Gallons.
Residual Fuel Additive:
Rich in Sludge forming unsaturates moistures, metal constituents.
Effect Refractories decrease its strength
Alumina, Talk, Silica etc.
Modify nature of Ash.
Mis. / 4