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ADDITIVES FOR FUELS & LUBRICANTS

ADDITIVES FOR FUELS & LUBRICANTS. OBJECT OF PETROLEUM INDUSTRY. To Provide Energy As Heat or Power Modern Engines are Designed to give maximum Power with Fuel Economy

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ADDITIVES FOR FUELS & LUBRICANTS

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

  11. OCTANE NUMBERIndication of Anti-knock Quality of FUEL for Spark Ignition EngineDeveloped by Grahm Edger 1926REFERENCE FUELSiso-Octane 100 n- Heptane 0 Proportion of iso-Octane (vol..%) in Standard Mixture Which Matches in Knocking Behavior with Test Fuel in CFR EngineON /2

  12. - 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 EngineON /3

  13. ADDITIVE TYPESMost Popular and Most Effective are TEL and TMLUNIQUE FEATURE OF LEAD ALKYLS-Effective in Minute Dosages- Good Response to All Types of Gasoline- Very Large Cost EffectivenessPROBLEMS WITH LEAD ALKYLS- Non Volatile Deposits (Mainly Oxides) on a) Combustion Chamber b) Spark Plug and c) Exhaust Line- LEAD POLUTIONON /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 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 Performance Index of Diesel Fuel REFERENCE FUEL CN n- Hexadecane 100 -Methyl Naphthalene 0 2,2,4,4,6,8,8-Hepta Methyl Nonane (HMN) 15 CETANE No. = % Cetane + 0.15 ( % HMN)

  19. HIGH CETANE VALUE • REFLECTS • 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 • - 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. 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) ROOH + Cu++ ROO. + H+ + Cu+ R + M+n R. + H+ + M+(n-1) O2 + M+n M+(n+1) + O2.- CH 3 CH - CH 2 N=C C=N CH - CH 2 2 N=C C=N OH HO CuCL 2 OH HO CH 3 CH - CH NN' - DISALICYLIDIENE - 1,2- 2 ETHYLENE DIAMINE N=C C=N Cu O O 4ppm DOSAGE

  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 0.002 - 0.02 % 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 0.3-10 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

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