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

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Presentation on theme: "ADDITIVES FOR FUELS & LUBRICANTS OBJECT OF PETROLEUM INDUSTRY To Provide Energy As Heat or Power –Modern Engines are Designed to give maximum Power with."— Presentation transcript:

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2 ADDITIVES FOR FUELS & LUBRICANTS

3 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

4 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

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

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

7 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

8 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

9 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

10 ANTI-KNOCK AGENTS

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

12 OCTANE NUMBER Indication of Anti-knock Quality of FUEL for Spark Ignition Engine Developed by Grahm Edger 1926 REFERENCE FUELS iso-Octane100 n- Heptane 0 Proportion of iso-Octane (vol..%) in Standard Mixture Which Matches in Knocking Behavior with Test Fuel in CFR Engine ON /2

13 - 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

14 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

15 OCTANE NUMBER OF HYDROCARBONS N- Paraffin upto C4Very Good n-Paraffin Beyond C4Very Poor Iso-ParaffinsHigh Cyclo-ParaffinsLower than iso- Paraffins Aromatics / OlefinsHigh Higher proportions of olefins not tolerated because of storage stability and gum forming problems » ON /4

16 METHYL TERT BUTYL ETHER (MTBE) CH3 CH3-COCH3 CH3 Gained Interest as High Octane Blending Component Advantages of MTBE Clean Fuel Provide Principal Fuel Outlet of Methanol ON /5

17 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

18 CETANE NUMBER IMPROVER

19 CETANE NUMBER Performance Index of Diesel Fuel REFERENCE FUEL CN n- Hexadecane100  -Methyl Naphthalene0 2,2,4,4,6,8,8-Hepta Methyl Nonane (HMN)15 CETANE No. = % Cetane + 0.15 ( % HMN)

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

21 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

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

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

24 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

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

26 OXIDATION INHIBITOR

27 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

28 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

29 EFFECT OF OXIDATION PRODUCTS In Diesel Engines –Increase Emissions –Increase Noise –Increase Engine Wear

30 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

31 MECHANISM OF ACTION AUTO - OXIDATION RHR · + H · RH + O 2 R· + ROO· ROOHRO· + ·OH 2ROOH RO· + ROO· +H 2 O 2ROO·2RO· + O 2 ROO + HAROOH + A· i ) Heat, ii) Light, iii) Metals INITATION

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

33 METAL DEACTIVATORS

34 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 Cu 2+ Ions These Metals are Active Catalysts for Oxidative Degradation of Fuel at Very Low Concentration (1.0 ppm) MD / 1

35 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

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

37 CORROSION INHIBITOR

38 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

39 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

40 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

41 ANTI-ICING AGENTS

42 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

43 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

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

45 DOSAGES Dosages Type - I (a) 0.5 - 2.0 % Type - I (b) 0.05 - 0.2 % Type - II0.002 - 0.02 % AI / 4

46 ANTI STATIC AGENTS

47 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

48 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

49 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

50 DETERGENT ADDITIVE

51 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

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

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

54 OTHER ADVANTAGES ANTI – ICING PROTECTION CORROSION PROBLEMS Dosages 30-300 PPM.

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

56 DEMULSIFIERS

57 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

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

59 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

60 BIOCIDES

61 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

62 ADDITIVE TYPES - Borate Ester - Glycol Ethers - MFA with Barium Dosages Very Low<10 ppm One Time Dosage of 100-1000 ppm recommended for Quick - Kill of Existing Bacteria Bio / 2

63 MULTIFUNCTIONAL ADDITIVES

64 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

65 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

66 ADDITIVE TYPES Mainly Highly Alkaline Organo-metallic Compounds Containing Metals Like Ba, Ca, Mg, or Mn having 4 - 20 %by weight of Metal Dosage 500 - 3000 ppm Depending on the Extent of Desired Benefit MFA / 3

67 MISCLANEOUS ADDITIVES

68 DYES 0.7-1.3 g/100 gallon

69 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

70 (5)Exhaust smoke controlling additive: Effective in reducing diesel exhaust Similar to metallic detergents dispersant containing metal, like Ba. (6)Cold Flow Improver Ethylene Vinyl acetate polymers Chlorinated hydrocarbons. Poly olefins Not effective universally. Mis. / 3

71 (7) LPG Additives Low mol. wt. Thiols 15 lb/10,000 Gallons. (8)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


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