FUELS

REFINERY PROCESSES

TYPICAL PRODUCTS PRODUCT WT% GAS 0.1 LPG 1.0 NAPHTHA 9.7 ATF / KEROSENE 10.8 HSD24.3 PRODUCT WT% LDO 4.8 FUEL OILS17.8 ASPHALT 9.7 VACCUM DISTILLATES 18.5 FUEL & LOSSES 3.0

REFINERY FUELS PRODUCTS PROPANE LPG GASOLINE (NORMAL) GASOLINE (PREMIUM) LOW AROMATIC NAPHTHA HIGH AROMATIC NAPHTHA AVIATION TURBO FUEL DEFENCE / COMMERCIAL HIGH SPEED DIESEL LIGHT DIESEL OIL KEROSENE FUEL OIL (NORMAL) FUEL OIL (DEFENCE) LSHS

GASOLINE - SPECIFICATIONS WHERE ARE WE GOING ? LEAD BENZENE SULFUR VOLATILITY –VLI –E 70, E 100, E 180 –FBP –RESIDUE OXYGENATES GUM CONTENT OLEFINS DENSITY ANTI KNOCK INDEX ENGINE TESTS

DIESEL - SPECIFICATIONS WHERE ARE WE GOING ? AROMATICS POLY AROMATICS CARBON RESIDUE SULFUR WATER CONTENT OLEFINS VISCOSITY VOLATILITY (T 95) HEATING VALUE COMPONENT COMPATIBILITY STABILITY CETANE INDEX LUBRICITY OXIDATION STABILITY ENGINE / RIG TESTS

WHY BEING DONE TIGHTER EMISSION NORMS CHANGES IN ENGINE DESIGNS CHANGES IN METALLURGY OF THE ENGINE USE OF CAT CONVERTORS FUEL EFFICIENCY INCREASED POWER

ALL THIS HAS LED TO DECREASED FUEL STABILITY DECREASED COMPATIBILITY INCREASED OCTANE REQUIREMENTS POOR DRIVEABILITY AND DURABILITY EXTENDED REFINERIES AND TECHNOLOGY OF REFINING TO MAXIMUM

SOLUTION ? FUEL ADDITIVE “HP DIESEL PLUS” & “HP PETROL PLUS”

BENEFITS IMPROVED FUEL ECONOMY FUEL INJECTION CLEANLINESS IMPROVED FUEL STABILITY REDUCED EXHAUST EMISSIONS DISPERSANCY FOR INSOLUBLE GUM IMPROVED LUBRICITY CORROSION PROTECTION PREVENTION OF STABLE FUEL WATER EMULSIONS REDUCTION IN FOAM

DIESEL SPECS

* LOWER THAN LOWEST AMBIENT

HEAVY FUEL OIL SPECS

TEST PROCEDURES

TEST SIGNIFICANCE DENISTY - ESSENTIAL FOR QUNTITY CALCULATIONS, SETTING PURIFIER, INDICATES SPECIFIC ENERGY AND IGNITION QULAITY API GRAVITY ° = (141.5 / RELATIVE 60 / 60°F) FLASH POINT - LEGAL REQUIREMENT POUR POINT - FUEL MUST BE MAINTAINED ABOVE POUR POINT

TEST SIGNIFICANCE CARBON RESIDUE - HIGH VALUES MAY GIVE DEPOSIT PROBLEMS ASH - IF EXCESSIVE CAN GIVE FOULING DEPOSITS WATER - CAN CAUSE SLUDGE AND COMBUSTION PROBLEMS VANADIUM AND SODIUM - POTENTIAL HIGH TEMPERATURE CORROSION CAN BE MINIMISED BY TEMPERATURE CONTROL AND MATERIALS SELECTION

TEST SIGNIFICANCE ALUMINIUM AND SILICON - USUALLY PRESENT AS CATALYST FINES WHICH ARE ABRASIVE, CAN NORMALLY BE REDUCED TO AN ACCEPTABLE LEVEL BY A CENTRIFUGE SULPHUR SEDIMENT & STABILITY - FUEL IS STABLE IF IT DOES NOT BREAK DOWN GIVING HEAVY SEDIMENT COMPATIBILITY - THE ABILITY OF TWO FUELS WHEN MIXED TO REMAIN STABLE

TEST SIGNIFICANCE SPECIFIC ENERGY - NET VALUE FOR DIESEL AND GROSS VALUE FOR BOILERS, USUALLY CALCULATED FROM EMPIRICAL EQUATIONS IGNITION QULAITY - RELATES TO PART OF THE COMBUSTION PROCESS –FOR RESIDUAL FUELS EMPIRICAL EQUATION FOR CCAI IS –CCAI = d log log (VK ) d = DENSITY VK = VISCOSITY

TEST SIGNIFICANCE VISCOSITY - DETERMINES INJECTION AND TRANSFER TEMPERATURES FUELINJ VISC INJ VISC 13 CST 17 CST

COMPARISON OF FUELS

CASE STUDY NAPHTHA DIESEL FUEL OIL

NAPHTHA

REACTIONS FOR BURNING CO + 1/2 O 2 =CO 2 H 2 + 1/2 O2=H 2 O C n H n+x + (n+1)/2O2=nCO 2 + yH 2 O EXCESS AIR NEEDED =( )/2 = 1.15

SOOT CONTROL FAULTY INJECTORS –DEGREE OF ENRICHMENT –AIR REQUIREMENT –VOLUME OF COMBUSTION PRODUCTS –FLAME TEMPERATURE –ATOMISATION / OVERFUELING RESTRICTED AIR INTAKE EXCESSIVE EXHAUST BACK PRESSURE INTAKE AIR HOT LEAKAGE OF AIR THRU GASKETS PREIGNITION WRONG FUEL

ADDITIVES FOR HEAVY FUEL OILS CRUDE OILS AND FUEL OILS HEAVY FUEL OILS COMBUSTION MECHANISM POTENTIAL PROBLEMS AND SOLUTIONS –ADDITIVE A & B

Viscosity,20°C % asphaltenes Gasoline (C5-80°) Heavy gasoline (80-160°) Kerosene ( °) Middle distillate ( °) Heavy distillate ( °) Residue (400 +) ARABIAN HEAVY ARABIAN LIGHT NIGERIAN BONNY FRACTIONS FROM 3 DIFFERENT CRUDES

CHARACTERISTICS OF SOME CRUDE OILS Viscosity,20 °C,cSt Sulfur,% Vanadium, ppm Nickel, ppm Asphaltenes, % Conradson carbon,% Arabian light Arabian heavy Ekofisk < Nigeria light Basrah heavy Boscan Ural

G as AD VD Reforming Visbreak. Hydrocr. Coking FCC DA Naphta Gasolines Kerosene Diesel oils Heavy fuels SR Gasolines Kero,Diesel Heavy fuels H2, no Heavy Fuels 4 Asphalts Heavy fuels REFINERY SCHEMES

CHEMICAL COMPOSITION RESIDUE OR HEAVY FUEL OIL ASPHALTENES MALTENES "OIL" "RESINS" SATURATED AROMATIC

MODEL OF ASPHALTENE MOLECULE S CH2 CH3 CH2 CH3 CH CH2 CH3 CH2 CH3 CH2 S S CH3 CH2 S CH CH2 CH3 CH2 CH3 CH CH2 CH3 CH2 CH3 N CH2 CH3 CH2 CH3 CH2 O S CH CH2 CH3 CH2 CH3

ASPHALTENES CHARACTERISTICS Polycondensed aromatic structures with few alkyl chains Contains hetero-atoms: S, N, O Contains metals: V, Ni, Na Not soluble in oil Size of the micellar unit: A Cannot boil even under reduced pressure Molecular structure depends on crude oil origin

RESINS CHARACTERISTICS Chemical structure close to asphaltenes structure but: LONGER ALKYL CHAINS LESS CONDENSED RINGS MORE SOLUBLE IN OIL Molecular structure depends on crude oil origin Presence necessary to provide a good stability to the fuel

HEAVY FUEL OILS DISPERSED AND STABLE FLOCULATED Resins ensure seperation of heavy asphaltene molecules. Flocculated Asphaltene molecules tend to form sludge and settle at the bottom of the tank.

COMBUSTION MECHANISM Atomisation Vaporization Combustion Viscosity Distillate cuts Density Metals Conradson Carbon C/H Ratio Ignition

SOOT UNBURNT PARTICLES FLAME FRONT FUEL DROPLET CENOSPHERE EMISSIONS OF PARTICLES 0.02  m 1 to 100  m LIGHT GASEOUS FRACTIONS Simple droplet combustion model SOLID ACCUMULATION

CENOSPHERES

PARTICULATE EMISSIONS SOOT (Soot number from 0 to 9 Bacharach) –GAS PHASE COMBUSTION –OH* increases the rate of oxidation of soot precursors UNBURNT PARTICLES (mg/Nm 3 ) –HETEROGENEOUS COMBUSTION (CENOSPHERES) 2 H 2 OH OH* Catalyst M CO + H 2 Catalyst M ’ Cenospheres + H 2 O v

POTENTIAL PROBLEMS STORAGE STABILITY AND COMPATIBILITY UNBURNT PARTICLES

STORAGE PROBLEMS –ASPHALTENES PRECIPITATION –CLOGGING OF FILTERS AND PIPES –SATURATION OF SEPARATORS –CLOGGING OF INJECTION SYSTEM ORIGIN –ASPHALTENES PRECIPITATION BLEND OF NON-COMPATIBLE FUELS STORAGE TEMPERATURE SOLUTION –ADDITIVES

ADDITIVE A Preventive action Curative action Fuel without additiveFuel with additive A

ADDITVE A DOSING RATE –1 LITRE FOR 2000 TO 5000 LITRES OF FUEL. IMPROVES HEAVY FUEL OIL STABILITY PREVENTS ASPHALTENE PRECIPITATION AVOIDS COMPATIBILITY PROBLEMS NON TOXIC PRODUCT NON TOXIC COMBUSTION PRODUCTS

UNBURNT PARTICLES PROBLEM –EMISSIONS OF UNBURNT PARTICLES –HEATING SURFACES FOULING –FREQUENT BOILER CLEANING –COST OF EMISSION LIMITATIONS ORIGIN –NEED OF COMBUSTION IMPROVER –VERY LOW METAL CONTENT SOLUTION –ADDITIVE B

EFFICIENCY OF ELF ADDITIVE B A B C FUEL : + ELF AC 13 S (1/3000 l) 2 : + ELF AC 13 S (1/2000 l) Unburnt HC mg/th Excess of air %

ADDITIVE B DOSING RATE: –1 LITRE FOR 2000 TO 4000 LITRES OF FUEL. REDUCES EMISSIONS OF UNBURNT PARTICLES –MORE THAN 50 % ALLOWS TO REDUCE EXCESS OF AIR. REDUCES FOULING ACHIEVES A MORE STABLE COMBUSTION YIELD. REDUCES DEPOSITS ON HEAT TRANSFERS. NON TOXIC PRODUCT NON TOXIC COMBUSTION PRODUCTS

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