Quality Monitoring of Petroleum

Products
Dr. Shashikant Yadav
API Gravity

• API Gravity is a measure of how heavy or light petroleum liquid is compared to

water.
• The gravity of crude oil determines its price commercially. It is generally expressed
as API gravity defined as:

• where SG is the specific gravity defined as the density of the crude oil relative to
the density of water both at 15.6 ⁰C (60 F). The API gravity can range from 8.5 for
very heavy crudes to 44 for light crudes.
Flash Point
• The flash point of a liquid hydrocarbon is the lowest
temperature at which sufficient vapours are produced
above the liquid such that spontaneous ignition will
occur if a spark is present.
• Flash point indicates the fire and explosion potential of
a fuel.
• A low flash point fuel is a higher fire hazard.
• It is an important specification for gasoline and naphtha
related to safety in storage and transport in high
temperature environments.
• One of the standard tests is ASTM D1711, D09 and
D1695.
Fire point
• The fire point of a fuel is the lowest
temperature at which the vapour of that fuel
will continue to burn for at least five seconds
if ignited by an outside ignition source.
• At the flash point, a lower temperature, a
substance will ignite briefly, but vapor might
not be produced at a rate to sustain the fire.
• In general the fire point can be assumed to be
about 10 °C higher than the flash point.
Auto Ignition
• The minimum temperature at which a fluid
will spontaneously ignite without an external
ignition source, such as a flame or spark.
• Never operate a system above a fluid’s auto
ignition temperature.
Comparison:

Property Flash Point Fire Point Auto Ignition Temp.

Ignition Source Required? Yes (open flame) Yes (open flame) No
Sustained Combustion? No Yes Yes
Smoke point
• This is an important test for evaluation of illuminating oils (kerosines) for their
ability to bum without producing smoke and the assessment of the burning quality
of aviation fuels. Higher the smoke point better is its domestic use. It also serves as
a guide to assess the aromatic content of kerosines.
• Smoke point is the maximum flame height in mm at which the fuel will burn
without smoking when determined in a smoke point apparatus under specified
conditions.
• One of the standard tests is ASTM D1322.

Significance:
• Indicator of Fuel Quality: Higher smoke point indicates cleaner combustion and
higher quality fuel.
• Relevance in Aviation: Critical in jet fuels to ensure clean burning in engines,
reducing the risk of soot deposition in turbines.
• Relation to Aromatics: Fuels with lower aromatic content generally have a
higher smoke point, as aromatics tend to produce more smoke during
combustion.
Aniline point
• The lowest temperature at which an equal volume mixture of the petroleum oil and aniline are
miscible is the aniline point.
• High aniline point indicates that the fuel is highly paraffinic and hence has a high diesel index
and very good ignition quality. In case of aromatics the aniline point is low and the ignition
quality is poor.
• This property is important for the specifications of diesel fuels. It is measured by ASTM
D611.
Significance:
• Indicator of Aromatic Content: Fuels with low aniline points contain higher concentrations of
aromatics, which tend to dissolve more easily in aniline.
• Fuel Quality: Higher aniline point generally indicates a lower aromatic content, signifying a
higher quality fuel with better combustion properties and less soot formation.
• Relevance in Refining: Helps in evaluating the knock resistance of fuels; higher aniline points
often correlate with better performance in engines due to fewer aromatic hydrocarbons.
Practical Implications:
• Fuels with high aromatic content (low aniline point) may cause increased engine wear, higher
emissions, and poorer combustion efficiency.
• Important in lubricant formulations: Higher aniline points in lubricants indicate lower aromatic
content, contributing to better oxidative stability and less deposit formation.
Carbon residue
• Carbon residue is a measure of the coke-forming tendencies of oil.
• It is determined by destructive distillation in the absence of air of the sample to a coke
residue. The coke residue is expressed as the weight percentage of the original sample.
Significance:
• Indicator of Fuel Quality: Higher carbon residue suggests a greater tendency of the fuel to form
deposits (such as carbon deposits in engine components) during combustion.
• Relevance in Refining: Carbon residue testing helps determine the fuel's propensity to form coke in
refining processes, especially in cracking units and catalytic reformers.
• Fuel Performance: Fuels with high carbon residue may cause engine fouling, piston ring sticking,
and excessive soot formation, reducing overall engine efficiency and increasing maintenance costs.
Testing Methods:
• Conradson Carbon Residue (CCR): A standard test method where the fuel is heated in a controlled
environment and the remaining solid residue is weighed.
• Ramsbottom Carbon Residue (RCR): Similar to CCR, this method applies different conditions of
heating, often used for heavier petroleum products.
Practical Implications:
• Low carbon residue fuels: Preferred for use in high-performance engines and gas turbines to
minimize deposit formation.
• High carbon residue fuels: Often used in marine engines and industrial boilers, but require more
frequent maintenance and cleaning due to deposit build-up.
Kinematic viscosity
• Kinematic Viscosity is a measure of a fluid's internal resistance to flow.
• The resistance to flow or the pumpability of the crude oil or petroleum fraction is
indicated by the viscosity.
• More viscous oils create a greater pressure drop when they flow in pipes.
• Viscosity measurement is expressed in terms of kinematic viscosity in centiStocks
(cSt) and can also be expressed in saybolt seconds.
• The viscosity is measured at 37.8 ⁰C (100 ⁰ F) by ASTM D445 and by ASTM D446
at 99 ⁰C (210 ⁰ F).

Applications:
• Lubrication Systems: High kinematic viscosity lubricants provide thicker oil films,
ensuring better protection but higher energy consumption.
• Fuel Systems: Lower viscosity fuels improve flow and atomization but may reduce
lubrication in fuel injectors.
Pour point
• The Pour Point is the lowest temperature at which a liquid, typically a petroleum-based oil,
ceases to flow under standard testing conditions. It represents the point where the oil
becomes too viscous or semi-solid to be pumped.
• It also indicates the aromaticity or the paraffinity of the crude oil or the fraction.
• A lower pour point means that the paraffin content is low.
• Pour points for the whole crude and fractions boiling above 232 ⁰C (450 F) are determined
by standard tests like ASTM D97.
Significance:
• Cold Flow Properties: Pour point is a critical indicator of a fuel’s low-temperature
performance, especially for diesel fuels, lubricating oils, and other petroleum products.
• Operational Implications: Fuels with high pour points may cause blockages in pipelines, fuel
lines, and engines during cold weather, leading to equipment failure or increased
maintenance costs.
• Used in Lubricant Selection: Helps in selecting appropriate lubricants for machines operating
in cold environments. Lower pour point lubricants ensure proper flow and protection in low-
temperature conditions.
Applications:
• Diesel Fuels: Low pour point fuels are preferred for cold climates to avoid gelling or
solidification.
• Lubricants: Pour point affects the performance of lubricants in automotive engines,
gearboxes, and hydraulic systems in cold weather.
Freezing point
• Heavy oils contain heavy compounds such as waxes or
asphaltenes.
• These compounds tend to solidify at low temperatures,
thus restricting flow.
• The freezing point is the temperature at which the
hydrocarbon liquid solidifies at atmospheric pressure.
• It is one of the important property specifications for
kerosene and jet fuels due to the very low temperatures
encountered at high altitudes in jet planes.
• One of the standard tests is ASTM D4790 and ASTM
D16.
Octane number
• This is an important test for measuring the antiknock quality of the gasoline (petrol
or motor spirit).
• The ability of a fuel to resist auto-ignition during compression and prior to the
spark ignition gives it a high octane number.
• The octane number of a fuel is determined by measuring its knocking value
compared to the knocking of a mixture of n-heptane and isooctane (2,2,4- trimethyl
pentane).
• Pure n-heptane is assigned a value of zero octane while isooctane is assigned 100
octane. Hence, an 80 vol% isooctane mixture has an octane number of 80.
• Two octane tests can be performed for gasoline. The motor octane number (MON)
indicates engine performance at highway conditions with high speeds (900 rpm).
On the other hand, the research octane number (RON) is indicative of low-speed
city driving (600 rpm). The posted octane number (PON) is the arithmetic average
of MON and RON. One of the standard tests is ASTM D2700.
• If the fuel meets the minimum requirements in respect of octane number it ensures
trouble free operation. Apart from being a nuisance, the knocking in an engine may
result in loss of energy and at times may cause severe damage to the engine.
Cetane number
• Cetane number is related to the ignition delay of a fuel in a diesel engine, i.e. how
rapidly combustion begins after injection of the fuel into the combustion chamber.
• The cetane number is the percentage of pure cetane (n-hexadecane) in a blend of
cetane and alpha methyl naphthalene which matches the ignition quality of a diesel
fuel sample.
• The cetane number measures the ability for auto ignition and is essentially the
opposite of the octane number. One of the standard tests is ASTM D976.
• The long chain, saturated, unbranched hydrocarbons have high cetane numbers,
while structural features such as branching or unsaturation lead to lower cetane
numbers.
• High cetane number fuels will facilitate easy starting of compression ignition
engines, particularly in cold weathers, and faster warm up.
• These also result in increased engine efficiency and power output, reduced exhaust
smoke and odour and combustion noise.
Viscosity index
• The rate of change of viscosity with temperature is expressed by the viscosity index of the oil.
• The higher the VI, the smaller its change in viscosity for a given change in temperature.
• The VIs of natural oils range from negative values for oils from naphthenic crudes to about
100 for paraffinic crudes.
• Specially processed oils and chemical additives can have VIs of 130 and higher. Additives,
such as polyisobutylenes and polymethacrylic acid ester, are frequently mixed with lube
blending stocks to improve the viscosity–temperature properties of the finished oils.
• Motor oils must be thin enough at low temperature to permit easy starting and viscous enough
at engine operating temperatures [180 to 250°F (80 to 120°C)] to reduce friction and wear by
providing a continuous liquid film between metal surfaces.
• The VI of an oil can be calculated from the equation
Diesel index
• A measure of the ignition quality of a diesel fuel. Diesel index is defined as

• The higher the diesel index, the more satisfactory the ignition quality of the fuel.
• DI serves as a substitute for Cetane Number when direct measurement is not available.
Relevance:
• Diesel Index vs. Cetane Number: While the Cetane Number directly measures ignition delay,
the Diesel Index is a more convenient and quicker method for assessing fuel quality in
refineries and testing labs, especially for routine checks.
Applications:
• Evaluates diesel fuel suitability for various engine types, particularly in high-performance and
heavy-duty diesel engines.
• Helps refineries optimize blends to meet quality standards and comply with regulations.
Limitations:
• DI is less accurate for fuels with high aromatic content since it does not account for the
hydrocarbon composition.
Calorific value
• Calorific value is a measure of the energy available in a fuel.
• This is the quantity of heat released per unit quantity of fuel, when it
is burned completely with oxygen and the products of combustion
returned to ambient temperature. It is expressed in units such as
kJ/kg
• The calorific value of hydrocarbons is a critical factor in assessing
fuel performance, and it varies significantly based on the molecular
structure and hydrogen-to-carbon ratio.
• Calorific Value Trends in Hydrocarbons:
– Methane (CH₄): ~55.5 MJ/kg
– Ethane (C₂H₆): ~51.9 MJ/kg
– Propane (C₃H₈): ~50.3 MJ/kg
– Butane (C₄H₁₀): ~49.5 MJ/kg
(Decrease in calorific value with increasing molecular weight due to
lower H ratio)
Burning test 24 hours
• The ability of kerosene to burn steadily and cleanly over an extended period is
an important property and gives some indication of the purity or composition
of the product.
• The 24-h burning test (ASTM D-187) involves noting the average oil consumption,
change in flame dimensions, and final appearance of wick and chimney.
• No quantitative determination of char value is made (IP-10).
• In this method the oil is burned for 24 h in the standard lamp with a flame initially
adjusted to specified dimensions. The details of operation are carefully specified
and involve the test room conditions, volume of sample, wick nature, pretreatment
of wick and glass chimney, method of wick trimming, and procedure for removal of
the char.
• At the conclusion of the test, the oil consumption and the amount of char formed on
the wick are determined and the char value is calculated as milligrams per kilogram
of oil consumed.
• A qualitative assessment of the appearance of the glass chimney is also made.
Characterization factor
• There are several correlations between yield and the aromaticity and paraffinicity of crude
oils, but the two most widely used are the UOP or Watson “characterization factor” (KW) and
the U.S. Bureau of Mines correlation index (CI).

• where TB = mean average boiling point, °R

• G = specific gravity at 60°F
• The Watson characterization factor ranges from less than 10 for highly aromatic materials to
almost 15 for highly paraffinic compounds.
• Crude oils show a narrower range of KW and vary from 10.5 for a highly naphthenic crude to
12.9 for a paraffinic base crude.
• The correlation index is useful in evaluating individual fractions from crude oils.
• The CI scale is based upon straight-chain paraffins having a CI value of 0 and benzene having
a CI value of 100.
• The CI values are not quantitative, but the lower the CI value, the greater the concentrations
of paraffin hydrocarbons in the fraction; and the higher the CI value, the greater the
concentrations of naphthenes and aromatics. It an indicator of the aromaticity of the oil.
Cloud Point
• Cloud point reports the temperature at which wax or other solid materials begin to separate
from petroleum products.
• For paraffinic oils, this is the starting temperature of crystallization of paraffin waxes.
• Cloud point gives a rough idea of the temperature above which the oil can be safely handled
without any fear of congealing or filter clogging.
Significance:
– Critical for Cold Weather Operations: Cloud Point is a key parameter for fuels used in cold
climates, as wax crystal formation can clog fuel filters and hinder flow in engines and storage tanks.
– Standard Measurement: ASTM D2500 is the standard test method for determining the Cloud Point
of petroleum products, particularly diesel fuels and biodiesel blends.
Factors Influencing Cloud Point:
• Hydrocarbon Composition:
– Paraffinic Content: Fuels with higher paraffinic content tend to have higher Cloud
Points due to the crystallization of paraffins.
• Fuel Blending:
– Biodiesel blends tend to have higher Cloud Points than conventional diesel due to their
chemical structure (higher saturation levels).
Vapour lock index
• A measure of the tendency of a gasoline to generate excessive vapors in the fuel line, thus
causing displacement of a liquid fuel and subsequent interruption of normal engine operation.
VLI=RVP+(7×T10)
– RVP (Reid Vapour Pressure): Indicates fuel volatility, measured in psi or kPa.
– T10: The temperature (in °C) at which 10% of the fuel has evaporated during distillation.
Factors Affecting Vapour Lock:
• Fuel Volatility:
– Fuels with higher volatility (high RVP) vaporize more easily, increasing the risk of vapour lock.
• Ambient Conditions:
– High temperatures and low air pressure (as in mountainous areas) enhance the potential for fuel to
vaporize.
Importance of VLI in Fuel Design:
• Seasonal Formulation: Refineries adjust the VLI of gasoline seasonally to balance cold-start
performance in winter (higher volatility) and vapour lock resistance in summer (lower
volatility).
• Fuel Blending: The VLI helps engineers blend gasoline to avoid vapour lock while
maintaining good engine performance across different climatic conditions.
• Reid vapor pressure (RVP) The vapor pressure at 100°F of a product determined in a
volume of air four times the liquid volume. Reid vapor pressure is an indication of the ease of
starting and vapor-lock tendency of a motor gasoline as well as explosion and evaporation
hazards; ASTM D-323. It is usually expressed in kPa or psig.
Carbon hydrogen ratio
• The ratio, either on a weight or on a molecular basis, of carbon-to-
hydrogen in a hydrocarbon material.
• Thus, if a given sample contains 80% carbon and 5% hydrogen, the
C/H ratio would be 80:5, or 16.
• Bituminous coals have a C/H ratio between 14 and 17, and most
anthracites have a ratio between 24 and 29.
• Materials with a high carbon/hydrogen ratio (e.g., coal) are solid.
• The ratio is useful as a preliminary indication of the hydrogen
quantity needed to convert the hydrocarbon to a gas and/or liquid
(AGA).
• The C/H results can be used to estimate the processing and refining
potentials and yields in the petrochemical industry.
• It is found that the hydrocarbon fuel with a higher C/H has a lower
net heating value
Calculated Ignition Index
• The Calculated Ignition Index (CII) is an index of the ignition quality of residual
fuel oil.
• The running of all internal combustion engines is dependent on the ignition quality
of the fuel. For spark-ignition engines the fuel has an octane rating. For diesel
engines the cetane numbers are used.
• Cetane numbers are tested using a special test engine and the existing engine was
not made for residual fuels.
• For residual fuel oil two empirical indexes are used CII and Calculated Carbon
Aromaticity Index (CCAI). Both CII and CCAI are calculated from the density and
kinematic viscosity of the fuel.

• Where:
D = density at 15°C (kg/m3)
V = viscosity (cST)
T = viscosity temperature (°C)
• Use: CII was designed to give out numbers in the same order as the cetane index
for residual fuel oil.
Calculated carbon aromaticity index
• The calculated carbon aromaticity index is an index of the ignition
quality of residual fuel oil.
• CCAI is the ratio of the fuel which indicates ignition quality because
ignition directly depends on the Aromatic Content in the fuel.

• Where:
D= density at 15°C (kg/m3)
V= viscosity (cST)
t = viscosity temperature (°C)
• This will normally give a value somewhere between 800 and 880.
The lower the value is the better the ignition quality.
• Fuels with a CCAI higher than 880 are often problematic or even
unusable in a diesel engine. CCAI are often calculated under testing
of marine fuel.
Water and sediment content
• When extracted from an oil reservoir, the crude oil will contain some amount of water and
suspended solids from the reservoir formation.
• The water content can vary greatly from field to field, and may be present in large quantities
for older fields, or if oil extraction is enhanced using water injection technology.
• The accurate analysis of a crude oil sample to determine the water content is important in the
refining, purchase, sale and transfer of crude oils as contracts are based on net dry oil, in
other words, no one wants to be paying crude oil prices for barrels of water.
• The water and sediment content of crude oil can cause corrosion of equipment and problems
in processing.
• Oil refineries may either buy crude to a certain Basic sediment and water (BS&W)
specification or may alternatively have initial crude oil dehydration and desalting process
units that reduce the BS&W to acceptable limits, or a combination thereof.
• ASTM method D4007 or API Manual of Petroleum Measurement Standards chapter 10.4 are
commonly used to measure BS&W.
• These methods consist of mixing equal volumes of solvent and crude oil then centrifuging in
order to separate any solids, free water, or suspended particles.
• More precise methods beyond BS&W are available to independently measure water or solids
present in a sample of crude oil.
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