Automotive engineering

Marek Kułażyński
Green fuels
BIOFUELS

Standards
 Biodiesel Standard EN 14214
Limits
Property Test method Unit
min max

Ester content EN 14103 96.5 %, m/m

EN ISO3675;
Density; 15oC 860 900 kg/m3
ENISO12185
EN ISO 3104;
Viscosity; 40°C 3.5 5 mm2/s
ISO 3105

Flash point EN ISO 3679 120 oC

EN ISO20346;
Sulphur content 10 Mg/kg
EN ISO 20384
Carbon residue
EN ISO 10370 0.30 %, m/m
(10% dist. residue)
Cetane number EN ISO 5165 51

Sulfated ash ISO 3937 0.02 %, m/m

 Biodiesel Standard EN 14214
Limits
Property Test method Unit
min max

Water content EN ISO 12937 500 Mg/kg

Total contamination EN 12662 24 Mg/kg

Copper strip corrosion

EN ISO 2160 1
(3 hr,50oC)
Oxidative stability,110°C EN 14112 6.0 hr

Acid value EN 14104 0.50 mgKOH/g

lodine value EN 14111 120 g I2/100 ml

Linolenic acid content EN 14103 12 %, m/m

Content of FAME with 4

EN 14112 1 %, m/m
double bonds
 Biodiesel Standard EN 14214
Limits
Property Test method Unit
min max

Methanol oontent EN 14110 0.20 %, m/m

Monoglyceride content EN 14105 0.80 %, m/m

Diglyceride content EN 14105 0.20 %, m/m

Triglyceride content EN 14105 0.20 %, m/m

Free glycerine EN 14105, EN 14106 0.02 %, m/m

Total glycerine EN 14105 0.25 %, m/m

Alkali metals (Na+K) EN 14103, EN 14109 5.0 mg/kg

Earth alkali metals (Ca+Mg) EN 14538 5.0 mg/kg

Phosphorus content EN 14107 10.0 mg/kg

 Basic physicochemical properties of most common oils.
Density at Lower heating Kinematic
Melting point Flash point
Oil 15oC value viscosity at 20oC Cetane number Iodine number
[oC] [oC]
[kg/dm3] [MJ/kg] [mm2/s]

Diesel O,84 42,7 4,6 50 - 80 -

Rapeseed 0,92 37,6 74 49 0..-3 317 94..113

Sunflower 0,93 37,1 66 35,5 -16..-18 316 118..144

Soybean 0,93 37,1 63,5 38,5 -8..-18 350 114..138

Linsed (flax) 0,93 37,0 51,0 (52) -18..-27 169..192

Olive 0,92 37,8 83,8 37,1 -5..-9 76..90

Cotton 0,93 36,8 89,4 4`1 -6..-14 320 90..117

Peanuts 0,91 37,2 71,0 (51) 340 (103)

Palm oil 0,87 35,3 21,7 (1) 14..25 7..10

Palm grease 0,92 37,0 29,4 (1) 42 27..43 267 34..61

Palm kernel 35,5 21,5 (1) 20..24 14..22

 Biodiesel Standards
EU Austria Germany USA
Standard
Specification - ON C1191 DIN E 51606 ASTM PS121-99

Water (mg/kg) - < 0,8 < 300 < 500

Methanol (% w/w) - < 0,3

Ester content
- - - -
(% w/w)

Standard /
EN 14214 ON C1191 DIN V 51606 ASTM D-6751
Specification
Density at
0.86 -0.90 0.85 - 0.89 0.875 - 0.90 -
15°C g/cm3
Viscosity at. 40°C mm2/s 3.5-5.0 3.5-5.0 3.5-5.0 1.9-6.0
Distillation 95% °C - - - 90% at 360°C
Ignition Temperature >120 >100 >110 >130 (150 av.)
CFPP °C (cold filter plugging differs in each
0/-15 0/-10/-20 -
point) country
 Biodiesel Standards
Czech
Standard Austria France Germany Italy Sweden USA
Republic
ON CSN 65 Journal DIN E UNI SS ASTM
Specification C1191 6507 Official 51606 10635 155436 PS121-99

Water (mg/kg) < 0,8 < 500 < 200 < 300 < 700 < 300 < 500
Acid value
(mg KOH/g)
< 0,20 < 0,5 < 0,5 < 0,5 < 0,5 < 0,5 < 0,8

Methanol
(% w/w)
- - < 0,1 < 0,3 < 0,2 < 0,2 -

Ester content
(% w/w)
- - > 96,5 - > 98 > 98 -

Monoglycerides
(% w/w)
- - < 0,8 < 0,8 < 0,8 < 0,8 -

Diglycerides
(% w/w)
- - < 0,2 < 0,4 < 0,2 < 0,1 -

Triglycerides
(% w/w)
- - < 0,2 < 0,4 < 0,1 < 0,1 -
 Biodiesel Standards
EN 14214 ASTM D6751
PROPERTIES
LIMIT LIMIT

Aspect NE (Absent on the specification) NE

Density at 20ºC NE NE
Kinematical Viscosity at 40°C, 3,5 - 5,0 1,9 - 6,0
Water, max. 500 mg/kg 500 mg/kg
Total Contamination 24 NE
Flash Point, min. 120 130
Ester Content 96,5 NE
Distillation; 90% vol. recovered, max. NE 360
Carbon Residue of 100% distillated NE max. 0,05
Ashes, max. 0,02 0,02
Total Sulfur 10 mg/kg 15 mg/kg
Na + K, max 5 NE
Ca + Mg 5 NE
Phosphorus (3) 10 10
 ASTM D 6751-02
Property Method Limits Units
Flash point, closed cup D 93 130 min °C
Water and sediment D 2709 0.050 max % volume
Kinematic viscosity, 40 ° C D 445 1.9 – 6.0 mm2/s
Sulfated ash D 874 0.020 max wt. %
Total Sulfur D 5453 0.05 max wt. %

Copper strip corrosion D 130 No. 3 max

Cetane number D 613 47 min
Cloud point D 2500 Report to customer °C
Carbon residue D 4530 0.050 max wt. %
Acid number D 664 0.80 max mg KOH/g
Free glycerin D 6584 0.020 wt. %
Total glycerin D 6584 0.240 wt. %
Phosphorus D 4951 0.0010 wt. %
Vacuum distillation end point D 1160 360 °C max, at T-90 % distilled
 ASTM D6751
Standard Specification for Biodiesel Fuel Blendstock (B100) for
Middle Distillate Fuels
Property Test Method Specification

Flash Point, Closed Cup ASTM D93 130°C min

Water and Sediment ASTM D2709 0.050 Vol. % Max
Kinematic Viscosity, 40°C ASTM D445 1.9-6.0 mm2/s
Sulfated Ash ASTM D874 0.020 Mass % Max
Sulfur ASTM D5453 0.0015 Mass %, Max
Copper Strip Corrosion ASTM D130 No. 3 Max
Cetane Number ASTM D613 47 Min
Cloud Point, °C ASTM D2500 Report
Carbon Residue ASTM D4530 0.050 Mass %, Max
Acid Number ASTM D664 0.80 mg KOH/g Max
Free Glycerin ASTM D6584 0.020 Mass %, Max
Total Glycerin ASTM D6584 0.240 Mass %, Max
Phosphorous Content ASTM 4951 0.001 Mass %, Max
Distillation Temperature ASTM D1160 360 °C Max
Atmospheric Equivalent Temperature
90% Recovered
 Properties of commercial diesel vs biodiesel

Characteristics Diesel Biodiesel

Specific gravity at 15 oC 0.82 0.88

Heating Value MJ/kg 43.0 41.8

Cetane Number 40-55 48 - 60

Flash Point, oC 60 – 80 100 - 170

Stochiometric Air / Fuel Ratio 15 13.8

 View of molecule methylester and cetane

CH3-O-CO-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3

Methylester

CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3

n-heksadekan (Cetane)
 List of C1–C4 alcohols and their relevant properties.
Molecular Boiling point Melting point Density
Formula
weight [oC] [oC] [kg/dm3]

Methanol CH3OH 32.042 65 -93.9 0.7914

Ethanol C2H5OH 46.069 78.5 -117.3 0.7893

1-propanol CH2OHCH2CH3 60.096 97.4 -126.5 0.8035

2-propanol (iso-
CH3CHOHCH3 60.096 82.4 -89.5 0.7855
propanol)

1-butanol (n-
CH3CH2CH2CH2OH 74.123 117.2 -89.5 0.8098
butanol)

2-butanol CH3CHOHCH2CH3 74.123 99.5 - 0.8080

3-methyl-1-propanol
CH2OHCH(CH3)CH3 74.123 108 - 0.8018
(iso-propanol)

3-methyl-2-propanol
CH2(CH3)CHOHCH3 74.123 82.3 25.5 0.7887
(tert-butanol)
 Diesel Fuel Specification - Specific Gravity
The specific gravity is a relative measure
of the density of a substance.
It is defined as the ratio of the density
of the substance, ρ, to a reference density, ρref. The
equation for the specific gravity (SG) is SG = ρ/ρref.
The most common reference density used in the
measurement of specific gravity is the density of water at
4°C, which corresponds to a reference density of 1
g/cm3.
The specific gravity of conventional diesel fuel is about
0.85 while a typical density of biodiesel is 0.88, which
means that biodiesel is more dense than conventional
diesel fuel.

Hydrometer for measuring

specific gravity.
 Biodiesel Blends - Density
0.93

0.92

0.91

0.9
Density 20oC/4oC

(1)Castor - (2)Cotton
(1)Soya - (2)Castor
(1)Rapeseed - (2)Castor
0.89
(1)Soya - (2)Rapeseed
Lower Limit EN 14214
Upper Limit EN 14214
0.88

0.87

0.86

0.85
0 10 20 30 40 50 60 70 80 90 100
(1)/(2), %
 Fuel Specification - Flash Point

A key property determining the flammability of a fuel is the

flash point.

The flash point is the lowest temperature at which an

applied ignition source will cause the vapours of a sample
to ignite.

The flash need not correspond to a sustained flame.

The "fire point" is sometimes used to designate the fuel
temperature that will produce sufficient vapor to maintain a
continuous flame.
 Fuel Specification - Flash point
The flash point is the lowest temperature at which a
combustible mixture can be formed above the liquid fuel.
It is dependent on both the lean flammability limit of the
fuel as well as the vapor pressure of the fuel constituents.
The flash point is determined by heating a sample of the
fuel in a stirred container and passing a flame over the
surface of the liquid. If the temperature is at or above the
flash point, the vapor will ignite and an easily detectable
flash can be observed. Diesel fuel is required to have a flash
point above 52°C. Some special applications, such as marine
fuels, may require higher flash points.
Biodiesel’s flash point is usually well above 150°C.
High flash point 260ºF vs. 125ºF for diesel safest fuel to use, handle, store
Test cup for ASTM D 93 ASTM D 93 Pensky-Martens
Flashpoint Test Flashpoint Apparatus
ASTM D 93 Pensky-Martens
Flashpoint Apparatus
Fuel Specification - Flash point
 ASTM D93 Standard Test Method for Flash Point
by Pensky-Martens Closed Cup Tester

• Performed to define and guarantee the product rating of

“non-hazardous”, or non-flammable

– Flash point of Methanol, <100 deg C

– Flash point of Biodiesel, >130 deg C min

• Indicates residual alcohol, methanol, left in final product

• Methanol residue can cause degradation of elastomers and seals within

engine

• Important to monitor at the production level

 Fuel Specification - Water and Sediment

This method used to measure water and sediment is only

sensitive to free water.
It uses a centrifuge to separate small water droplets and
particles to be sure they do not exceed 0.05% (500 ppm).

This test is particularly important when working with

biodiesel because biodiesel is usually water-washed to
remove traces of soap and free glycerol.

Vacuum drying is usually needed to remove residual water

following the washing process.
Fuel Specification - Water and Sediment
 ASTM D2709
Standard Test Method for Water & Sediment
in Middle Distillate Fuels by Centrifuge

• Indicator of the cleanliness of the fuel

– 0.050 Volume % Max

• Water and Sediment are both contaminant in the fuel

– Water reacts with the esters to produce Free Fatty Acids (back reaction)

– Water Supports microbial Growth

– Sediment plugs fuel filters

• Both may be sourced from feedstock, treatment during process or storage

conditions
 Fuel Specification - Distillation Curve
The distillation curve is determined by relating the fraction of a fuel
sample that is removing by heating a fuel sample to progressively higher
temperatures.
Typically, the curve is characterized by the initial point,
the temperature at which the first drop of liquid leaves the condenser,
the temperatures at each 10% of the liquid, and the end point.
Since diesel fuel consists of hundreds of different compounds,
a distillation curve provides important information about the
composition of the fuel. However, biodiesel usually only contains 4 to 5
major compounds that all boil at about the same temperature.

In addition, the boiling temperature is so high at

atmospheric pressure that the biodiesel compounds
usually decompose (crack) during the distillation test.
 Distillation Temperature
A property related to the flash point is the boiling point,
which is the temperature at which a liquid transitions to a
gas. For a pure substance the boiling point is a single
temperature value. However, for a mixture of hydrocarbons
as exists in diesel fuel there is a range of boiling points for
the different constituent chemical species.

The distillation test is used to determine the boiling range

characteristics of a hydrocarbon sample.

As one would expect, the distillation characteristics, i.e.,

the boiling point range, have an important effect on the
performance, storage, and safety of fuels.
 Distillation Temperature
Distillation limits are commonly included in petroleum
product specifications due to the number of chemicals
species that can be present. To run the test, a simple batch
distillation process is conducted on a sample of the fuel and
boiling point data are collected.
These data include the initial boiling point, the final boiling
point, and the boiling temperature corresponding to
increments of the volume of fuel distilled (5%, 10%, 20%,
etc.).
The boiling temperatures of the compounds in biodiesel are
so high at atmospheric pressure that the compounds may
decompose (crack) during the distillation test.
Fuel Specification - Distillation Curve
 ASTM D1160
Standard Test Method for Distillation of
Petroleum Products at Reduced Pressure

• Indicator of adulterants in the final product

– 360°C, 90% recovered Max

• Distillation curve of biodiesel is unique, saturated hydrocarbons

effect the curve type

• Not a production level quality control parameter

 ASTM D4530
Standard Test Method for Determination of Carbon Residue (Micro Method)

– Indicator of the carbon depositing tendencies of the fuel

• 0.050 Mass % Max

– Performed on the 100% fraction due to the distillation characteristics of

the fuel
• (ie. Difficult to get the 10% bottoms for analysis)
 Fuel Specification - Kinematic Viscosity

Viscosity is a measure of a fluid’s resistance to flow.

The greater the viscosity, the less readily the liquid flows.
The viscosity of petroleum oils is a strong function of
temperature with the viscosity decreasing as the
temperature increases.
Biodiesel is more viscous than diesel fuel but only by a
small amount. Depending on feedstock and amount of
oxidation, biodiesel viscosity will vary between 4.0 and
6.2, while diesel fuels tend to fall in the a narrower range
of 2.4 to 2.6.
 Biodiesel Blends - Viscosity
16

14

12
Viscosity @ 40oC, mm2/s

10
(1)castor - (2)Cotton
(1)Soya - (2)Castor
8 (1)Rapeseed - (2)Castor
Lower Limit EN 14214
Upper Limit EN 14214
6

0
0 10 20 30 40 50 60 70 80 90 100
(1)/(2), %
 Fuel Specification - Kinematic Viscosity
Simply stated, viscosity, which is also called dynamic viscosity (η), is the
ease with which a fluid will flow. We intuitively understand viscosity as
evidenced by the fact that we know, for example, honey is more viscous
than water. There is a hydrodynamic definition of viscosity as well.

Technically it is the ratio of the shear stress to the shear rate for a fluid.

In contrast, the kinematic viscosity (ν) is the resistance to flow of a fluid

under gravity.
The kinematic viscosity of a fluid (ν) is related to the dynamic
viscosity (η) through the density (ρ),
ν = η /ρ.
 Fuel Specification - Kinematic Viscosity
The summary of the test method as presented in the standard is “The
time is measured for a fixed volume of liquid to flow under gravity
through the capillary of a calibrated viscometer under a reproducible
driving head and at a closely controlled and known temperature.”
The test is usually conducted by measuring the time required for a
volume of liquid to flow under gravity through a calibrated glass capillary
tube.
The kinematic viscosity is then equal to the product of this time and a
calibration constant for the tube.
Biodiesel is more viscous than diesel fuel, but only by a small amount.
Depending on feedstock and the amount of oxidation, biodiesel’s
viscosity will vary between 4.0 and 6.2, while diesel fuels tend to fall in
the a narrower range of 2.4 to 2.6.
Fuel Specification - Kinematic Viscosity

A Cannon-Fenske style glass capillary tube

that is commonly used for ASTM D 445.

Biodiesel is more viscous than diesel fuel, but

only by a small amount.

Depending on feedstock and the amount of

oxidation, biodiesel’s viscosity will vary between
4.0 and 6.2, while diesel fuels tend to fall in the a
narrower range of 2.4 to 2.6.
Fuel Specification - Kinematic Viscosity
 ASTM D445
Standard Test Method for Kinematic Viscosity of Transparent or Opaque Liquids
• Viscosity of the fuel is considered when design engine
specifications, flow and lubricating properties
• Specification Established with a Min/Max Range 1.9-6.0
mm2/s
• Viscosity of Biodiesel considered due to its use as a blend
component for the diesel product
• Blendstock should not change overall diesel properties
• Biodiesel specifications designed to allow for optimal
blending without compromising overall flow properties
• Injector performance can be compromised if viscosity is
compromised
 Fuel Specification - Cetane Number
Perhaps the most important measure of ignition characteristics of diesel and/or
biodiesel fuels is the cetane number, since it directly pertains to ignition within
compression ignition engines.
The analog of cetane number in gasoline is the octane number.
It is based on a special engine produced by Waukesha Engine Company
that is similar to the Octane Test Engine used for rating gasoline.
The cetane number relates to the readiness of the fuel to self-
ignite when exposed to the high temperatures and pressure in the
diesel engine combustion chamber.
It is not directly related to the energy content of the fuel. On-highway
diesel fuels in the U.S. are required to have cetane numbers of 40 or
higher. Most will be in the range of 40 to 45.
In Europe, cetane numbers are higher and tend to be in the 50-55
range.
 Fuel Specification - Cetane Number
The engine is a single cylinder, indirect injection diesel
engine. The engine speed is fixed at 900 rpm and while the
engine is naturally aspirated, the intake air temperature is
held at 150°F.
The test is based on a careful adjustment of the fuel/air
ratio and the compression ratio to produce a standard
ignition delay (the period between the start of fuel
injection and the start of combustion) of 13 degrees while
operating on the test fuel.
Then the engine is switched to operate on a blend of two
reference fuels.
Different blends are tested until a formulation is found
that restores the ignition delay to 13 degrees.
 Fuel Specification - Cetane Number
The primary reference fuels are n-cetane (n-hexadecane), which has a
cetane number of 100 and heptamethylnonane (HMN), which has a
cetane number of 15. When the ignition delay is restored to 13
degrees, the cetane number is computed from the following
relationship:
Cetane Number = % n-cetane + 0.15 (%HMN)
It is important to note that if a 50/50 blend is made of fuels with
cetane numbers of 40 and 50, respectively, the blended fuel will likely
not have a cetane number of 45. This phenomenon is due to the fact
that the cetane number of a blend is not directly proportional to the
cetane numbers of its constituents.

The cetane number of biodiesel is typically higher than standard

diesel fuel and its addition to a standard diesel fuel will generally
increase the cetane number of the subsequent blended fuel.
Fuel Specification - Cetane Number
 Fuel Specification - Cetane Index
The cetane index is a calculated quantity that is intended to
approximate the cetane number.
It is much cheaper to determine than the engine-based cetane number
but its accuracy is limited to the type of fuel on which the equation is
based.
It generally does not provide an accurate indication of cetane number if
the fuel contains cetane improving additives or for non-petroleum-based
alternative fuels.
ASTM standard D 976 gives the following empirical equation for the
cetane index:

Cetane Index = 454.74 - 1641.416 D + 774.74 D2 - 0.554 T50 + 97.803[log10(T50)]2

Where:
D = fuel density at 15°C in g/ml.
T50 = the temperature corresponding to the 50% point
on the distillation curve in degrees C.
 ASTM D613
Standard Test Method for
Cetane Number in Diesel Fuel

Indicator of the ignition characteristics of the fuel in compression ignition

engines, influences smoke and combustion roughness
Specification, 47 min
Feedstock ultimately determines the cetane number obtained in the final
product

Performed on full scale cetane engine, Cetane Index Calculated is not

applicable to biodiesel product

Not a production level analysis, cost for engine extremely high

Low-temperature properties

> CP
CFPP
CP Cristal layer:
3 mm
PP
 Low-temperature properties

• CP: Cloud Point

• CFPP: Cold Filter Plugging Point
• SFPP: Simulated Filter Plugging Point
• PP: Pour Point
Equippment:
• ISL- apparatus (CP, CFPP, PP)
• NORMALAB-device (SFPP)
 Fuel Specification - Cloud point

A fuel property that is particularly important for the low temperature

operability of diesel fuel is the cloud point.
The cloud point is the temperature at which a cloud of
wax crystals first appears in a liquid upon cooling.
Therefore, it is an index of the lowest temperature of the fuel’s utility
under certain applications. Operating at temperatures below the cloud
point for a diesel fuel can result in fuel filter clogging due to the wax
crystals. The cloud point is determined by visually inspecting for a haze
in the normally clear fuel, while the fuel is cooled under carefully
controlled conditions. The cloud point is an important property for
biodiesel.Biodiesel fuels typically have higher cloud points,
i.e., crystals begin to form at higher temperature, than standard diesel
fuel. This feature has implications on the use of biodiesel in cold weather
applications.
Cloud Point Apparatus
 Fuel Specification - Cloud Point
The cloud point is the temperature at which a cloud
of wax crystals first appears in a fuel sample that is
cooled under conditions described by ASTM D 2500.
Fuel Specification - Cloud Point
 ASTM D2500
Standard Test Method for
Cloud Point in Petroleum Products

• Indicator of temperature in which cloud or haze of crystals appears under

prescribed conditions, crystal precipitation
– No current specification in place for D2500

• Producers should measure this property internally although there is no

specification for the product

• Consideration to use in cold climates, ie. Northeast

• Controlled by blending of feedstocks

 Fuel Specification - Pour Point
A second measure of the low temperature performance of diesel/biodiesel
fuels is the pour point.
The pour point is the lowest temperature at which
a fuel sample will flow.
Therefore, the pour point provides an index of the lowest temperature of
the fuel’s utility for certain applications. The pour point also has
implications for the handling of fuels during cold temperatures.
The standard procedure for measuring the pour point of fuels is
ASTM D 97.
A summary of the procedure steps is:
1) the sample is cooled at a specified rate,
2) the sample is examined at 3°C intervals for flow, and
3) the lowest temperature at which sample movement is observed is noted.
Ekodiesel treated with R442 depressant

CP: Cloud Point

CFPP: Cold
Filter Plugging
Point

SFPP:
Simulated Filter
Plugging Point

PP: Pour Point

BIODIESEL B20 blend+ R442 additive

CP: Cloud
Point

CFPP: Cold
Filter Plugging
Point

SFPP:
Simulated
Filter Plugging
Point

PP: Pour Point

Sedimentation test

Temp: -17 oC
Time: 64 h
 After winterization

CP, CFPP determination

Δ CP = CP (before test) – CP (lower layer after test)

ΔCFP = CFPP (before test) – CFPP (lower layer after test)
 Fuel Specification - Copper Strip Corrosion
Many of the compounds in diesel fuel can be corrosive.
The corrosiveness of a fuel is measured using the copper
strip corrosion test, which is ASTM D 130.
Copper and copper compounds tend to be particularly
susceptible to chemical attack.
The corrosivity of a fuel has implications on storage and
use of the fuel.
As an indicator of the tendency of a fuel to cause corrosion,
polished copper strips are placed in the fuel for 3 hours
at 50°C.
Then the strips are washed in a solvent and compared to the
descriptions of Copper Strip Classifications.
 Fuel Specification - Copper Strip Corrosion
The test results are given as a number followed by a letter. For example, a strip
that was slightly tarnished with a dark orange colour would be designated as “1b.”
Classification Designation Description

a. Light orange, almost the same as freshly polished strip

1 Slight Tarnish
b. Dark orange
a. Claret red
b. Lavender
c. Multicolored with lavender blue or silver, or both,
2 Moderate Tarnish
overlaid on claret red
d. Silvery
e. Brassy or gold
a. Magenta overcast on brassy strip
3 Dark Tarnish b. Multicolored with red and green showing (peacock),
but no gray

a. Transparent black, dark gray or brown with peacock green

barely showing
4 Corrosion
b. Graphite or lusterless black
c. Glossy or jet black
Fuel Specification - Copper Strip Corrosion
 ASTM D130
Standard Test Method for the Determination of
Copper Corrosion by Copper Strip Tarnish Test

Indicator of the relative corrosively of the product

No. 3 Max Specification (rating on a 1-4, a-c scale)

Also indicator of presence of acids or free fatty acids derived from

unreacted materials in the production process

Total Sulfur (ASTM D5453) is not always indicator of the sulfur species
effecting the corrosively of other sulfur species
Fuel Specification - Fuel Stability Measurement

Figure shows part of the apparatus used

for ASTM D 2274. Oxygen is bubbled
through the fuel for 16 hours while the
fuel is held at 95°C. Then, the fuel is
filtered to measure the amount of any
insoluble's that are formed.
 Fuel Specification - Lubricity
Lubricity is actually a very difficult property to characterize. In spite of the
definition's attempt to separate the lubricity as a fluid property, it is also
strongly dependent on the method used to measure it and on the characteristics
of the solid surfaces being lubricated. For example, as friction occurs, small
particles of the solid material may be removed and entrained in the lubricant. In
some applications, these particles will be swept away by a flow of lubricant
while in others, the particles stay in the vicinity of the surface contact. Particles
that are present in the area of surface contact may act very differently. In some
cases, they may act as an abrasive to increase wear while in other cases, the
particles may shield the surface from further wear. When trying to characterize
lubricity, it is important to use a measurement technique that correlates well
with the actual lubrication situation. In the case of diesel fuel, the fuel acts
as a lubricant for the finely fitting parts in the diesel fuel injection system.
While all diesel fuel injection systems depend on the fuel to act as a
lubricant, rotary pump style injection systems seem to be the most sensitive
to fuel lubricity.
 Fuel Specification – Lubricity test

Scuffing Load Ball On Cylinder High Frequency Reciprocating Rig

Lubricity Evaluator (SLBOCLE - (HFRR - ASTM D 6079-99)
ASTM D 6078-99)
 Lubricity test

The same effect for diesel fuel that has also

Results for diesel fuel with small amounts been treated to lower the sulfur contain to
of biodiesel. 1% biodiesel could change less than 15 ppm. In this case, the lubricity
the diesel fuel (15 ppm sulphur) from an of the original diesel fuel was so low that
unacceptable level to an acceptable even 2% biodiesel was not able to bring the
level. lubricity back up to the acceptable level of
3150 grams.
 Biodiesel Performance

High lubricity

2% biodiesel improves fuel lubricity by up to 66%

protects, extends engine life
 Materials

Neat diesel oils: Neat biodiesel (FAME):

• ON Ekodiesel • RME, rapeseed oil
• ON Citydiesel (Rrafineria Trzebinia
S.A.)
(PKN Orlen)
• SME, soybean oil
(AGH)
Neat diesel oils: Neat biodiesel (FAME):
• ON Ekodiesel • RME, rapeseed oil
• ON Citydiesel (Rrafineria Trzebinia S.A.)
(PKN Orlen) • SME, soybean oil
Wear scar diameter WS 1,4 (µm)

Ekodiesel Citydiesel SME RME PN-EN 590

554 617 184 201 max. 460

 Properties of the Ekodiesel and the Citydiesel
Prpperty Unit Results
Ekodiesel Citydiesel
Cetane number — 50,0 55,1
Density (15 ºC) kg/m3 840,1 811,0
Sulfur mg/kg 26 8
PAH % (m/m) 1,9 1,6
Flash point ºC 82 61
Viscosity (40 ºC) mm2/s 3,048 2,099
Oxidation stability g/m3 5,2 5,2
Corrosiveness (Cu) 1a 1a
Water mg/kg 48 21
Distillation:
up to 250 ºC recovered % (V/V) 30,0 52,0
up to 350 ºC recovered % (V/V) 100 100
95 % (V/V) recovered oC 338,0 281,0
Cloud point (CP) oC -7 -29
Cold filter plugging point (CFPP)
HFRR lubricity ( WS1,4) oC -10 -35
µm 555 617
 Aparatus (High Frequency Reciprocating Rig HFRR, PCS
Instruments) Polish test method PN-EN 12156-2001
Load Ball – 6 mm

oscilation oscilation

Test ball Test plate sample

diameters of the wear scar

WS1,4 [µm] – diameter of wear scar corrected.

(diameter of wear scar corrected for normal pressure of water vapour
equal1,4 kPa)
Impact of the soybean ester (SME) content on the HRFF
lubricity of the Ecodiesel and Citydiesel fuels.
Impact of the soybean methyl ester (SME) content (a) and the rapeseed methyl ester
content (b) on the relative lubricity of the Ekodiesel and Citydiesel diesel fuels.

Ekodiesel Citydiesel Ekodiesel Citydiesel

70 5960 6060 70 57 56 56
52 49 51

Relative lubricity, SWP (%)

Relative lubricity, SWP (%)

50 50
31 3237
30 30 30 19
7
10 10

-10 -10
-7 -5
-14 -12 -11
-30 -21 -21 -30 -21 -22
-28
-34 -36 -30 -34 -30 -34
-50 -50
0,0 0,1 0,2 0,5 1,0 5,0 20,0 100 0,0 0,1 0,2 0,5 1,0 5,0 20,0 100
a SM E content (wt %) b RM E content (wt %)

SME is better lubricity enhancer: O,5% of SME – WS1,4 lower then limit
of 460 micrometers
Ekodiesel is more sensitive
 Fatty acids profile of the soybean (SME) and the rapeseed (RME)
methyl esters.
Methyl ester content [wt %]
Fatty acid methyl ester
SME RME
C16:0 (methyl palmitate) 11,1 4,0
C16:1 (methyl palmitoleate) < 0,1 0,4
C18:0 (methyl stearate) 4,5 1,5
C18:1 (meyhyl oleate) 24,3 60,1
C18:2 (methyl linoleate) 51,9 18,4
C18:3 (methyl linolenate) 7,1 10,3
C20:0 (methyl arachdate) 0,3 0,8
C20:1 (methyl eicosenoate) 0,1 2,6
C20:2, C20:3 and C20:4 < 0,1 0,3
C22:0 (metyl behenate) 0,3 0,2
C22:1 (metyl erucate) < 0,1 1,5
C24:0 (mehtyl lignocerate) 0,3 < 0,1
C24:1 (methyl nervonate) 0,1 < 0,1

More of influence the esters C18 i C20 with few duble bonds.
1. The methyl esters (SME, RME) derived from vegetable oils in
compositions with low-sulphur diesel fuels have a beneficial
effect on fuel lubricating ability, which manifests itself in a
decrease of the corrected wear scar of the testedball in the
HFFR test.

2. The soybean ester turned out to be a better lubricity enhancer

for petroleum diesel fuels than the rapeseed ester; a smaller
concentrations of the SME ester in the blends with base diesel
fuels resulted in an increase of the lubrication ability.

3. Characterized by higher sulphur content and better lubricity,

the Ekodiesel was more susceptible to changes in the
lubricating ability due to ester additives than the Citydiesel.
 Fuel Specification - Ash

Ash consists of the residue left when the fuel is heated to a

sufficiently high temperature that combustible material
burns and leaves as CO2 and H2O.

It primarily consists of inorganic compounds and their

oxides. These materials can be abrasive and contribute to
engine wear.

Diesel fuels are generally very low in ash and ASTM D 975
allows no more than 0.01%, by weight.
Fuel Specification - Ash
Fuel Specification - Ash
 ASTM D874
Standard Test Method for Sulfated Ash
from Lubricating Oils and Additives

Indicator of mineral ash residue left over after fuel

is burned 0.020 Mass % Max

Indicates residual metals from catalyst, spent Na or K salts

Importance is dependent on type of product

 Fuel Specification - Sulphur
Before 1993, diesel fuel was allowed to contain up to 0.5%
(5000 ppm) sulphur.
This level is still acceptable for off-highway fuels, but after
1993, on-highway fuels were required to contain less than
0.05% (500 ppm) sulphur.

In 2006, the sulphur specification for on-highway fuels will be

lowered to 15 ppm.
This is an extremely low level of sulphur and will be difficult
to measure.
The current method, D 2622, will need to be changed to a
new method when the sulfur level drops.
Fuel Specification - Sulphur
Fuel Specification - Sulphur
 ASTM D5453
Standard Test Method for Determination of Sulfur Content by UV Fluorescence
Indicator of contamination by protein material of feedstock or
carryover from the catalyst material
0.0015 Mass % Max, or 15 ppm
Sulfur should be measured in feedstock-virgin oil versus the
rendered product
Critical as Diesel Specifications will change in 2006 to Ultra Low
Sulfur (500 ppm versus new 15 ppm as delivered)

Biodiesel should not be a contributor to the overall sulfur of the

final blended product

Biodiesel adds lubricity properties lost by reduction in sulfur in

diesel product
 Biodiesel Blends – Iodine Number
140

130

120

110
Iodine Number

(1)Soya - (2)Castor
(1)Cotton - (2)Soya
100
(1)Soya - (2)Rapeseed
Max Limit EN 14214

90

80

70

60
0 10 20 30 40 50 60 70 80 90 100
(1)/(2), %
 ASTM D6584
“Free and Total Glycerin in B100 by Gas Chromatography”
– Free and Total Glycerin Specification and Definition

0.020 Mass % Max Free Glycerin

0.240 Mass % Max Total Glycerin
Total Glycerin-the sum of Free and Bonded Glycerin
Free Glycerin-unbound, incomplete esterification products
Bonded Glycerin-includes mono, di and triglycerides

– Why is this property important?

Due to the nature of the glycerides in the final product

Can cause operability problems at low temperatures
Saturates monoglycerides cause filter clogging
Should be part of production level quality control
 Important parameters RME

B100 may adversely affect some elastomers such as

natural or nitrile rubbers over time.

Most elastomers used after 1993 are compatible with B100

(Viton, etc.)

Biodiesel (B100) is a solvent.

 Important parameters RME
● Calorific Value
– amount of energy in the fuel measured in kJ/kg
(with B100 reduced by -13%)

● Flash Point
– measure of a fuel's flammability.
– with biodiesel 130°C
● Lubricity
– is defined as the ability of a lubricant to reduce friction
and wearing.
– Addition of 1-2% Biodiesel can vastly improve the
lubricating properties of diesel fuels.
 Important parameters RME

● Cetane number
– tendency to ignite
– similar or higher compared to fossil diesel ~52

● Sulphur
– Biodiesel contains much less Sulphur (3ppm)
● Oxygen
– Unlike Petroleum Diesel, Biodiesel molecules contain
oxygen atoms on their hydrocarbon chains.
– oxygen atoms allow to combust more completely
● Carbon residue
– much lower (<0.02%)
 Important parameters RME

● CFPP
– higher viscosity creates problems in filters at low
temperatures
– Cold filter plugging point for RME -10 - -14°C
– CFPP lower than the cloud point, mostly equal to the pour
point (higher compared to the pour point with RME with additives)
● Additives
– Pour point depressant improving viscosity at low
temperatures (only during winter)
– Biodiesel stabilizer /Enzyme based biodiesel additive may
lengthen the storage possibility
– Defoamer helps if foam is build in the presence of water
 Improvements

● Particle trap
– may be used additionally, even with B100
– alternative solution preferred to regenerate the filter
(avoid late injection of biodiesel because of motor oil
dilution)

● SCR
– selective catalytic reduction using ammonia or urea helps
to achieve EURO V
– higher urea-water dosage may be necessary to reach the
same NOx level
 Product Qualities Important to Biodiesel
Outside of the ASTM D6751 Specification
• Lubricity- ASTM D6079, provides indicator of the lubricating
properties of the fuel
• Biodiesel Content in Blended Middle Distillation
• EN 14078-European Standard Method
– Applies to blends from 1.7-25 Volume %
– IR Method
• Methanol Content EN 14110 GC-FID
• Linoleic and Linolenic Methyl Esters
• Oxidation Stability
• Storage Stability-D4245
 ASTM D4951
Standard Test Method for Determination of
Additive Elements in Lubricating Oils by ICP-AES

• Feedstock Driven Property, not typically a problem in the US biodiesel

production industry
– 0.240 Mass % Max

• Phosphorous can damage catalytic converters used in emission control

systems. Cat Converters becoming more common on diesel-powered
equipment

• Not a production level quality control parameter

 ASTM D664
Standard Test Method for Acid Number
by Potentiometric Titration
• Direct measurement of the FFA’s, free fatty acids, processing acids or
degradation by-products in the final product

– 0.80 mg KOH/g Max

– FFA’s are unreacted materials

• High Acid characteristics may cause corrosion, fuel system deposit or filter
plugging problems

• May be a symptom of water in the fuel product

Thank You!