A P P L I C A T I O N
Biodiesel or FAME (Fatty Acid Methyl Ester):
Mid-Infrared Determination of Ester Concentration in Diesel Fuel
G. Patrick Ritz Ph.D. & Michael C. Croudace Ph.D.
When Rudolf Diesel designed his prototype diesel
engine nearly a century ago, he ran it on peanut oil.
He envisioned that diesel engines would operate
on a variety of vegetable oils. But when petroleum-
based diesel fuel hit the marketplace, it was cheap,
reasonably efficient, and readily available, and there-
fore quickly became the diesel fuel of choice. In the
mid 1970s, fuel shortages spurred interest in diver-
sifying our fuel resources, and thus prompted ac-
tion in development of biodiesel as an alternative
to petroleum diesel.
Now, increasing concerns about the potential of
global climate change is adding more impetus to
biodiesel’s development. Since biodiesel is made from
feedstocks that take carbon dioxide out of the atmo-
sphere, the use of this alternate fuel adds no net car-
bon dioxide to the atmosphere — an important step in
reducing the buildup of greenhouse gases.
Biodiesel is a renewable diesel fuel consisting of
fatty-acid alkyl esters, known in Europe as FAME
(fatty-acid methyl ester). Fatty-acid alkyl esters are
actually long chains of carbon molecules (12 to 22 car-
bons long) with an alcohol molecule attached to one
end of the chain. In a process called transesterification,
organically derived oils (vegetable oils, animal fats
and recycled restaurant greases) are combined with
alcohol (usually methanol) and chemically altered to
form fatty esters such as methyl ester. The biomass-
derived esters can be blended with conventional die-
sel fuel or used as a neat fuel (100% biodiesel).
Biodiesel made from animal fat or vegetable oil
works just like petroleum diesel, but with far lower
toxic air emissions. Pure biodiesel requires special
treatment in cold weather, but can otherwise be
used without modification in most newer trucks.
Typically, though, biodiesel is used as a fuel addi-
tive in 20% blends (B20) with petroleum diesel (al-
though other blend levels can be used depending on
the cost of the fuel and the desired benefits). Blends
such as B20 work very well in any diesel engine
and reduce pollution roughly proportionately with
the amount blended.
N O T E
US biodiesel use is growing rapidly, increasing
from about 7 million gallons in 2000 to more than 20
million gallons in 2001, with additional production
capacity available to quickly accommodate further
growth. US producers use mostly soy oil and recycled
cooking oils. Mixing biodiesel into the petroleum die-
sel supply can reduce our need to import or produce
more petroleum diesel fuel in the future.
Biodiesel, mostly B20, is used in federal, state,
and transit fleets, private truck companies, ferries,
tourist boats and launches, locomotives, power gen-
erators, home heating furnaces, and other equip-
ment. Regulated fleets are being rewarded for imple-
menting biodiesel use into their heavy-duty ve-
hicles. For every 450 gallons of biodiesel used in
any blend level per year, a provision under the En-
ergy Policy Act of 1992, as amended in 1998, credits
these fleets with one required alternative-fuel light-
duty vehicle. Furthermore, there is growing inter-
est in using biodiesel where workers and school
children are exposed to toxic diesel exhaust, in air-
craft to control local pollution near airports, and in
locomotives and power generators that face re-
stricted use unless emissions can be reduced.
QUANTIFYING THE AMOUNT OF ESTER IN A BLEND
A major challenge in introducing biodiesel blends to
the countries’ diesel pool is determining how to de-
pendably and simply quantify the amount of biodiesel
present. In the US, 2% biodiesel blends have been
found to actually contain anywhere between 0% and
8% biodiesel.
Distribution systems are presented with a second
challenge: determining the resulting Cetane Number
of diesel/biodiesel blend. Most customers currently
use cetane index (a mathematical model using distil-
lation and density as a correlation to cetane number)
rather than cetane number to evaluate their diesel
fuel’s combustion quality. However, biodiesel blends
dramatically change the distillation qualities of die-
sel, making the current cetane index equation unus-
able. The blender is forced to use cetane engines or a
correlative cetane method.
 In an effort to produce a tool that would allow Shell
to monitor diesel quality worldwide, Shell Research
approached PetroSpec with an idea for determining
cetane number through the detailed analysis of mid-
and near-infrared spectra. Shell Research provided
PetroSpec with a European calibration set in which
each of the diesel samples included a minimum of
three independent ratings. Many were rated 17 times.
The results were an average of these multi-ratings,
optimizing the accuracy or “trueness” of results. An
Ethyl Corporation calibration set was also produced,
including over 600 samples with varying amounts of
cetane improved from all over the United States.
This co-development project between BP, Shell
Research Laboratories and PetroSpec culminated in
a portable diesel fuel analyzer, the CETANE 2000,
which is fully automated for easy operation and
accurate results by both technical and non-techni-
cal personnel. PetroSpec built this product using the
rugged, industry tested, temperature-controlled plat-
form of their portable gasoline GS1000 instrument,
which has been trusted by the US EPA for field use
since 1995. The CETANE 2000 provides accurate,
fast, portable analysis and requires no sample prepa-
ration, no waste chemicals and no consumables. It
is the first analytical tool to combine analyses for
density, cetane number and cetane index plus cet-
ane improver, total aromatics, polynuclear aromatic
and biodiesel content in one portable instrument.
Each instrument comes pre-calibrated using fuels
from around the world. Furthermore, this robust
analytical technology not only brings the laboratory
into the field, but has also been successfully applied
for process/on-line use; custom calibration data (de-
veloped with the included user calibration software)
can be shared between portable and on-line units.
HOW DOES MID-IR DETECT THE BIODIESEL
In the Mid-IR spectral range (400–4000 cm-1) there
are two spectral positions that uniquely identify
biodiesel in diesel fuel: at 1745 cm-1 (C–O stretch, large
absorbance), and at 1160 cm-1 (C–O stretch, medium
absorbance), as shown below.
Biodiesel
Diesel
1745 cm -1 1160 cm -1
PAC • 3234 Pasadena Fwy • Pasadena, TX 77503 • p: (800) 444-TEST or (713) 590-7260 • f: (713) 590-7266 • sales@paclp.com • www.paclp.com
Absorbances in the mid-IR region for biodiesel are
unique and are thus separated from other component
absorbances in the fuel. The absorption of light is di-
rectly proportional to the quantity of biodiesel. Thus,
by using a gravimetrically produced calibration set of
biodiesel in diesel, the amount of biodiesel in the fuel
can be quantified. This spectroscopic separation al-
lows for the characterization and quantification of
biodiesel in much the same way as a physical separa-
tion that is produced via gas chromatograph.
CETANE 2000 — 1160 cm -1
35
4 R2 = 0.9999
30 3 SEC = 0.9
2
25
1
Gravim etric
20 0
0 1 2 3 4
15
10
5
0
0 5 10 15 20 25 30
Predicted
The accuracy of this method is outstanding. In the
range that the instrument above has been calibrated
(0–30% biodiesel) the standard error for the calibra-
tion is 0.09.
CONCLUSION
It is now easy for anyone to accurately analyze
biodiesel blends. Designed for laboratory or field
use, the CETANE 2000 quickly provides important
diesel fuel quality information wherever it is
needed. Refiners and regulators can monitor blend-
ing operations and measure final specifications
more efficiently. Marketers and distribution groups
are provided a cost-effective quality control tool for
monitoring diesel fuels as the fuels move through
the distribution system. This virtually eliminates
the sale of non-branded product throughout the dis-
tribution system and the liability of selling product
that is off-specification.