Diesel Fuel Hydrocarbon Composition

Distribution of PIONA in Gasoline Fuels

GCMS chromatogram of Gasoline sample

Gasoline Fuel

Intens.
9
x10

GC- MS Chromatogram Diesel Sample / KSA Sample

Diesel Fuel C10-C25

APCI_FTICR MS Diesel Sample / KSA Sample

341.305036

1.5

225.163775
193.049538

239.179425

1.0
301.288986
315.304640

167.033896
0.5

133.101180
391.284301
119.085526
427.378178

0.0
100

The

molecular

hydrocarbon

classes

Composition Profile
PIONA/DHA

within

gasoline are comprised of normal, iso-alkanes,

Diesel fuel is composed of

hundreds
of
hydrocarbons
(C10-C25) that varies among
saturated and
unsaturated
components. The array of
classes present in a diesel
sample
exhibit
unresolved
complex mixture in a gas
chromatograph. Here a Diesel
sample is measured using high
Resolution
FTICR
mass
spectrometry.

cycloalkanes and aromatics found in inexact

proportions. The abundance of such classes in
variable

amounts

can enhance

combustion

processes

20

Distribution of Hydrocarbon in Base oil

Sample

250

300

350

400

m/z

20
100

Class Distribution Data of Diesel Fuel

Distribution of Hydrocarbon in Diesel

DBE

15

80

60
10

40
5
20

HC

NO

S1

GC-MS

APCI

Intens.
x10 8

200

10

20

30

Carbon No.

Methods for Complex Fuel Analysis

Base Oil Chemistry

DBE

150

+is CID MS
+is CID MS

BaseOil G I SN100 and SN500

solariX
FTICR

6
66 3.4 53 638

15

Sheath liquid

5 13 .448 88 7

Nebulizer gas (N2)

APCI spray
needle

10

Corona discharge
needle

34 1.0 65 576

Heater (400C)
Spray shield

367 .04 485 1

Heated
drying gas (N2)

74 1.1 95 118
27 9.1 590 93
0

0
0

10

20

30

40

50

300

400

500

600

700

m/z

Carbon No.

Glass capillary
inner 0.5 mm
Capillary cap

Lubricant oils are

composed of 90%
refined base oils that
are composed of a
myriad of saturated
hydrocarbons along
with S containing
hydrocarbons.

The Carbon vs DBE plot

shows the distribution of
Class CH and S containing
compounds within a base oil
sample. Compounds of DBE
6-9
have
the
highest
abundance. Carbon range
spans from C14-C44.

The molecular compositions of various

base oils samples with different
viscosity were successfully unraveled
by the virtue of FTICR MS using APCI
as ionization source. The composition
of base oil SN100 and SN500
comprised mainly saturated and
unsaturated hydrocarbons.

Spray chamber

Waste

The analysis of Gasoline was performed by Agilent GC-MS using a PIONA for establishing the identity
and quantity of low boiling point hydrocarbons. However for Diesel and Base oil samples, atmospheric
pressure chemical ionization/fourier transform ion cyclotron resonance at Bruker Daltonics,
Bremen,Germany was used. Ionization of hydrocarbon was obtained in APCI using positive ion mode.
Protonated species were produced for the heavy hydrocarbons in the spectra.

References

Conclusion

Gasoline Chemistry was displayed using GC-MS.

The quantity of Parafins, Isoparaffins,Olefins, Naphthenes and
Aromatics were measured for a Gasoline Sample. The
composition of hydrocarbon in a Saudian Diesel sample

Carbon
number
range

exhibited a major unsaturated class of hydrocarbons with some

S containing species.
The composition of a base oil sample was for the first time
established by employing APCI/FTICR MS.

Ignition chemistry and

kinetics of engine

Molecular level information such as molecular formula and

oil surrogates, experimental

double bond equivalence (D.B.E) were acquired after the

data for validating chemical

measurement of the samples. Characterization of Base oils

kinetic models.

using advanced analytical chemistry tools will assist to study the

ignition chemistry and kinetics of engine lubricant oil surrogates,
and to provide experimental data for validating chemical kinetic
models.

SAS-CI 2013 3rd Annual Meeting , April 29, Dhahran, Saudi Aramco

1.Technical Note # TN-34, Rapid Analysis of Complex Mixtures Using the solariX-CM, FTMS Platform, Jens Fuchser,
Matthias Witt, Bruker Daltonik, Bremen Germany
2. Application Note # FTMS-44, Analysis of sulfur-rich crude oil and bitumen by FTMS, Dr. Matthias Witt, Bruker
Daltonik GmbH, Fahrenheitstr. 4, D-28359, Bremen, Germany
3. Application Note # FTMS-41, Analysis of Gas Oil by GC/APCI FTMS, Matthias Witt, Thomas Arthen-Engeland,
Bruker Daltonik GmbH.
4. Hourani, N., Kuhnert, N, Development of a novel direct-infusion atmospheric pressure chemical ionization mass
spectrometry method for the analysis of heavy hydrocarbons in light shredder waste, Anal. Methods, 2012, DOI:
10.1039/c2ay05249k
5. Hourani, N., Kuhnert, N, High molecular weight non-polar hydrocarbons as pure model substances and in motor oil
samples can be ionized without fragmentation by atmospheric pressure chemical ionization (APCI) mass spectrometry,
Rapid Commun. Mass Spectrom. 2012, 26, 23652371, DOI: 10.1002/rcm.6338.
Abbreviations:
APCI
Atmospheric pressure chemical ionization
DBE
Double bond equivalence
GC- MS
Gas chromatograpy mass spectrometry
FTICR MS Fourier Transform ion cyclotron resonance mass spectrometry
FW
Formula Weight
Achnowledgement:
Analytical Core Laboratory (ACL)-KAUST
Bruker Daltonics, Bremen, Germany

CLEAN COMBUSTION RESEARCH CENTER

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