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Petroleum Products - Gas Chromatography
Petroleum Products - Gas Chromatography
PETROLEUM PRODUCTS
Figure 1 Chromatogram of a commercial gasoline following the NF N07-086 standard. Operating conditions: column,
50 m;0.20 mm i.d.; stationary phase 0.5 m OV1; oven, 353C for 10 min, then 1.13C min\1 up to 1143C, and 1.73C min\1 to 2503C,
held 5 min; detector, 2803C; carrier gas, helium at a constant flow of 0.8 mL min\1.
30 years, the methods have been standardized only In reRning, the two main processes, reforming and
relatively recently (ASTM D5134-90, NF07-086). catalytic cracking, require increasingly detailed in-
The chromatogram of a commercial gasoline, ob- formation regarding the gasoline range fraction. The
tained as speciRed in the French standard NF M07- complete detailed analysis data for the naphtha feed
086, is shown in Figure 1. By using a procedure and efSuents from the reforming units make follow-
standardizing a number of parameters and speciRca- ing and modelling the conversion and optimization of
tions, capillary chromatographic methods with tem- the control of the units possible. A major application
perature programming are reproducible from one Reld for automated capillary chromatography is in
chromatographic system to another and identiRcation the use of micro-pilot plants involving small amounts
of complex chromatograms can be automated. This of feeds and efSuents. The methods developed for the
automation has led to the development of numerous catalytic cracking micro-pilot plants allow detailed
applications in the petroleum Reld. The large amounts analysis of the gasoline cut and determination of
of data supplied by the detailed analysis are normalized, octane numbers directly on the total efSuent (Rnal
after processing, to determine the physical properties boiling point 5803C) by using a pre-column to elimin-
(molecular weight, gross caloriRc value, octane number, ate the heavier compounds.
etc.), to optimize the thermodynamic or kinetic models, Commercial gasolines are formulated using around
and to predict the quality of the conversion products. 10 petroleum basestocks. New environmental con-
3680 III / PETROLEUM PRODUCTS / Gas Chromatography
straints mean that the resulting mixtures require more separates parafRns and naphthenes, while a 5A mo-
rigorous optimization. With all the constraints con- lecular sieve column separates normal parafRns and
cerning benzene, other aromatics and oleRns, isoparafRns. The unsaturated components are re-
together with the additional octane number require- tained in an oleRn trap, released by heating the trap
ments brought about by the progressive elimination and then hydrogenated. These separations allow de-
of lead from fuels, there is an increasing demand for termination of the distribution by hydrocarbon type
the detailed characterization of basestocks and mix- and carbon number.
tures. Analyses are now carried out on a regular basis
in control laboratories.
One of the main causes of errors in modelling the
Heavy Hydrocarbon Liquid Analysis
behaviour of Suids in petroleum reservoirs has been The high resolution of capillary columns, which pro-
the lack of reliable analytical data. Using a thermo- vides separation of a major fraction of the hydro-
dynamic model based on an equation of state for carbons with boiling points up to 2003C, is not
calculating the properties of these Suids requires ac- sufRcient for the heavier petroleum cuts owing to
curate knowledge of the molecular weights and their their increasing complexity. Although detailed in-
distribution. The large amount of information pro- formation is not directly available, GC is nevertheless
vided by the detailed and direct analysis of the frac- very extensively used. The chromatogram can serve
tion up to C20 with the molecular weight distribution as a qualitative plot for determining the presence of
has modiRed the methodology of describing reservoir speciRc compounds or classes of compounds. Quan-
Suids. tiRcation of normal parafRns in crude petroleum
Characterization of the C3}C15 fraction of oils and (compounds that are clearly distinguished from
extracts from source rocks is an important parameter the unresolved material) and waxes can be made.
for studying the origin and migration of hydrocar- However, the most important applications concern
bons. Until recently only a proRle or Rngerprint was the characterization and quantiRcation of the frac-
available, but now this fraction can be quantiRed by tions in hydrocarbon types, obtained, in particular,
automated capillary methods. Various parameters by liquid chromatography (LC). In most cases, the
(parafRn, aromatic numbers, etc.) have been obtained compounds are identiRed by mass spectrometry (see
from the detailed analysis to follow variations in below). The development of online coupling of high
chemical composition and show biodegradation or performance liquid chromatography (HPLC) and GC
leaching phenomena. Soil pollution by hydrocarbons, has led to several petroleum applications: measure-
particularly fuels, requires pollutant monitoring. The ment of aromatics in gas oils, and measurement of
replacement of global methods, like solvent extrac- polyaromatics in diesel engine exhausts and mineral
tion, by detailed analysis of the fuel, can provide oils.
a better follow-up of the decontamination operations.
Figure 1 shows a chromatogram of commercial gaso-
line following the NF N07-086 standard.
GC/MS Coupling
Mass spectrometry (MS) coupled with GC (GC-MS)
Hydrocarbon Type Analysis of Light
is now the main identiRcation technique. From bench
Hydrocarbons
equipment (increasingly numerous) to more sophisti-
Hydrocarbon type analysis (ParafRns/IsoparafRns/ cated systems providing high resolution measure-
Aromatics/Naphthenes/OleRns (PIANO)) can be ob- ments, the identiRcation is facilitated by computer
tained from detailed analysis with a data system that processing of libraries containing thousands of mass
identiRes each of the peaks and combines them into spectra. This technique has made an essential contri-
their respective groups. Because there are some co- bution to analysis of hydrocarbons, in particular for
elutions, this analysis may not be accurate with gaso- the detailed analysis of fuels and their bases, geo-
lines containing signiRcant amounts of oleRnic and chemical studies and pollution problems. Up to
naphthenic constituents eluted before n-octane. around 1000 compounds have been identiRed in
Some methods of type analysis have been de- oils. For two decades numerous data for different
veloped with the multidimensional GC technique; columns, retention times or indices of hydro-
these are commonly referred to as PIANO analysis. carbons identiRed by GC-MS have been published for
A four-column system with automatic valve switch- compounds in gasolines and kerosenes. For the me-
ing and cold traps has been utilized to determine dium distillates, where direct detailed analysis is not
normal parafRns, isoparafRns, naphthenes, oleRns possible, the distribution per carbon number of the
and aromatics. A polar column separates aromatics MS analysis can be obtained by combining the separ-
and non-aromatics, a 13X molecular sieve column ation by boiling point and carbon number from GC
III / PETROLEUM PRODUCTS / Gas Chromatography 3681
Sulfur
The most widely used detector for many years has
been the Same photometric detector (FPD). In spite of
its limitations (non-linearity, variable response, Figure 2 Chromatogram of sulfur compounds from a catalytic
quenching), methods have been standardized for the cracking gas oil (LCO) before and after hydroprocessing obtained
light petroleum cuts. The recent development of with a chemiluminescent detector. Operating conditions: column,
a more sensitive chemiluminescence detector for sul- 30 m;0.32 mm i.d.; stationary phase 4 m SPB-1; oven, 603C to
fur without these limitations has allowed extension of 3203C at 53C min\1. DBT, dibenzothiophene; C1, methyl; C2,
dimethyl or ethyl; C3#, three or more branched carbons.
the application Reld to heavier cuts, such as gas oils
and crude oils. The chromatograms of sulfur com-
pounds from a catalytically cracked gas oil before and
after hydroprocessing obtained with this detector are Halogens
shown in Figure 2. Comparison of the two chromato-
grams shows the changes in the sulfur compounds The electron-capture (ECD) and electrochemical
during the hydroprocessing. detectors are used to determine the halogens. The
ECD is very sensitive when the molecule is poly-
halogenated; sulfur hexaSuoride, used as a tracer,
Nitrogen
can be directly detected at the p.p.b. level. The main
The situation is identical to that of sulfur, the nitro- applications concern chloroSuorocarbon gases,
gen}phosphorus detector (NPD) also having limita- chlorinated solvents and polychlorinated biphenyls
tions (variable response, relatively low selectivity). (PCBs).
The arrival of a chemiluminescence detector for nitro-
gen has provided access to semi-quantitative analysis Multielement Detectors
of nitrogen compounds in gasoline and gas oil cuts
While all the speciRc detectors mentioned above can
from conversion processes.
detect only one element at a time, the atomic emission
detector is multielement, with some restrictions con-
Oxygen
cerning the number of elements that can be detected
The development of a detector speciRc to oxygen per analysis and the sensitivity to some of these
(O-FID) has met the need for the measurement of elements. This is a powerful identiRcation tool
oxygenated compounds such as methyl t-butyl ether (complementary to MS). The main applications are
in commercial gasolines. Several methods have been measurement of oxygen compounds in gasolines,
standardized (EN 1601-96, ASTM D5599-93). Due multielement simulated distillation (H, C, S), and the
to its low sample capacity, this detector cannot be determination of nickel and vanadium in crude
used for measuring traces of oxygen. oils.
3682 III / PETROLEUM PRODUCTS / Gas Chromatography
Figure 3 Chromatogram of a light crude oil with a final boiling point of 6503C. Operating conditions: column, 10 m, deactivated metal;
stationary phase 0.5 m OV1; oven, 353C for 1 min, then 103C min\1 up to 3903C, held 14 min; detector, 4003C; carrier gas, helium at
a constant flow of 10 mL min\1.
III / PETROLEUM PRODUCTS / Liquid Chromatography 3683
a powerful tool for the detailed analysis of hydro- Di Sanzo F and Chawla B (1992) Journal of Chromatogra-
carbons. phy 271: 589.
Dressler M (1986) Selective Gas Chromatography De-
See also: I / Chromatography. II / Chromatography: tectors. Amsterdam: Elsevier.
Gas: Column Technology; Detectors: General (Flame Ion- Durand JP, BeH boulène JJ and Ducrozet A (1995) Analysis
ization Detectors and Thermal Conductivity Detectors; De- 23: 481.
tectors; Mass Spectrometry; Historical Development; Grob K (1991) On-line Coupled LC-GC. Heidelberg:
Multidimensional Gas Chromatography; Theory of Gas HuK thig Buch Verlag.
Chromatography. Grob RL (ed.) (1995) Modern Practice of Gas Chromato-
graphy. New York: Wiley.
Korth J, Ellis J, Crisp PT and Hutton AC (1998) Fuel 67:
Further Reading 1331.
Adlard ER (ed.) (1995) Chromatography in the Petroleum Lin R and Wilk ZA (1995) Fuel 74: 1512}1521.
Industry. Amsterdam: Elsevier. Quimby BD and Sullivan JJ (1990) Analytical Chemistry
Benner RL and Stedman DH (1989) Analytical Chemistry 62: 1027.
61: 1268.
Liquid Chromatography
V. L. Cebolla, L. Membrado and J. Vela, preparative isolation of hydrocarbon types; in addi-
Instituto de CarboqumH mica, Consejo Superior de tion to molecular size distribution and average mo-
Investigaciones CientmH ficas (CSIC), Zaragoza, Spain lecular weight determination.
Copyright ^ 2000 Academic Press
In general, complete molecular separation of the
components of petroleum distillates is not possible
using liquid chromatography owing to their complex
Introduction nature and the limited resolution of current tech-
Techniques based on liquid chromatography are used niques. As the boiling range of the product to be
in the petroleum industry for process monitoring, analysed increases, the greater its complexity due to
compliance with environmental regulations, the the increase in the number of isomers and the broader
evaluation of product quality, catalyst performance variety of compound types present. Furthermore, the
and feed processability, as well as for determining concentration of polar compounds (e.g. heterocyclic
hazardous compounds, and understanding and solv- compounds) increases as the products become
ing basic research problems. heavier. Therefore, the heavier the product, the poorer
Chromatographic techniques and methods used for the chromatographic resolution obtained, and the more
analysing petroleum products are chosen depending difRcult it is to achieve good separations. In most cases,
on their boiling point range, which is related to their extensive separations are meaningless in the petroleum
carbon number. In order to simplify the further dis- industry, but determination of particular target com-
cussion, classiRcation of petroleum products into pounds in various distillates is sometimes useful.
light, middle and heavy distillates is considered Determination of hydrocarbon types (which in-
throughout this work. cludes separation and quantiRcation) of all types of
Techniques based on capillary gas chromatography distillates is usually carried out by liquid chromato-
(GC) can perform molecular characterization of some graphy. Hydrocarbon types in petroleum products
light distillates, such as gasolines and others. How- can be roughly summarized into saturates (n-paraf-
ever, this technique has limitations when it comes to Rns, branched parafRns, and cycloalkanes or naph-
analysing heavier distillates. As the complexity of thenes), oleRns (alkenes and cycloalkenes), aromatics
petroleum products rapidly increases with the in- (hydrocarbons containing one or more rings of the
creasing boiling range of distillates, liquid chromato- benzenoid structure), and polars (which include het-
graphic techniques play a crucial role in the analysis erocycles and/or high molecular weight material).
of middle and heavy distillates. They are also com- This simple scheme becomes more complicated with
plementary to GC for analysing light distillates. Most increasing sample boiling range because of the many
of the applications of liquid chromatography to pe- possible combinations of compound types (e.g. alkyl-
troleum products include separation, identiRcation aromatics, aromatic oleRns, etc.). Therefore, separ-
and, in some cases, quantiRcation of individual com- ation designs may vary depending on nature of the
ponents; separation, quantiRcation, and, sometimes, sample and information required by the analyst.