Fuel 115 (2014) 190202

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Characterization of polar compounds in a true boiling point distillation

system using electrospray ionization FT-ICR mass spectrometry
Guilherme P. Dalmaschio a, Majorie M. Malacarne a, Vinicius M.D.L. de Almeida a, Thieres M.C. Pereira a,
Alexandre O. Gomes b, Eustaquio V.R. de Castro a, Sandro J. Greco a, Boniek G. Vaz c,,
Wanderson Romo a,d,
a

Department of Chemistry, Federal University of Esprito Santo, 29075-910 Vitria, ES, Brazil
Petrleo Brasileiro S/A PETROBRAS, CENPES, Rio de Janeiro, RJ, Brazil
Chemistry Institute, Federal University of Gois, 74001-970 Goinia, GO, Brazil
d
Federal Institute of Education, Science and Technology of Esprito Santo, 29106-010 Vila Velha, ES, Brazil
b
c

h i g h l i g h t s
 We describe the typication of polar compounds of twelve cuts obtained from a true boiling point system.
 We examine changes in the cuts composition by ESI() FT-ICR MS analysis.
 A correlation between the composition and TAN, total sulfur and the corrosion process was performed.
 The structures of some naphthenic acids, phenols and pyridines were conrmed using ESI()-MS/MS.

a r t i c l e

i n f o

Article history:
Received 4 May 2013
Received in revised form 28 June 2013
Accepted 1 July 2013
Available online 14 July 2013
Keywords:
Petroleomics
Distillation system
Mass spectrometry
FT-ICR MS
Methylation reactions

a b s t r a c t
In this work, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry
(ESI()-FT-ICR MS) was applied in the chemical characterization of polar compounds. These compounds
were identied as the oxygen-containing compound classes (naphthenic acids, O2 class, and phenols, O1
class), the sulfur-containing compound classes (mainly suldes, S1 class), and the basic and non-basic
nitrogen-containing compound classes (carbazoles and pyridines, N class). For access the sulfurcontaining compounds were employed the methylation reactions. As the increasing of distillation cut
temperature, the amount of O2 compounds increased (from 9 for cut 2 to 66 for cut 12), and the average
molecular weight distribution, Mw, shifted to higher m/z values (Mw = 169 ? 321 Da). These results were
consistent with the increase of TAN with the boiling point. Plots of the DBE versus the carbon number for
the O2 class of heavy distillation cuts (cuts 412) suggested a maximum abundance of the carbon numbers located at C12C18 with a constant DBE of 3. For the nitrogen-containing compounds, 100 compounds were detected with m/z ranging from 160 to 414. Similar to O2 class, the amount of nitrogen
species increased, and the Mw shifted for high values in function of distillation cut temperature: 6 species
and Mw = 206 Da for cut 3; and 64 species and Mw = 340 Da for cut 12. The structures and the connectivity
of naphthenic acids, phenols and pyridines were conrmed using ESI()-MS/MS. The most abundant sulfur compounds in heavy distillation cuts presented a carbon number of C23 (for cut 11) and C25 (for cut
12) with constant DBE of 3. Results of ESI()-FT-ICR MS contributed to the understanding of the chemical
composition of Brazilian crude oil and the establishment of a correlation with the corrosion process.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The chemical composition of crude oil consists predominantly
of hydrocarbon compounds such as naphthenes, parafns, and aro Corresponding authors. Tel.: +55 62 3521 1016xR261 (Boniek G. Vaz), tel.: +55
27 3149 0833 (W. Romo).
E-mail addresses: boniek@quimica.ufg.br (B.G. Vaz), wandersonromao@gmail.
com (W. Romo).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.07.008

matic hydrocarbons (90%). The remainder (10%) consists of polar compounds containing N, O, and S heteroatoms and metal
atoms (only vanadium and nickel exist at concentrations >1 ppm)
[1]. Despite the small percentage of polar compounds, approximately 20,000 polar organic compounds with different elemental
compositions (CcHhNnOoSs) have been found in crude oil [2]. These
polar compounds sometimes cause problems during the production, rening and storage of petroleum. These problems include
corrosion, the formation of emulsions, the poisoning of catalysts,

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

coke formation, the development of poisonous and carcinogenic

characteristics, and contamination. Oil consumption is continuously growing, which creates the demand to use the limited oil reservoirs and the heavier fractions more efciently. Therefore, it is
extremely important to know the composition of crude oils from
different origins to optimize the rening processes.
Among the polar components of petroleum that contain heteroatoms, naphthenic acids and phenols are the two most common
oxygen-containing compound classes in crude oil. There are other
minor acidic classes, such as aromatic, olenic, hydroxyl, and dibasic acids [3]. Naphthenic acids are dened as carboxylic acids that
include one or more saturated ring structures, with ve- and sixmembered rings being the most common. In addition to the ringcontaining acids, linear carboxylic acids are often included in the
naphthenic acid class [4]. Naphthenic acids are known to be a signicant source of corrosion in oil-rening equipment [5]. Corrosion
is associated with the total acid number (TAN), which is dened as
the mass of potassium hydroxide (KOH) in milligrams required to
neutralize 1 g of crude oil. However, it has been argued that there
is no clear correlation between the TAN and the level of corrosion
[6,7].
Recently, there has been growing interest in the chemical characterization of naphthenic acids and sulfur species from crude oils
and its distillation cuts because of the problems that these components have caused for the oil renery business [8]. These compounds induce corrosion in regions of the reneries that operate
at temperatures above 100.0 C. Sulfur compounds are the most
notorious and undesirable petroleum contaminants, and a large
portion of these compounds can be transferred to diesel oil during
rening process. In general, sulfur appears in the form of hydrogen
sulde, organic suldes and disuldes, benzothiophene, dibenzothiophene, and their alkylated derivatives [9]. Upon diesel combustion, sulfur compounds are converted to sulfur oxides (SOx), which
contribute to acid rain and environmental pollution [10]. Although
environmental regulation has been applied in many countries to
reduce the sulfur levels in diesel and other fuels, sulfur removal
still represents a major operational and economic challenge for
the petroleum rening industry.
Other well-known polar components in petroleum are the neutral and basic nitrogen species. The non-basic nitrogen compounds
usually include pyrrole, indole, carbazole, and their alkylated
derivatives, and these compounds correspond to less than 30% of
all organic nitrogen compounds [11]. The basic nitrogen compounds include amines, aniline, pyridine, quinoline, benzoquinoline, and their alkylated and hydrogenated derivatives. It is well
known that the presence of the nitrogen compounds in liquid
hydrocarbon streams, even at very low concentration, strongly
deactivates the catalysts that are used in the fuel-rening processes, such as hydrodesulfurization (HDS), hydrodearomatization
(HDA), hydrocracking, and reforming [12]. Therefore, the identication and quantication of the various nitrogen compounds and
the clarication of their distribution in different liquid hydrocarbon streams are essential to develop either a novel process [13],
more efcient catalysts or more efcient adsorbents for the denitrogenation of various liquid hydrocarbon streams and to understand the mechanism in ultradeep HDS, hydrodenitrogenation
(HDN), adsorptive denitrogenation (ADN), and extractive denitrogenation (EDN) [14].
Fourier transform ion cyclotron resonance mass spectrometry
(FT-ICR MS) offers the highest available mass resolution, mass
resolving power, and mass accuracy, which enable the analysis of
complex petroleum mixtures on a molecular level [15]. High-resolution MS data have shown that it is possible to discriminate different compounds [1618] because of the different ionization
efciencies of the crude oil constituents [19]. In this study, one Brazilian offshore acidic crude oil sample (TAN = 3.19 mg KOH g1)

191

was submitted to primary characterization using a homemade distillation process (where the boiling points changed from 100.4 to
372.9 C). Twelve cuts and distillation residues were produced
and characterized according to the density, TAN, total sulfur and
ESI()-FT-ICR MS analyzes. The ESI technique is not suitable to detect neutral aromatic compounds such as sulfur compounds. Thus,
the methylation reaction was introduced, and the sulde compounds were converted from the neutral species to methyl sulfonium salts, which can now be easily transferred into the gas
phase in the ESI source [20]. Herein, we apply this approach to
investigate the sulfur compound species in the heavy-boiling-point
cuts and the distillation residue.
2. Experiment
2.1. Reagents
Anhydrous propan-2-ol, toluene, potassium hydroxide (KOH,
analytical grades with purity higher than 99.5%), dichloromethane
(CH2Cl2), and silver nitrate (AgNO3) were used for the TAN measurements and the methylation reactions. These chemicals were
supplied by Vetec Qumica Fina Ltda, Brazil. Ammonium hydroxide
(NH4OH), sodium triuoroacetate (NaTFA), formic acid (HCOOH),
and methyl iodide (CH3I) were purchased from SigmaAldrich
Chemicals USA and used for the ESI()-FT-ICR MS measurements.
All reagents were used as received.
2.2. Petroleum characterization
A sample of offshore oil from Esprito Santo state (ES), Brazil,
were collected in 2011 and used in this work. The oil was characterized according to the standards of the American Society for Testing and Materials (ASTM) by Laboratory of Petroleum
Characterization of Federal University of Esprito Santo (LabPetro/
UFES-Brazil). A primary characterization was conducted to determine the density (ASTM D5002-99) [21], the API degree (ASTM
D1298-99) [22], the total acid number (ASTM D664-09) [23], the
kinematic viscosity (ASTM D7042-04) [24], and the total sulfur
(ASTM D4294) analyses [25]. Because the emulsied water and
sediment value was less than 1.0% v/v, it was not necessary to
dehydrate the crude oil sample. The data obtained from the characterization of crude oil are as follows: density = 0.9541 g cm3,
API degree = 16.2, TAN = 3.19 mg KOH g1, viscosity = 150.45 cSt,
at 40 C, and total sulfur = 0.60 wt% (these information are described in more detail in Table 1).
2.3. True boiling point distillation
A homemade distillation process was implemented in accordance with ASTM D 2892 (Standard Test Method for Distillation
of Crude Oil) [26] by LabPetro/UFES (Fig. 1). In general, the laboratorial distillation process (homemade) has the basic principle of
operation adopted by the Petroleum Renery Industry. The main
differences relate to loading the crude oil (the renery operates
in a continuum mode, whereas the laboratorial process has been
conducted in batches). In other words, the furnace is replaced by
a glass ask (Fig. 1). In addition, the differences are related to the
heating rate (in the laboratorial process, the heating rate is controlled by an electric mantle).
In the homemade distillation system, the process starts by submitting the dehydrate crude oil to a heating rate (from a distillation ask, see to scheme shown in Fig. 1). The light fraction is
vaporized and separated by a column fractionation that contains
approximately fourteen to eighteen theoretical plates. After liquefying the gases, the cuts of distillation (from gasoline to diesel) and

192

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

Table 1
Physicalchemical characterization of crude oil, its cuts and distillation residue.
Samples

Boiling point range (C)

Weight (wt%)

Density 20/40 C

Sulfur content (wt%)

TAN (mg KOH g1)

Cut 1
Cut 2
Cut 3
Cut 4
Cut 5
Cut 6
Cut 7
Cut 8
Cut 9
Cut 10
Cut 11
Cut 12
Crude oil
Residue

100.4170.9
170.9207.5
207.5242.3
242.3262.3
262.3279.4
279.4305.9
305.9315.2
315.2325.0
325.0339.1
339.1354.4
354.4364.2
364.2372.9

>372.9

2.15
2.25
2.20
2.13
2.59
2.04
1.90
2.08
2.00
2.18
2.04
2.45
100
72.60

0.7623
0.8207
0.8426
0.8592
0.8704
0.8846
0.8895
0.8959
0.9046
0.9140
0.9201
0.9234
0.9541
0.9854

0.02
0.03
0.06
0.09
0.14
0.21
0.26
0,28
0.32
0.38
0.42
0.43
0.60
0.71

0.08
0.19
0.45
0.76
1.17
1.36
2.18
3.05
4.13
4.93
5.31
5.43
3.19
3.16

ance (weight, w,%) was performed for the distillation cuts and the
residual oil from the relation in mass values between the crude oil
and its respective distillation cuts and residue. Twelve cuts (named
cuts 112) were extracted according to their mass percentages in
the oil source and characterized in terms of the density, TAN, total
sulfur and ESI()-FT-ICR MS analyses. The density, the total sulfur
and the TAN values are shown in Table 1.
2.4. ESI()-FT-ICR MS

Fig. 1. Illustration of the homemade true boiling point distillation system developed by LabPetro/UFES/Brazil.

the residual oil are produced. The liqueed gases are lost to the
atmosphere, whereas the cut distillations are collected in a glass
ask located behind the cooler. Finally, the distillation residue remains inside the distillation ask (Fig. 1). Herein, a Brazilian crude
oil sample was submitted to a heating rate from 20 to 373 C at
atmospheric pressure and reduced pressures (from 760 to
0.1 mmHg). In the end, this distillation process produced twelve
cuts (with the boiling points varying from 100.4 to 372.9 C) and
a nal residue with a boiling point above 373 C. The material bal-

Petroleum samples were analyzed by both ion modes: positive

and negative electrospray ionization, ESI(). Briey, the crude
oil and the distillation residue samples were diluted to
0.41.2 mg mL1 and distillation cuts of 0.15 mg mL1 in 50:50
(v/v) toluene/methanol (which contained 0.1% m/v of HCOOH for
ESI(+) and NH4OH for ESI()). The resulting solution was directly
infused at a ow rate of 5 lL min1 into the ESI source. The mass
spectrometer (model 9.4 T Solarix, Bruker Daltonics, Bremen, Germany) was set to operate over a mass range of m/z 2001300. The
ESI() source conditions were as follows: a nebulizer gas pressure
of 0.51.0 bar, a capillary voltage of 2.54.1 kV, and a transfer capillary temperature of 250 C. The ion accumulation time in the
hexapole was 0.010.2 s, which was followed by the transportation
to the analyzer cell through the electrostatic lens system. Each
spectrum was acquired by accumulating 200 scans of time-domain
transient signals in 4 mega-point time-domain data sets. The front
and back trapping voltages in the ICR cell were 0.60 V and
0.65 V for ESI() and +0.80 V and +0.85 V for ESI(), respectively.
All mass spectra were externally calibrated using a NaTFA solution
(m/z from 2001200) after they were internally recalibrated using
a set of the most abundant homologous alkylated compounds for
each sample. A resolving power (m/Dm50%  500,000, in which
Dm50% is the full peak width at half-maximum peak height) of
m/z 400 and a mass accuracy of <1 ppm provided the unambiguous
molecular formula assignments for singly charged molecular ions.
The mass spectra were acquired and processed using a custom
algorithm developed specically for petroleum data processing,
Composer software (Sierra Analytics, Pasadena, CA, USA). The MS
data were processed, and the elemental compositions of the compounds were determined by measuring the m/z values. To help
visualize and interpret the MS data, a typical plot was constructed,
such as a carbon number versus the double bond equivalents
(DBE), where DBE is dened as the number of rings plus the number of double bonds in a molecular structure. The aromaticity of a
petroleum component can be deduced directly from its DBE value
according to the following equation:

DBE c  h=2 n=2 1

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

where c, h, and n are the numbers of carbon, hydrogen, and nitrogen

atoms, respectively, in the molecular formula.
2.4.1. ESI()-MS/MS
Tandem mass spectrometry (MSn) experiments were performed
on a linear quadrupole ion-trap, LTQ, (Thermo Scientic, Bremen,
Germany). The spectra were collected in ESI(+) and ESI() using
a max ion source (Thermo Scientic, Bremen, Germany). The typical ESI conditions were: (i) n infusion ow rate at 2 lL min1; (ii) a
nebulizing temperature of 240 C; (iii) a sheath gas ow of 16
(arbitrary unit); (iv) an auxiliary gas ow of 5 (arbitrary unit);
(v) and an iso spray voltage of 3.10 kV. Other experimental parameters for ESI(+) and ESI() sources were used are, respectively: (vi)
capillary temperature of 220 C; (vii) tube lens of 120 and 100 V;
and (viii) capillary voltage: 35 and 39 V. The ESI()MS/MS spectra
were acquired with automatic gain control averaging 5 microscans for each spectrum with isolation window of 1.0 (m/z units)
and 2545% of the collision energy. The spectra were processed
using the Xcalibur Software (Thermo Scientic, Bremen, Germany).
2.4.2. Methylation reactions
The methylation procedure for sulfur compounds has been reported in 2010 and 2011 by Liu et al. [27,28] Herein, the methylation reactions (Fig. 2) were performed only for heavy distillation
cuts such as cuts 11 and 12 and the residual oil because of the high
sulfur content (0.42, 0.43 and 0.71 wt%, respectively (Table 1)).
First, 100 mg of samples were weighted and dissolved in a solution
of methyl iodide (0.1 mmol mL1 in dichloromethane) under continuous stirring. Afterwards, an alcoholic solution containing
1.0 mmol of silver nitrate was added, and a yellow precipitate silver iodide was spontaneously formed (silver iodide, see Fig. 2). The
reaction remained under a reduced pressure and constant stirring
during 48 h. Finally, the formed precipitate was removed by centrifuge and ltration, and the remaining solution, which contained
sulphonium salts (Fig. 2), was evaporated to ensure a total removal
of impurities such as methyl iodide and dichloromethane. The produced sulphonium salts were analyzed using ESI(+)-FT-ICR MS.
3. Results and discussion
The physicalchemical characterization (boiling point, weight,
density, total sulfur and TAN) of crude oil and its respective distillation cuts and residue is shown in Table 1. For the crude oil distillation cuts, the total sulfur and TAN values increase by thirty and
seventy times, respectively, when the boiling point increases. The
result is mainly evident when we compare the values obtained
for cut 1 (S = 0.014 wt% and TAN = 0.077 mg KOH g1) and cut 12
(S = 0.43 wt% and TAN = 5.43 mg KOH g1). When the light fractions, which contain mainly hydrocarbons, are removed from the
crude oil, an increase of the S content is also observed from the
crude oil to its distillation residue (0.60 ? 0.71 wt%). However, a
little reduction in the TAN values is observed (3.19 ? 3.16 mg
KOH g1). For sulfur heteroatom compound species (Sx classes,
where x = 13), this reduction is due to the higher thermal stability
in comparison with the naphthenic acids species. This last can
experience thermal-degradation reactions during the distillation

CH3

AgNO3

H2O
EtOH

CH3

Ag

NO3

CH3
S

S
+

CH3

Ag

Fig. 2. Methylation reactions.

AgI(S)

193

process and produce low chain length naphthenic acids (C1C4),

which are improved by its low aromaticity (maximum of DBE 4)
[29,30] and low boiling point or can also undergo decarboxylation
reactions as a consequence of this poor thermal stability [31,32].
3.1. ESI(-)-FT-ICR MS
Fig. 3a shows the ESI(-)-FT-ICR mass spectra for cuts 112,
which were extracted by the laboratorial petroleum distillation
system, where the naphthenic acids species are detected as deprotonated molecules: [MH] ion. In the light distillation cuts such as
cut 1, the ESI(-)-FT-ICR mass spectrum identies only ions that correspond to the impurities from the background: [C15H24OH]: m/z
219.1755, [C16H32O2H]: m/z 255.2330, [C18H32O2H]: m/z
279.2330 and [C18H34O2H]: m/z 281.2487, which most likely
correspond to butylated hydroxytoluene, and palmitic, linoleic
and oleic acids, respectively. These ions do not represent the typical homologous series observed for naphthenic acid as shown in
the ESI(-)-FT-ICR mass spectra (see cuts 212). Additionally, these
impurities are also detected in the other light crude-oil cuts (cuts
14), where the naphthenic acid concentration is low (TAN values
vary from 0.08 ? 0.76 mg KOH g1) and disappears with the increase in the distillation cut temperature. In general, the presence
of naphthenic acids with low m/z cannot be disregarded because of
the width of the bulk of light distillation cuts such as cut 1 (mainly,
the linear naphthenic acid that contains a number carbon varying
from C1 to C7). An alternative to identify these light acids species
with a low boiling point T < 171 C and m/z < 150 is to use the other
MS analyzers (such as quadrupole, ion traps, TOF or Orbitraps) or
other analytical techniques (ion chromatography [33] and electrophoresis capilar).
The ESI(-)-FT-ICR mass spectra from cuts 2 to 12 show the
detection of 122 naphthenic acid species with m/z ranging from
153 to 421 (see Fig. 3a and Table 1S (Supplementary material)).
Table 1S shows the predicted molecular formulas and their possible chemical structures from the measured and theoretical m/z values, the DBE and the mass error (which is generally lower than
1 ppm). These results are summarized in Fig. 4. Note that besides
the naphthenic acid species that are the majority, phenol analogue
species (O1 Class, DBE = 4)) are also detected with m/z ranging
from 163 to 357, DBEs from 4 to 5 and carbon number from C9
to C25. When the distillation cut temperature increases, the
amounts of O2 species (O2 class) or naphthenic acids also increase
(from 9 compounds for cut 2 to 66 compounds for cut 12), and the
average molecular weight distribution, Mw, shifts to higher m/z values (Mw = 169 ? 321 Da) (Fig. 3a). These results are consistent
with previously results obtained by Marshall et al. [34]. Moreover
these results match with the increasing of TAN as the boiling point
increases (Table 1) [24].
One method to display the similarities or differences between
the signal patterns of the crude oil samples and the distillation cuts
is to construct certain types of plots such as the plots of DBE versus
the carbon number. These plots have proven to be useful tools to
differentiate complex organic mixtures based on the chemical
composition [35,36], which shows the distribution of all components from a specic class. Each line in the diagram represents a
homologous series with a specic DBE value (Fig. 3b).
Fig. 3b shows the plots of the DBE versus the carbon number for
the O2 class of distillation cuts (cuts 112), which contain compounds with DBEs ranging from 1 to 9 and carbon numbers ranging
from C9 to C26. For distillation cuts 2 and 3, the most abundant
compounds show a carbon number of C10C11 with a constant
DBE of 2 (Mw = 169183 Da). These species are mainly composed
of one naphthenic ring (ve- or six membered) and one carboxyl
group. For the other distillation cuts (cuts 412), the maximum
abundance is located for high carbon numbers (varying from C12

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G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

Fig. 3. (a)ESI()-FT-ICR MS for the distillation cuts and (b) plots of DBE versus carbon number for the O2 class of distillation cuts.

to C22) with a constant DBE of 3, which is now composed of two

naphthenic rings and one carboxyl group (see the proposed structure in Fig. 4 and Table 1S).
Some studies in literature report the correlation between the
chemical composition of crude oil and the corrosion process
[24,37]. In 2012, Huang et al. [29] studied the synergy effect of
naphthenic acid corrosion and sulfur corrosion at high temperature (280 C) in a crude oil distillation unit using Q235 carbon
manganese steel and 316 stainless steel. In a corrosion media
containing only sulfur (from 1 to 5 wt%), the corrosion rate of

Q235 and 316 rst increased and then decreased with the
increasing of sulfur content. However, when the naphthenic acid
and the sulfur compounds were added together (in the rst case,
the TAN ranged from 3 to 15 mg KOH g1 with S of 1 wt%, and in
the second case, TAN = 6 mg KOH g1, and S ranged from 1 to
5 wt%), a synergy effect on the corrosion rate was observed in
Q235 and 316. In the same year, Freitas et al. [24] studied the effect of composition of heavy distillation cuts from heavy crude oil
(density = 0.93 and TAN = 1.93 mg KOH g1) on the corrosion process. The cuts with boiling temperatures lower than 315 C and

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

195

Fig. 4. Possible chemical structures for O2, O1 and N classes present in the crude oil distillation cuts, which contain their respective DBE, m/z and carbon number values.

TANs (ranging from 0.47 to 1.83 mg g1) were studied. According

to the ESI(-)-FT-ICR MS results, the naphthenic acid species were
detected in the six cuts studied (cuts 27), with m/z < 300 and
DBEs ranging from 2 to 4. Similarly, the relative abundance of
heavy naphthenic acids and the TAN increase with the distillation
cut temperature. This information correlated with the corrosion
mechanism for AISI 1020 steel in the heavy oil and the distillation
cuts, where the corrosion was more evident in the oil distillation
cuts that were characterized as alveolar and pitting. In addition,
Piehl [38] and Slavcheva et al. [39] show that the corrosion rate
had increased (from 0.30 mm/y to 1.27 mm/y) as a function of
boiling point (from 204 C to 371 C) for cuts with TAN 2 mg
KOH g1. It also increased (from 1.27 mm/y to 2.08 mm/y) as a
function of TAN (from 2 mg KOH g1 to 10 mg KOH g1) at
371 C [40]. Therefore, it is expected that the heavy distillation
cuts will be more corrosive than the light distillation cuts. In
other words, the corrosion rate will increase in the following order: naphtha (cuts 12) < kerosene (cuts 34) < gas oil (cuts 5
12). Additionally, the corrosion process can be contributed by
the sulfur compound species [29], which mainly present in the
heavy distillation cuts (cuts 512) (Table 1).
Finally, alternative methods have recently been developed to
reduce the amount of naphthenic acid species and consequently
the corrosion rate [41,42,31]. These processes normally involve
critical and expensive conditions such as high temperatures
(300400 C) and an inert N2 atmosphere [33], the use of supercritical water in a batch reactor at 500 C and 50 MPa [34], or thermal
cracking and catalytic decarboxylation over alkaline earth-metal
oxides and ZnO catalysts [35].

Fig. 5a and b shows the ESI(-)-FT-ICR mass spectra for the crude
oil (5a) and its respective distillation residue (5b), with m/z range
from 200 to 1000, which correspond primarily to naphthenic acids
and carbazole analogue species. An expansion in the m/z region of
400410 allows the comparison of the relative intensity of the two
main species identied (the insets in Fig. 5a and b). Note that the
relative abundance of the heavy naphthenic acids decreases from
the crude oil to its residue distillation. This reduction is due to
the migration of light species during the distillation process from
the crude oil studied to the cuts; consequently, the Mw is shifted
and broadened to high values (603 Da ? 627 Da1). It is more evident when we analyze the plots of DBE versus carbon number for
the O2 and N classes of crude oil (Fig. 5ce) and its residue distillation (Fig. 5df). Both classes are affected by the atmospheric distillation process. Initially, the high abundance of hydrocarbon
homologous series of polar markers for the N class ranged from
C34 (Fig. 5c, crude oil) to C44 (Fig. 5d, residue distillation), with the
maximum DBE constant in aromaticity, DBE = 14. It is due to the ionic suppression phenomenon, which is caused by removing the
naphthenic acids with carbon numbers than lower C20 from the
crude oil and dissolving them along the distillation cuts at temperatures between 100 and 373 C (see the highlighted area in bold in the
region of number carbon between C10 and C20, Fig. 5e and f). Generally, for the O2 class, the maximum values of the abundance distribution remained constant: C31 and DBE 3. These results are similar
to reported in the literature [43].
1
Mw was obtained from the petroleum data processing using Composer software,
where 92% signals were assigned.

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G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

Fig. 5. ESI()-FT-ICR MS for (a) crude oil and (b) residue distillation; plots of DBE versus carbon number for the N and O2 classes that correspond to (ce) the crude oil and (d
f) the residue distillation. The carbon number abundance distribution maximum (red arrow) shifts from C34 (crude oil, 3c) to C44 (residue distillation, 3d) for the N class.
The DBE values remained constant in aromaticity: DBE = 14. For the O2 class, the maximum values of the abundance distributions remained constant: C31 and DBE = 3. (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

3.2. ESI(+)-FT-ICR MS
Similar to the ESI(-)-FT-ICR MS results, the ESI(+)-FT-ICR mass
spectra for the distillation cuts 112 (Fig. 6a and b), the crude oil
and its residue (Fig. 7ad) are shown. Now, the polar species from
pyridine derivatives (Nx class) are detected as the protonated molecules: [M + H]+ ion. Again, for the light distillation cuts (cut 1), the
ESI(+)-FT-ICR mass spectrum identies the ions corresponding to
impurities such as m/z 301 (which originated from methanol that
is used in the preparation of the solution). For the other cuts (cuts

212), the ESI(+)-FT-ICR mass spectra show the detection of 100

compounds (the number is lower than that observed for the naphthenic acidic species). These species show m/z ranging from 160 to
414 (Fig. 6a). Table 2S (Supplementary material) shows the predicted molecular formulas and their possible chemical structures
of most pyridine derivative species, which are obtained from the
measured and the theoretical m/z values, DBE and mass error.
The results are summarized in Fig. 4. Note that when the distillation cut temperature increases, the amount of nitrogen species
identied (N class) increases, and the Mw shifts toward higher

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

197

Fig. 6. (a) ESI(+)-FT-ICR MS for the distillation cuts: detection of 100 pyridine derivative species that show m/z ranging from 160 to 414; (b) plot of DBE versus carbon
number for the N class: for the light distillation cuts (36), the most abundant compounds show carbon numbers of C12C18 with DBE = 4; whereas for the heavy distillation
cuts (812), we observed carbon numbers of C20C24 and DBE = 6.

values (6 species and Mw = 206 Da for cut 3; and 64 species and

Mw = 340 Da for cut 12) (Fig. 6a).
Fig. 6b shows the plots of the DBE versus the carbon number for
the N class of distillation cuts (cuts 112), which there are compounds with DBEs ranging from 3 to 10 and carbon numbers ranging from C11 to C29. For distillation cut 3, the most abundant
compounds show a carbon number of C12 and a constant DBE of
4. These species are mainly composed of one pyridine ring (six
membered containing an N atom) and one alkyl group (R)
(Fig. 4). For the other distillation cuts (cuts 812), the maximum
abundance is located at high carbon numbers (changing from C20

to C24) with a constant DBE of 6, which is now composed of one

pyridine ring and two naphthenic ring (ve- or six-membered).
Fig. 7a and b shows the ESI(+)-FT-ICR mass spectra for crude oil
(7a) and its respective distillation residue (7b), where m/z ranges
from 200 to 1000. Generally, the Mw is subtlety shifted and broadened to high values (500 Da ? 550 Da), which is more evident
when we compare the plots of DBE versus carbon number for the
pyridine derivative species (N class) of crude oil (Fig. 7c) and its
residue distillation (Fig. 7d). The high abundance hydrocarbon
homologous series of polar markers for the N class ranges from
C35 (Fig. 7c, crude oil) to C40 (Fig. 7d, residue distillation), and the

198

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

Fig. 7. ESI(+)-FT-ICR MS for (a) crude oil and (b) residue distillation; plots of DBE versus carbon number for the N class of (c) crude oil and (d) its residue distillation.

maximum DBE is constant in aromaticity: DBE = 9. The result is

due to the removal of nitrogen species with low chain length (from
C11 to C29) from the crude oil during the atmospheric distillation
process (see the highlighted area in bold in the region of number
carbon between C10 and C30 in Fig. 7c and d).
For both oils, the N compound class is the most abundant class
(90%). The N2 class is the second most abundant (7%), followed
by the NO class (3%). The distillation process removes primarily
nitrogen compound species (N class) from the crude oil to the distillation cuts (Fig. 6), and consequently, a small decrease in the relative intensity of the N class (90 ? 88%) and an increase of the N2
class (7 ? 9%) is observed.
3.3. Methylation reaction
Fig. 8ac shows the ESI(+)-FT-ICR mass spectra for the heavy
distillation cuts (cuts 11 and 12, 8a and b) and the distillation residue (8c) derived from methyl sulfonium salts with Mw = 326, 340
and 767 Da, respectively. An expansion in the m/z regions of m/z

316340 (8a), m/z 360380 (8b) and m/z 730740 (8c) summarizes
the identication of the presence of sulfur class species. A total of
51, 53 and 304 sulfur species were detected from distillation cuts
11, 12 and the residue. Note that the basic nitrogen class species
are also identied due to the lower pKa values (pKa 5.3)
(Fig. 8a and b) when compared to the sulfur class species (benzothiophene, pKa  33 and thiols groups, pka  10.5). In all cases,
the presence of the S1 class is observed to correspond to suldes
and thiophenic compounds.
The S1 class can be visualized similarly to the plots of the DBE
versus the carbon number of the heavy distillation cuts (cuts 11,
and 12, Fig. 9a and b) and the distillation residue (Fig. 9c). For
the heavy distillation cuts, there are compounds with DBEs ranging
from 0 to 6 and carbon numbers ranging from C18 to C30. The most
abundant compounds show carbon numbers of C23 (for cut 11) and
C25 (for cut 12) with a constant DBE of 3 (Fig. 9a and b). For the distillation residue, DBEs and carbon number ranging from 0 to 8 and
C35 to C70, respectively, were observed with maxima of DBE = 4 and
C43 (Fig. 9c).

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

199

Fig. 8. ESI(+)-FT-ICR MS spectra for cuts (a) 11 and (b) 12, and (c) distillation residue derived from methyl sulfonium salt.

In 2011, Liu et al. [22] studied the elemental composition and

distribution of sulde and thiophenic compounds in four subfractions of Kazakhstan vacuum gas oil (the simulated distillation
curves of the VGO subfractions ranged from 150 to 600 C). The

samples had Mw ranging from 250 to 500 Da with the S1 class species being the majority, where DBE values P6 are likely thiophenic
compounds, whereas those with DBE values 66 are suldes. Therefore, for the heavy distillation cuts and residue, the sulde class

200

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

Fig. 9. Plots of DBE versus carbon number for S1 class of heavy distillation cuts (cuts 11 and 12) and distillation residue derived from methyl sulfonium salts.

100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0

(b)

m/z 185
C11H21O2
DBE = 1

167.2

Relative Abundance

Relative Abundance

(a)

- CH3COOH
- CO2

He
141.2

- C2H4
151.2

- H2O

157.2
59.2

60

125.2

97.1

70

80

170.2

185.3

100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0

m/z 219
C15H23O
DBE = 4

- C6H13

133.2

- C5H11
- C4H9

He

- C3H7
134.2
147.2

- C2H5
162.2

113.1 119.2

- H2O
176.2 190.2

203.3 219.3

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220

90 100 110 120 130 140 150 160 170 180

m/z

m/z
-C2H4
-C2H4
296.3
-C2H4

-C2H4

Relative Abundance

(c) 10095
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0

-C2H4

m/z 326
C26H36N
DBE = 6

-C2H4
-C2H4
-C2H4

-C2H4

-C2H4

268.3
254.3
282.3

240.3

- CH3
311.3

-C2H4

326.3

226.3
214.3
-C2H4
200.3
186..2
172.2

He

158.2
146.2
132.1

100 120 140 160 180 200 220 240 260 280 300 320

m/z
Fig. 10. ESI()-MS/MS spectra of typical (a) O2, (b) O and(c) N compound classes.

species are the majority. The sulfur compounds with DBE = 0 are
aliphatic suldes. Those with DBEs =1 and 2 are one- and two-cyclic-ring suldes, respectively. For the S1 class, the species with DBE
=3 are likely tricyclic-ring suldes. The S1 class species with DBEs
P4 are likely cyclic-ring or aromatic suldes. The S1 class species
with DBEs P6 are presents only in the distillation residue and correspond to benzothiophene and dibenzothiophene compounds
[9,22]. In 2010, the same group [21] worked in methylsulfonium
salt characterization in crude oil and its fractions (saturates, aromatics, resins, and asphaltenes). For crude oil and its light fractions
(saturates and aromatics), the S1 class had the highest relative

intensity, which is in good agreement with our results. Additionally, the other sulfur class species were also identied (S2, O2S1,
O1S1, N1S1, S3, O1S2 and O2S1).
3.4. ESI()-MS/MS
To conrm the structures and the connectivity of some compound classes that are more abundant (O2, O and N classes), which
were identied using ESI()-FT-ICR MS, the ESI()-MS/MS spectra
were acquired for the ions [C11H22O2H] and [C15H24OH] of
m/z 185.1549 and 219.1755 and ESI(+)-MS/MS for ion

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

[C26H35N + H]+ of m/z 326.2840 (Fig. 10ac). This approach identies the characteristic loss and conrms the existence of O2 compounds such as the carboxylic acids, O compounds such as
phenolic alkylated (which has DBE = 4), and N compounds such
as the pyridinic derivatives.
Initially, for Fig. 10a, the CID experiment of ion [C11H22O2H]
of m/z 185.1549 produces fragments with m/z 167, 141 and 125,
which correspond to the neutral losses of 18 Da (H2O), 44 Da
(CO2) and 60 Da (acetic acid, CH3CO2H), respectively. Meanwhile,
the ESI()MS/MS of the ion [C15H24OH] of m/z 219.1755 produces fragments of m/z 201 (via neutral loss of H2O) and a series
of signals (m/z 190, 176, 162, 147 and 133), which are attributed
to the alkyl chain fragmentation (Fig. 10b). These fragmentation
patterns allow for the identication of phenolic derivative species
(O1 class) with DBE = 4, where its alkyl chain varies as a function of
the carbon number. Finally, for the ESI(+)MS/MS spectrum of ion
[C26H35N + H]+ of m/z 326.2840, a classic fragmentation pattern
of the alkyl chain is observed (in most cases, the neutral loss of
C2H4 and 28 Da are observed), which is proposed to represent a
pyridinic ring and a large alkyl chain (Fig. 10c).

4. Conclusion
Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI()-FT-ICR MS) had been demonstrated as a powerful analytical tool in the chemical typication
of polar compound species. For oxygen-containing species, the
ESI()-FT-ICR MS spectra showed the detection of 122 naphthenic
acid species in the distillation cuts with m/z ranging from 153 to
421. When the distillation cut temperature increased, the amount
of O2 species increased (from 9 for cut 2 to 66 for cut 12), and the
average molecular weight distribution, Mw, shifted to higher m/z
values (Mw = 169 ? 321 Da). These results were consistent with
the increase of TAN with the boiling point. The plots of the DBE
versus the carbon number for the O2 class for the heavy distillation
cuts (cuts 412) suggested a maximum abundance for the carbon
numbers of C12C18 with a constant DBE of 3. The basic structure
of these species is composed of two naphthenic rings and one carboxyl group. The phenol analogue species were also detected (O1
Class, DBE = 45) with m/z ranging from 163 to 357 and carbon
number ranging from C9 to C25. For the ESI(+)-FT-ICR MS spectra,
approximately 100 nitrogen compound species were detected with
m/z ranging from 160 to 414. Similar to the ESI()-FT-ICR results,
the amount of nitrogen species increased, and the Mw shifted for
high values (6 species and Mw = 206 Da for cut 3; and 64 species
and Mw = 340 Da for cut 12). The structures and the connectivity
of naphthenic acids, phenols and pyridines were conrmed using
ESI()-MS/MS, where the typical neutral losses were detected such
as 18 Da, 44 Da and 60 for naphthenic acid and 18 Da for phenolic
derivative species. A classic fragmentation pattern corresponding
to the alkyl chain was observed for the pyridine species.
Methylation reactions have been demonstrated as an efcient
analytical method to detect sulfur compound species. The most
abundant compounds in the heavy distillation cuts presented C23
(for cut 11) and C25 (for cut 12) with a constant DBE of 3. For the
distillation residue, the maxima of DBEs and the carbon number
were DBE = 4 and C43. These results suggested the presence of sulde class species as the majority structure (cyclic-rings or aromatic
suldes), i.e., the S1 class.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2013.07.008.

201

References
[1] (a) Hughey CA, Rodgers RP, Marshall AG, Walters CC, Qian K, Mankiewicz P.
Acidic and neutral polar NSO compounds in smackover oils of different
thermal maturity revealed by electrospray high eld Fourier transform ion
cyclotron resonance mass spectrometry. Org Geochem 2004;35:86380;
(b) Hughey CA, Rodgers RP, Marshall AG, Qian K, Robbins WK. Identication of
acidic NSO compounds in crude oils of different geochemical origins by
negative ion electrospray Fourier transform ion cyclotron resonance mass
spectrometry. Org Geochem 2002;33:74359.
[2] Marshall AG, Rodgers RP. The next grand challenge for chemical analysis. Acc
Chem Res 2004;37:539.
[3] Brient JA. Commercial utility of naphthenic acids recovered from petroleum
distillates. In: Symposium on acidity in crude oil, presented before the division
of petroleum chemistry, Inc., 215th National Meeting, American Chemical
Society, Dallas, TX, March 29-April 3; 1998.
[4] Barrow MP, Headley JV, Peru KM, Derrick PJ. Data visualization for the
characterization of naphthenic acids within petroleum samples. Energy Fuels
2009;23:25929.
[5] Wu Z, Rodgers RP, Marshall AG. Compositional determination of acidic species
in Illinois #6 coal extracts by electrospray ionization Fourier transform ion
cyclotron resonance mass spectrometry. Energy Fuels 2004;18:14248.
[6] Barrow MP, McDonnel LA, Feng X, Walker J, Derrick PJ. The continued battle
against corrosion. Anal Chem 2003;75:8606.
[7] Vaz BG, Abdelnur PV, Rocha WFC, Gomes AO, Pereira RCL. Predictive
petroleomics: measurement of the total acid number by electrospray Fourier
transform mass spectrometry and chemometric analysis. Energy Fuels
2013;27:187380.
[8] Hemmingsen PV, Kim S, Pettersen HE, Rodgers RP, Sjoblom J, Marshall AG.
Structural characterization and interfacial behavior of acidic compounds
extracted from a north sea oil. Energy Fuels 2006;20:19807.
[9] Kim Y, Kim S. Improved abundance sensitivity of molecular ions in positive-ion
APCI MS analysis of petroleum in toluene. J Am Soc Mass Spectrom
2010;21(3):38692.
[10] Hur M, Yeo I, Park E, Kim YH, Yoo J, Kim E, et al. Combination of statistical
methods and Fourier transform ion cyclotron resonance mass spectrometry for
more comprehensive, molecular-level interpretations of petroleum samples.
Anal Chem 2010;82:2118.
[11] Tervinem MJ, Pakarinem JMH, Wickstrm K, Vainiotalo P. Comparison of the
composition of Russian and north sea crude oils and their eight distillation
fractions studied by negative-ion electrospray ionization Fourier transform ion
cyclotron resonance mass spectrometry: the effect of suppression. Energy
Fuels 2007;21:26673.
[12] Furimsky E, Massoth FE. Hydrodenitrogenation of petroleum. Catal Rev Sci Eng
2005;47(3):297489.
[13] Van Looij F, Van der Laan P, Stork WHJ, DiCamillo DJ. Key parameters in deep
hydrodesulfurization of diesel fuel. J Appl Catal A Gen 1998;170(1):112.
[14] Wu Z, Rodgers RP, Marshall AG. Comparative compositional analysis of
untreated and hydrotreated oil by electrospray ionization Fourier transform
ion cyclotron resonance mass spectrometry. Energy Fuels 2005;19:10727.
[15] Hsu CS, Hendrickson CL, Rodgers RP, McKenna AM, Marshall AG. Petroleomics:
advanced molecular probe for petroleum heavy ends. J Mass Spectrom
2011;46:33743.
[16] Gaspar A, Schrader W. Expanding the data depth for the analysis of complex
crude oil samples by Fourier transform ion cyclotron resonance mass
spectrometry using the spectral stitching method. Rapid Commun Mass
Spectrom 2012;26:104752.
[17] Benassi M, Arton B, Romo W, Babayev E, Rompp A, Spengler B. Petroleum
crude oil analysis using low-temperature plasma mass spectrometry. Rapid
Commun Mass Spectrom 2013;27:82534.
[18] McKenna AM, Purcell JM, Rodgers RP, Marshall AG. Heavy petroleum
composition. 1. Exhaustive compositional analysis of athabasca bitumen
HVGO distillates by Fourier transform ion cyclotron resonance mass
spectrometry: a denitive test of the Boduszynski model. Energy Fuels
2010;24:292938.
[19] Klein GC, Angstrom A, Rodgers RP, Marshall AG. Use of saturates/aromatics/
resins/asphaultenes (SARA) fractionation to determine matrix effects in crude
oil analysis by electrospray ionization fourier transform ion cyclotron
resonance mass spectrometry. Energy Fuels 2006;20:66872.
[20] Purcell JM, Merdrignac I, Rodgers RP, Marshall AG, Gauthier T, Guibard I.
Stepwise structural characterization of asphaltenes during deep
hydroconversion
processes
determined
by
atmospheric
pressure
photoionization (APPI) Fourier transform ion cyclotron resonance (FT-ICR)
mass spectrometry. Energy Fuels 2010;24:225765.
[21] ASTM D5002-99 Standard Test Method for density; 2010.
[22] ASTM D1298-99 Standard Test Method for API degree; 2005.
[23] ASTM D664-09 Standard test Method for Acid Number of Petroleum Products
by Potentiometric Titration.
[24] ASTM D704204 Standard Test Method for Dynamic Viscosity and Density of
Liquids by Stabinger Viscometer (and the calculation of kinematic viscosity);
2004.
[25] ASTM D429410 Standard Test Method for Sulfur in Petroleum and Petroleum
Products by Energy Dispersive X-ray Fluorescence Spectrometry; 2000.
[26] ASTM D 2892. Standard Test Method for Distillation of Crude Oil; 2005.

202

G.P. Dalmaschio et al. / Fuel 115 (2014) 190202

[27] Liu P, Shi Q, Chung KH, Zhang Y, Pan N, Zhao S, et al. Molecular characterization
of sulfur compounds in Venezuela crude oil and its SARA fractions by
electrospray ionization Fourier transform ion cyclotron resonance mass
spectrometry. Energy Fuels 2010;24(9):508996.
[28] Liu P, Shi Q, Pan N, Zhang Y, Chung KH, Zhao S, et al. Distribution of suldes
and thiophenic compounds in VGO subfractions: characterized by positive-ion
electrospray Fourier transform ion cyclotron resonance mass spectrometry.
Energy Fuels 2011;25:301420.
[29] Colati KAP, Dalmaschio GP, de Castro EVR, Gomes AO, Vaz BG, Romo W.
Monitoring the liquid/liquid extraction of naphthenic acids in brazilian crude
oil using electrospray ionization FT-ICR mass spectrometry (ESI FT-ICR MS).
Fuel 2013;108:64755.
[30] Freitas S, Malacarne MM, Romo W, Dalmaschio GP, Castro EVR, Celante VG,
et al. Analysis of the heavy oil distillation cuts corrosion by electrospray
ionization FT-ICR mass spectrometry, electrochemical impedance
spectroscopy, and scanning electron microscopy. Fuel 2013;104:65663.
[31] Ding L, Rahimi P, Hawkins R, Bhatt S, Shi Y. Naphthenic acid removal from
heavy oils on alkaline earth-metal oxides and ZnO catalysts. Appl Catal A Gen
2009;371:12130.
[32] Zhang A, Ma Q, Wang K, Liu X, Shuler P, Tang Y. Naphthenic acid removal from
crude oil through catalytic decarboxylation on magnesium oxide. Appl Catal A
Gen 2006;303:1039.
[33] Ferreira FN, Carneiro MC, Vaitsman DS, Pontes FVM, Monteiro MIC, da Silva
LID, et al. Matrix-elimination with steam distillation for determination of
short-chain fatty acids in hypersaline waters from pre-salt layer by ionexclusion chromatography. J Chromatogr A 2012;1223:7983.
[34] Stanford LA, Kim S, Rodgers RP, Marshall AG. Characterization of
compositional changes in vacuum gas oil distillation cuts by electrospray

[35]

[36]
[37]

[38]
[39]
[40]
[41]

[42]

[43]

ionization Fourier transformion cyclotron resonance (FTICR) mass

spectrometry. Energy Fuels 2006;20:166473.
Hughey CA, Hendrickson CL, Rodgers RP, Marshall AG. Kendrick mass defect
spectroscopy: a compact visual analysis for ultrahigh-resolution broadband
mass spectra. Anal Chem 2001;73:467681.
Van Krevelen DW. Graphical-statistical method for the study of structure and
reaction processes of coal. Fuel 1950;29:26984.
Huanga BS, Yinb WF, Sang DH, Jianga ZY. Synergy effect of naphthenic acid
corrosion and sulfur corrosion in crude oil distillation unit. Appl Surf Sci
2012;259:66470.
Piehl RL. Naphthenic acid corrosion in crude distillation units. Mater Perform
1988;27:3743.
Slavcheva E, Shone B, Turnbull A. Review of naphthenic acid corrosion in oil
rening. Br Corr J 1999;34:12531.
Alvisi PP, Lins VFC. An overview of naphthenic acid corrosion in a vacuum
distillation plant. Eng Fail Anal 2011;18:14036.
Smith DF, Rodgers RP, Rahimi P, Teclemariam A, Marshall AG. Effect of thermal
treatment on acidic organic species from athabasca bitumen heavy vacuum
gas oil, analyzed by negative-ion electrospray fourier transform ion cyclotron
resonance (FT-ICR) mass spectrometry. Energy Fuels 2009;23:3149.
Mandal PC, Wahyudiono, Sasaki M, Goto M. Reduction of total acid number
(TAN) of naphthenic acid (NA) using supercritical water for reducing corrosion
problems of oil reneries. Fuel 2012;94:6203.
Shi Q, Zhao S, Xu Z, Chung KH, Zhang Y, Xu C. Distribution of acids and neutral
nitrogen compounds in a Chinese crude oil and its fractions: characterized by
negative-ion electrospray ionization fourier transform ion cyclotron resonance
mass spectrometry. Energy Fuels 2010;24:400511.