Fuel 234 (2018) 643–649

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Determination of flash point and Reid vapor pressure in petroleum from T

HTGC and DHA associated with chemometrics
Márcia H.C. Nascimento, Betina P. Oliveira, Karla P. Rainha, Eustáquio V.R. Castro,
⁎
Samantha R.C. Silva, Paulo R. Filgueiras
Center of Competence in Petroleum Chemistry – NCQP, Laboratory of Research and Development of Methodologies for Analysis of Oils – LabPetro, Chemistry Department,
Federal University of Espírito Santo, Av. Fernando Ferrari, 514, CEP: 29075-910 Vitória, Espírito Santo, Brazil

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Flash point (FP) and Reid vapor pressure (RVP) are physicochemical properties of crude oil that are used as
Crude oil safety and environmental parameters. In this paper, we propose a methodology for estimating the FP and RVP
Flash point for crude oil by means of detailed hydrocarbon analysis (DHA) and high temperature gas chromatography
Reid vapor pressure (HTGC) associated with partial least squares (PLS) regression. These techniques were used due to their direct
HTGC
relationship to FP and RVP. We studied 107 crude oil samples (with an API gravity range of 11.4–54.0) collected
DHA
PLS
from a Brazilian sedimentary basin. The curve data derived from these two techniques were merged to better
describe the true boiling point curve. Using fusion information drawn from the two chromatographic techniques
(DHA and HTGC), we estimated the flash point with an average error of 5.3 °C and a coefficient of determination
of approximately 0.9. While the data fusion represents an information gain in the estimation of the flash point,
for to estimate the Reid vapor pressure, the HTGC data are sufficient. The PLS regression generated the best Reid
vapor pressure results, with an average error of 0.4 kPa and with a coefficient of determination of above 0.99.

1. Introduction levels of evaporative emissions and on the risks of a fire occurrence

during the transport and processing of oil or petroleum derived pro-
Flash point (FP) and Reid vapor pressure (RVP) are physicochemical ducts [1–5].
properties that are directly related to oil volatility and are used as safety Butler et al. reported the first study to predict the FP of petroleum
and environmental parameters. FP and RVP provide information on the fractions, by means of mathematical methods [6]. They used

⁎
Corresponding author.
E-mail address: filgueiras.pr@gmail.com (P.R. Filgueiras).

https://doi.org/10.1016/j.fuel.2018.07.050
Received 19 January 2018; Received in revised form 5 July 2018; Accepted 11 July 2018
Available online 21 July 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
M.H.C. Nascimento et al. Fuel 234 (2018) 643–649

Fig. 1. Chromatograms of oil samples by DHA technique with information related to the volatility of each sample (RVP – Reid vapor pressure; FP – flash point). (A)
Light oil; (B) medium oil; (C) heavy oil.

Fig. 2. Chromatograms of oil samples by HTGC technique, with box in the peaks in retention time of 0–5 min. (A) Light oil; (B) medium oil; (C) heavy oil.

Fig. 3. Comparison between curves the medium oil sample for DHA, HTGC and merged curve of DHA/HTGC data. (A) DHA curve; (B) HTGC curve; (C) Merged DHA
and HTGC curve data.

Table 1 information on the molecular weight, boiling point and vapor pressure
Main statistical parameters to PLS models for flash point prediction. values for the FP predictions. FP estimations for pure hydrocarbons, for
Model/ 1 2 3 4 5
mixtures of hydrocarbons or for fractions of petroleum have been
Parameters DHA1 HTGC1 DHA2 HTGC2 FUSION1 conducted by theoretical methods, involving empirical correlations,
studies of the quantitative structure-property relationship (QSPR), and
Preprocessing SNV SNV SNV Center Center group contribution methods. However, the QSPR and group contribu-
Samples 66 51 42 42 31
Calibration set 47 36 31 31 23
tion methods cannot be applied to petroleum, because the compositions
Test set 19 15 11 11 8 and molecular structures must be known to use such methods [6–8].
Min Cal (°C) < −30 < −30 < −30 < −30 < −30 Dai et al. employed the group contributions to determine the FP values,
Max Cal (°C) 56.5 59.5 56.5 56.5 56.5 for mixtures of hydrocarbons using chemometric techniques [7]. Al-
VL 2 4 4 7 7
qaheem and Riazi described and evaluated several theoretical methods
RMSEC (°C) 11.3 9.0 7.3 4.1 3.5
RMSECV (°C) 12.6 17.6 14.4 16.1 6.1 applied to pure hydrocarbons and to oil fractions [8]. They proposed a
RMSEP (°C) 8.0 12.4 11.6 17.2 5.3 predictive method for the FP of petroleum fractions, from correlations
R2c 0.5820 0.8518 0.8684 0.9634 0.9797 between the boiling point data and the flash point.
R2cv 0.4503 0.3998 0.4282 0.3665 0.9092 FP and RVP values are widely studied by analytical methods asso-
R2p 0.5373 0.7393 0.8211 0.6950 0.8963
biasa 1.0000 0.7934 1.0000 1.0000 0.8124
ciated with the chemometrics of fractions and products of petroleum
biasb 0.2660 0.3372 0.0639 0.0532 0.0770 [9–16]. Alves et al. used a support vector regression (SVR) to determine
p-valuec 0.0742 0.0642 0.2473 0.1425 0.1552 the FP values of diesel fuel, from near-infrared spectroscopy (NIR) data
p-valued 0.2509 0.4953 0.5012 0.4253 0.2308 [9]. Côcco et al. employed gas chromatography with detailed hydro-
a carbon analysis (DHA) associated with the artificial neural networks
p-value of the bias test to evaluate systematic errors in calibration set.
b (ANNs), to determine the RVP of Brazilian commercial gasoline [14].
p-value of the bias test to evaluate systematic errors in prediction set.
c
p-value of the random test to evaluate trend errors in calibration set.
However, few studies have estimated these properties in crude oil,
d
p-value of the random test to evaluate trend errors in prediction set. which is possibly due to the complexity of its matrix.

644
M.H.C. Nascimento et al.
Fig. 4. Correlation between reference values and flash point prediction. (A) Model 1, DHA1; (B) Model 2, HTGC1; (C) Model 3, DHA2; (D) Model 4, HTGC2; (E) Model
5, FUSION1.
The true boiling point (TBP) curve is the main property to be
identified in petroleum. The TBP curve is determined by physical dis-
tillation, which requires between 20 and 40 L of a sample [17,18]. On
the other hand, the simulated distillation method using high tempera-
ture gas chromatography (HTGC) [19] can be applied to estimate the
TBP curve of crude oil [20–24]. Espinosa et al. compared the effec-
tiveness of the simulated distillation and physical distillation methods,
when applied to Mexican heavy oil [20]. Austrich et al. compared two
approaches to simulated distillation (ASTM D5307 and ASTM D7169)
[21], and correlated their results with those of the Espinosa [20]. Coto
et al. used the simulated distillation method to obtain the distribution
of n-paraffins of petroleum and compared it with that derived from
standardized experimental methods [22]. The authors in turn evaluated
the influence of this distribution on the thermodynamic models used to
study the precipitation of paraffins [22,23].
However, it is difficult to determine the initial part of a TBP curve
from the HTGC because lighter compounds are lost through volatili-
zation. Thus, the initial TBP value may not reflect standard test results
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Fuel 234 (2018) 643–649
(ASTM D2892) [19,24–26]. The detailed hydrocarbon analysis (DHA),
which is also a gas chromatography method, is used to provide com-
ponents with elution levels of up to n-C14. It is applied to volatile oil
fractions and to class analyses that determine the content levels of
Paraffin, Isoparaffin, Olefin, Naphthene and Aromatic (PIONA)
[14,15,25–28]. The light hydrocarbons are important to refining op-
erations, as decisions made regarding catalysts, on mixing operations or
even on the economic value of refinery fractions require a prior de-
termination of such compounds [25–27]. The fusion of information
from these two techniques can generate better results for the descrip-
tion of oil and of its physicochemical properties [26].
Many methodologies to estimate the physicochemical properties of
petroleum have employed spectroscopy associated with PLS
[9–16,22–24,29–35]. However, few works have used chromatographic
data involving multivariate calibration. Morales-Medina and Guzmán
determined the density and viscosity of crude oil, using chromato-
graphic data, with correlations of the NIR and NMR data [24]. Due to
the direct relationship of the flash point and vapor pressure with the
M.H.C. Nascimento et al. Fuel 234 (2018) 643–649

Table 2 The test was conducted under the following chromatographic condi-
Main statistical parameters to the PLS models for Reid vapor pressure predic- tions: carrier helium gas; a pre-column temperature of 200 °C; injector
tion. and detector temperatures of 300 °C; and oven temperatures of 35 °C to
Models 1 2 3 4 5 200 °C (1 °C min−1 and, from the 60 °C of 2 °C min−1, and 20 min iso-
Data DHA1 HTGC1 DHA2 HTGC2 FUSION1 therm).
The HTGC assay followed the ASTM D7169 standard [19] with the
Parameters
extension of the calibration (C5-C120) of n-paraffins. The oil samples
Preprocessed Center Center SNV Center Center
Samples 50 84 39 39 28 were analysed in quadruplicate in a chromatograph with a metallic
Calibration set 36 60 28 28 20 capillary column internally coated with polydimethylsiloxane,
Test set 14 24 11 11 8 5 m × 0.53 mm in internal diameter, 0.09–0.15 µm of stationary phase
Min Cal (kPa) 10.0 23.2 20.2 20.2 20.2
thickness and fitted with a flame ionization detector (FID). The chro-
Max Cal (kPa) 62.8 51.0 53.3 53.3 53.3
VL 8 4 6 5 2
matographic conditions under which the assay was carried out were set
RMSEC (kPa) 3.7 0.6 3.3 5.5 3.5 as follows: the initial oven temperature was set to −20 °C, program-
RMSECV (kPa) 11.0 0.6 9.1 9.7 4.7 ming was set from 10 °C·min−1 to 430 °C, this temperature was main-
RMSEP (kPa) 6.8 0.4 8.1 7.4 3.6 tained over 2 min; the injector temperature was set to 430 °C; and the
R2c 0.9285 0.9954 0.9057 0.7303 0.8851
detector temperature was set at 435 °C, with helium used as a carrier
R2cv 0.2783 0.9945 0.2154 0.1615 0.7588
R2p 0.7581 0.9976 0.6989 0.4616 0.8933 gas.
biasa 0.9998 0.9737 0.8121 1.0000 0.9487
biasb 0.0538 0.9564 0.0348 0.8047 0.6459 2.3. Data processing
p-valuec 0.4157 0.3455 0.0530 0.4500 0.4441
p-valued 0.3923 0.0835 0.5059 0.2151 0.0874
The chromatograms were pre-processed with alignment using the
a
p-value of the bias test to evaluate systematic errors in calibration set. icoshift algorithm [37]. To execute alignment, the chromatograms were
b
p-value of the bias test to evaluate systematic errors in prediction set. configured at 50 equally spaced intervals of retention time, and over
c
p-value of the random test to evaluate trend errors in calibration set. these intervals peaks, they were aligned individually based on an
d
p-value of the random test to evaluate trend errors in prediction set. average chromatogram, which was used as a reference (Fig. 1S). Then,
variations in the baselines were removed using the AirPLS algorithm
volatile components of the oil [27,28], in this paper, we present a [38].
means to estimate these two properties of crude oil, from gas chroma- The merger of the distribution curves by the boiling points and the
tographic data, through multivariate calibration. mass recovery of the HTGC and DHA techniques followed the ASTM
D7169 standard [19]. We graphically analysed each curve obtained
2. Methodology from the same sample using both methods; we identified the merger
point of both curves, defined as T10%, which is the point equivalent to
2.1. Physicochemical properties temperature observed under elution at approximately 10% mass re-
covery. At the merger point of T10% corresponding to elution up to n-
In this study, we used 107 crude oil samples from a Brazilian se- paraffin C9 (nonane) [26–28], we calculated the correction made to the
dimentary basin. These oils presented American Petroleum Institute mass recovery value of the HTGC simulated distillation curve, as its
(API) gravity, which is an arbitrary scale used to measure density levels, initial extreme can be compromised by a lack of data on volatile
from light (54.0) to heavy (11.4) oils [36]. To measure the flash point compounds. From this merger point, for each next point of the HTGC
and Reid vapor pressure, ISO 13736 [4] and ASTM D323 [5] were curve, we added the mass difference measured between the DHA and
applied, respectively. To determine the flash point (°C), the sample was HTGC curves at the merge point.
cooled, and then a test portion was placed in the test cup of an Abel For the construction of a complete curve, we employed linear in-
apparatus (Abel closed-Cup method) and was heated with constant terpolation to estimate the values of the function at intermediate points
agitation. Over small temperature intervals of between 1 °C and 2 °C, a of the interval generated between the two curves. The values of the
spark was directed through an opening in the cover of the test cup. The DHA and HTGC curves, at the merger point, were the inputs in this
lowest temperature at which the oil surface ignited momentarily with function for the interpolation. The final curve obtained was softened, by
the test spark was recorded as the flash point, which is equivalent to the means of polynomial equations, selected via the adjustment of each
ambient atmospheric pressure [4]. curve, used at the order of 6 or 7. The Supplementary materials illus-
For the Reid vapor pressure (kPa) assay, the sample was cooled and trate the fit for a curve (Figs. 2S, 3S and 4S).
maintained at between 0 and 1 °C. It was then heated in a vapor We developed five PLS prediction models from the chromatogram
chamber equipped with a manometer and immersed in a thermostatic data for each property. For the flash point, we created: Model 1 – DHA1,
bath at 37.8 °C (60°F). The RVP was the pressure recorded after con- with 66 samples derived from DHA data; Model 2 – HTGC1, with 51
secutive measurements were drawn from the manometer, according to samples derived from HTGC data; Model 3 – DHA2 and Model 4 –
which system reached an equilibrium [5]. HTGC2, both with the same 42 samples derived from DHA and HTGC
data, respectively; and Model 5 – FUSION1, with 31 samples derived
2.2. Gas chromatography analyses from fusion data. In the same way, the models for the Reid vapor
pressure were developed, with a different number of samples for model
Of the 107 samples used in this work, 98 were analysed via the 1 and model 2 (50 and 84 samples, respectively).
HTGC method, and 67 were analysed by the DHA method. The data For the FUSION1 model, we employed high-level data fusion [39],
merger involved the use of data from 42 samples derived from both and the results derived via DHA and HTGC were combined to obtain the
chromatographic methods. final result. The Supplementary materials show histograms with re-
The DHA assay followed the standard ASTM D7900 method [25]. ference to the FP and RVP value distributions (Figs. 5S and 6S) for the
The chromatograph was equipped with a pre-column DB-5, 1 m; an oil samples.
analytical column HP-1, 100 m × 0.25 mm, coated movie poly- All of the models were developed following the same procedure.
dimethylsiloxane, 0.5 μm; a valve for backflush, enabling volatile First, a dataset was pre-processed via Standard Normal Variation (SNV)
components to enter the analytical column and eliminating components [40]. For each model, a dataset was separated into calibration (70%)
of roughly n-C15+ by backflush; and a flame ionization detector (FID). and prediction (30%) data using the rank_KS algorithm [41]. The

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M.H.C. Nascimento et al. Fuel 234 (2018) 643–649

Fig. 5. Correlation between reference values and Reid vapor pressure prediction. (A) Model 1, DHA1; (B) Model 2, HTGC1; (C) Model 3, DHA2; (D) Model 4, HTGC2;
(E) Model 5, FUSION1.

number of latent variables included in each model was optimized via prediction (R2p) of the model sets was evaluated as a linearity para-
cross validation using the venetian blind-5-fold. meter of the model using Eq. (3).
The models were evaluated for accuracy using the metric of the root
∑i (yi −yi )̂ 2
mean square errors of calibration (RMSEC) and prediction (RMSEP) R2 = 1−
using Eqs. (1) and (2), respectively. A model with greater accuracy ∑i (yi −y¯i )2 (3)
generates little prediction error.
where ȳ is the average reference value. All of the models were eval-
1 ncal uated through statistical tests to verify the presence of systematic errors
RMSEC = ·∑ (yi −yi )̂ 2 via a bias test [42], and tendentious errors in prediction residues were
ν i=1 (1)
identified through a non-parametric permutation test [42]. Further-
more, the models were evaluated based on their accuracy. A statistical
1 npre
RMSEP = ·∑ (yi −yi )̂ 2 F-test was applied to verify the equality between the accuracy of the
npre i=1
(2)
two prediction models via the root mean square error of prediction
where ncal and npre are the number of calibration and prediction (RMSEP) [29] with a 95% confidence level, as follows:
samples, respectively, yi and yi ̂ are, respectively, the reference and es- RMSEP12
timated values, and ν is the number of degrees of freedom (here, it Fcalculated =
RMSEP22 (4)
equals the number of calibration samples minus the number of variables
latent in the PLS model minus 1 because the models are mean centred) where RMSEP2 must be equivalent to the model that should be more
[42]. accurate; thus, RMSEP1 > RMSEP2. When the p-value of the F-test is
The coefficient of determination for the calibration (R2c) and lower than the confidence level, the hypothesis of uniform accuracy is

647
M.H.C. Nascimento et al.
rejected, revealing a significant difference in the accuracy levels of the
models evaluated through the test.
3. Results and discussion
The peaks corresponding to n-alkanes of up to n-C10 were observed
at DHA chromatograms (Fig. 1). These peaks are described in the lit-
erature as poorly resolved for first five minutes according to the chro-
matograms when using the HTGC approach [24,26–27]. A peak of si-
milar intensity was reached over approximately 17 min (Fig. 1(A)–(C))
and corresponded to the internal standard 3,3-dimetylbutene used for
the chromatogram alignment. The n-alkane components were found to
be more intense in the light oil sample (Fig. 1(A)), as this oil type in-
cludes more volatile components and, consequently, more substances
that can evaporate, thus creating an inverse relationship with the flash
point value. The chromatogram of the medium oil (Fig. 1(B)) presents
the same peaks, but with a considerable reduction of intensity levels, as
was expected for this type of oil. It also shows (the region covering
36–39 min) an enlargement of the peak corresponding to isomers n-
heptane and methyl-cyclohexane. The chromatogram for the heavy oil
(Fig. 1(C)) presents an absence of such peaks.
Fig. 2 shows the HTGC chromatograms for the samples presented in
Fig. 1. A predominance of n-alkane peaks were found for the light oils
(Fig. 2(A)). Peaks within the first five minutes of elution and in the
highlighted region shown in the box, correspond to n-alkane
[24,26–28]. The initial and final regions of the chromatogram show
similarities between different API gravity samples with a reduction in
the predominance of n-alkanes with a decline in API gravity. From the
medium oil chromatogram (Fig. 2(B)), we consequently find an impact
on the baseline resulting from an increase in the detector’s response to
the mass flow of the heavier components [20,24]. This effect is more
visible on the largest chromatogram shown for heavy oil. The heavy oil
chromatogram (Fig. 2(C)) shows a profile of biodegraded oil presenting
a reduced n-alkane level. However, within a 20-minute period, peaks
are found between n-C24 and n-C32, and these may correspond to
hopane biomarkers, which are pentacyclic compounds (C30 and C31)
that are more resistant to biodegradation than n-alkanes [43]. The
alignment chromatogram peaks at the icoshift [37] corrected retention
time displacement.
3.1. TBP simulated curve
To obtain the TBP curve through merging of the gas chromato-
graphic data, the corrected HTGC curve and a linear interpolation by
polynomial functions, as described above (Methodology), are needed.
The merged curve made a stronger contribution to the compositional
data on the oil studied. The light-end before the T10% included the data
generated from the DHA technique, and that from the T10% point
forward was generated via the HTGC technique.
The polynomial smoothed the final curve. The degree of the poly-
nomial was defined according to best adjustment of the curve data,
varying it by between 6 and 7 degrees for the 42 samples. The curve is
softer for the initial region after the data is merged (Fig. 3(C)), due to
the elution of several components at very close boiling temperatures in
the DHA.
3.2. Estimation of physicochemical properties
The models exhibiting more predictive capacity in estimating the
flash point from the chromatographic data are presented in Table 1.
Graphs showing correlations between the predicted and reference va-
lues for the flash point are shown in Fig. 4. We found no evidence of
systematic errors and trends in residues (non-parametric permutation
test) at a significance level of 5% [12,42] for any of the models.
Among the models developed for data from each technique for FP
prediction, Model 3 (DHA2) generated an RMSEC of 7.3 °C, an RMSEP
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Fuel 234 (2018) 643–649
of 11.6 °C, an R2c of 0.8684 and an R2p of 0.8211. While Model 1
(DHA1) generated a smaller RMSEP (8.0 °C) than Model 3 (DHA2), the
F-test reveals no statistically significant difference between the RMSEP
values of the two models (p-value of 0.1488). The model developed
through data fusion (Model 5) shows an information gain with an
RMSEC of 3.5 °C, an RMSEP of 5.3 °C, an R2c of 0.9797 and an R2p of
0.8963. The F-test shows an improvement in the accuracy of Model 5.
According to the standard method [4], repeatability and reproducibility
are valued at 1 °C and 1.5 °C, respectively, falling below the RMSEP
values obtained for the models.
The results for the crude oil FP present expected and acceptable
values compared with the results reported in the literature for petro-
leum derivatives. Dai et al. used a model of molecular contribution of
groups and multiple linear regression (MLR) to determine the flash
point of hydrocarbon mixtures and obtained an RMSEP of 10.5 K and an
R2p of 0.8730 [7]. Alves et al. reported estimation results for the flash
point of diesel fuel, with an RMSEP of 3.8 °C and an R2p of 0.698, via
PLS, and by support vector regression, an RMSEP of 1.98 °C and an R2p
of 0.936 [9]. Filgueiras et al., in studying diesel oil, obtained an RMSEP
of 3.75 °C and an R2p of 0.844 [12].
For RVP, the results show a close relationship to the reference va-
lues (Table 2). The Model 2 (HTGC1) achieved an R2c of 0.9954 and an
R2p of 0.9976 (Fig. 5). This model presents more accuracy, generating
an RMSEC of 0.6 kPa and an RMSEP of 0.4 kPa, which fall below the
repeatability and reproducibility values of the standard method [5] of
3.2 kPa and 5.2 kPa, respectively. The F-test reveals a significant dif-
ference in the accuracy of Model 2 (HTGC1). However, the F-test shows
no statistically significant difference between Models 1 (DHA1), 3
(DHA2), 4 (HTGC2) and 5 (FUSION1) at the 5% significance level.
A reduction in the number of samples generated less accurate
models, which is more visible from the model based on HTGC data. The
F-test reveals a significant difference between Models 2 (HTGC1) and 4
(HTGC2), and no significant difference between Models 1 (DHA1) and 3
(DHA2).
While data fusion did not result in an increase in available in-
formation, the approach reduced the error values for the models based
on fewer samples. The model employing high-level data fusion
(Fusion1) generated an RMSEC of 3.5 kPa and an RMSEP of 3.6 kPa. The
F-test shows a difference in accuracy levels of the Fusion1 only with
HTGC2 models (p-value of 0.034). Thus, data fusion did not improve
the accuracy but reduced the RMSEP values (44% and 48%) of Models 3
(DHA2) and 4 (HTGC2), respectively.
The results show that the HTGC data can better predict the Reid
vapor pressure in petroleum. The limitations of this technique in ad-
dressing the most volatile compounds did not interfere with the results
derived at Reid vapor pressure levels of 23.2 kPa–51.0 kPa. This direct
relationship with vapor pressure may reflect a principle of gas chro-
matography. From the models, we found no evidence of systematic
errors (t-test) or residue trends (non-parametric permutation test) at a
significance level of 0.05 [12,42].
The results for RVP in crude oil are stronger, when evaluated with
those reported in the literature for the estimation of the gasoline RVP.
Mendes et al. used gasoline samples of between 49.1 kPa and 67.4 kPa
and achieved an R2p of 0.97, from distillation data and PLS [16]. Côcco
et al. determined the RVP of Brazilian gasoline, using used DHA data
and regression non-linear ANNs, with an average error of 1.67% [14].
Choudhury et al. evaluated RVP values experimentally and made pre-
dictions via a computational model simulated, with relative standard
deviations (RSD) at 4.0%–6.7% for five gasoline blends [44]. Silva et al.
evaluated the effects of the addition of oxygenates and nonoxygenated
additives (e.g., isooctane and toluene) on the RVP values at gasoline
compositions of 28 kPa and 47 kPa [45]. The results were compared to
the RVP values derived from the different formulations with additives.
Here, we predicted the RVP of the crude oil from the HTGC1 PLS model
with an RMSEP of 0.4 kPa. We consider crude oil, which is more
complex than products such as gasoline, due to its larger number of
M.H.C. Nascimento et al.
components.
4. Conclusion
In this paper, we propose a means of estimating the flash point and
Reid vapor pressure for crude oil via detailed hydrocarbon analysis
(DHA) and high temperature gas chromatography (HTGC) involving
multivariate calibration. From the fusion information derived from two
chromatographic techniques (DHA and HTGC), it is possible to estimate
the flash point with an average error of 5.3 °C and with a coefficient of
determination of approximately 0.9. Data fusion represents an in-
formation gain in the flash point estimation; however, to estimate Reid
vapor pressure, an HTGC chromatogram is sufficient. The PLS regres-
sion exhibits the best results for Reid vapor pressure, with an average
error of 0.4 kPa and coefficient of determination above 0.99.
Acknowledgements
The authors thank the Centro de Pesquisas e Desenvolvimento
Leopoldo Américo Miguez de Mello (Cenpes-Petrobras) for providing
the samples and physicochemical analyses, and FAPES
(33530.503.20537.12092017), CAPES and CNPq (process number
422515/2016-7) for the financial support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.fuel.2018.07.050.
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