Vibrational Spectroscopy 109 (2020) 103071

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

An effective and rapid approach to predict molecular composition of T

naphtha based on raw NIR spectra
Ling Zhua,b, Shao Hua Lua, Yao Heng Zhangb, Hong Lin Zhaia,*, Bo Yina, Jia Ying Mia
a
College of Chemistry & Chemical Engineering, Lanzhou University, Lanzhou, 730000, China
b
Research Institute of Lanzhou Petrochemical Corporation of Petrochina, Lanzhou, Gansu, China

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

Keywords: Molecular management has become an important trend in petroleum refining, which relies on the information of
Near infrared (NIR) petroleum composition. In this contribution, a simple and effective analytical approach is proposed for the rapid
Tchebichef curve moment (TCM) prediction of the more detailed molecular composition of naphtha samples based on raw near infrared (NIR)
Molecular composition spectroscopy for the first time. The 101 samples of reformed naphtha were collected and determined, and
Naphtha
Tchebichef curve moments (TCMs) were calculated directly from the raw NIR spectra and employed to establish
PIONA
Pretreatment
linear models for the quantitative analysis of 26 hydrocarbons (PIONA) with different carbon numbers and
components. For the obtained models, the average of RMSE of prediction is 0.10. According to the ratio of
performance to deviation (SD/RMSEp), the 23 obtained TCM models achieved “excellent” predictive quality. By
means of the conventional PLS method with spectral pretreatment, there were only 15 models with “excellent”
predictive quality, which indicated that TCM method without any spectral preprocessing could provide more
simple, accurate and reliable analytical results, and meet the requirements of fast assessment. This work suggests
the feasibility of the proposed method for the rapid and non-destructive analysis of molecular composition in
naphtha, which is significant in the determination of refinery operating conditions.

1. Introduction composition is very important. Furthermore, the hydrocarbon compo-

Nowadays, an important goal in the petroleum refining industry is
to achieve maximum utilization of resources. The deeply characterizing
petroleum and related products at the molecular level has been re-
cognized as a critical future direction during the last decades, with
more emphasis on the molecular composition of refining products [1].
Molecular management [2], which breaks through the traditional un-
derstanding of petroleum refining [3], requires to generate the most
valuable molecules from refining products at the right place, right time
and rational price [4]. This is not an easy work due to the challenge of
analyzing the molecular composition in crude oil that is a complex
mixture. Therefore, one key step is to develop the effective methods to
rapidly characterize and predict the detailed molecular composition
information of complex petroleum products [5].
Naphtha is expensive and a much-valued component in petroleum
industry. It is a complex mixture of low molecular weight paraffins,
isoparaffins, naphthenes and aromatic in the C5–C12 range of compo-
sitions [6]. The paraffins can be used for hydrocracking to ethylene, and
the naphthenes can be used to catalytically reformate aromatics. When
selecting proper catalysts, the information of the hydrocarbon
sitional data has also become very important due to environmental
concern related to emission and its control [7].
In terms of petroleum refining, to accomplish the maximum utili-
zation of naphtha, we should make management of the processing at
the molecular level. Thus the detailed, rapid and accurate analysis of
hydrocarbon mixtures is the first step. After that, it allows to predict
refinery operating conditions in further processing and applications [8].
A great number of analytical techniques are used for the detailed
analysis of hydrocarbons present in petroleum and distillates. Gas
chromatography [9], for instance, is capable of providing the con-
centrations of different compounds present in petroleum content. Pet-
rochemical products consists of thousands of compounds, flame ioni-
zation detector (FID) is considered to be the most suitable detector for
routine and quantitative hydrocarbon analysis because it is assumed
that all compounds have similar response factors when they belong to
the same compound class [10]. The common fractionation methods
used in the oil industry to express crude oil compositions are: PNA
(Paraffins, Naphthenes, Aromatics), PIONA(Paraffins, Isoparaffins,
Olefins, Naphthenes, Aromatics), SARA(Saturates, Aromatics, Resins,
Asphaltenes) [1].

⁎
Corresponding author.
E-mail address: zhaihl@163.com (H.L. Zhai).

https://doi.org/10.1016/j.vibspec.2020.103071
Received 5 March 2020; Received in revised form 30 March 2020; Accepted 13 April 2020
Available online 25 April 2020
0924-2031/ © 2020 Elsevier B.V. All rights reserved.
L. Zhu, et al.
PIONA is employed in the study of the composition of light oils,
which generate distillates with lower boiling points [11]. As detailed
hydrocarbon analysis of reformed naphtha samples, PIONA has great
importance in the petrochemical industry. It allows a correct char-
acterization of samples to predict their behavior in further processing
and applications [8]. Now there is well-developed ASTM method
(ASTM D-5134-r03) for the parameter. The obtained gas chromato-
graphic data was processed by the PONA software. If the chromato-
graphic peak has shift caused by other chemical bonds, make appro-
priate correction by comparing with standard chromatogram.
Quantitative analysis can be carried out when the chromatographic
peak matching degree with the standard spectrum reaches more than
90 %. Then the percentages content of PIONA were obtained. But the
procedures need a long analysis time (it may cost 2 h for one sample)
[12] and the rich experience of technicians, require expensive and
maintenance–intensive equipment, and are not well suitable for on-line
determination [13].
The combination of the near infrared spectroscopy (NIR) and mul-
tivariate calibration methods has many advantages in petroleum ana-
lysis [14], such as simple, high speed, cheapness, efficiency, eco-
friendly, non-destruction and so on [15]. In recent years, the NIR based
on chemometric algorithms has been widely applied to the in-line or
on-line monitoring and controlling of refinery processes, such as crude
distillation, catalytic cracking and gasoline blending [16]. Many im-
portant parameters of petroleum and petroleum products have been
predicted accurately and precisely [17,18]. Balabin et al. [19] built an
effective calibration model to predict four properties (fractional com-
position, iodine value, and cold filter plugging point) of biodiesel fuel,
based on near-infrared (NIR) spectroscopy data and an artificial neural
network (ANN). By comparison, the ANN approach was superior to the
other calibration methods, such as PLS. Li et al. [13] based on NIR
spectroscopy and Monte Carlo virtual spectrum to determine the hy-
drocarbon groups of gasoline samples. The results meet the require-
ments of fast analysis. But PLS, ANN, Monte Carlo and other methods
need spectra preprocessing, which may loss some useful information. At
the same time, the hydrocarbon information is not detailed enough to
guide refinery operating conditions in petroleum processing.
Partial least square (PLS) is the most popular method to build the
quantitative model. However, due to the weak absorption and the
broad peaks of NIR spectra, the quantitative or qualitative results ob-
tained by PLS method generally yields low sensitivity and low se-
lectivity. At the same time, especially in complex samples, the inter-
ferences of irrelevant information, overlapping and shifts of peaks
appear mostly in NIR spectra, which seriously affected the accuracy of
the PLS models. Therefore, in order to cover these shortages before
modeling several, spectral pretreatment techniques were developed,
such as the orthogonal signal correction [20], standard normal variate
[21], multiplicative scattering correction [22], continuous wavelet
transform [23] and iPLS [24], which have been removed the noise and
background in the raw spectra so as to enhance the reliability of NIR
spectral analysis. Nevertheless, these pretreatment methods are still the
risk that might result in loss of useful information. Thus, it is necessary
to develop some simple and effective chemometric methods to realize
on-line monitoring of the NIR spectroscopy.
As one of the discrete orthogonal moments, the Tchebichef image
moment (TIM, also called Chebyshev image moment) has an excellent
description ability with multiresolution and invariance properties and
has been widely applied in image processing. Although TIM has been
employed successfully in analytical chemistry to determine multi-
compounds in complex samples based on the several chemical 3D
spectra [25], for the analysis of chemical curve spectra, image moments
are not convenient. Then, the Tchebichef curve moment (TCM) method
was extended [26].
In this work, TCM was applied to the simultaneous quantitative
analysis of the 26 components (PIONA) with different carbon numbers
and components in naphtha based on the raw NIR spectra. As the
2
Vibrational Spectroscopy 109 (2020) 103071
comparisons, classical PLS methods with spectral pretreatment were
also carried out.
2. Experimental
2.1. Samples and their NIR spectra
A total number of 101 naphtha samples were collected over a period
of one year from the refining unit.
NIR spectra were recorded on a Fourier-transform near infrared
spectrometer (SupNIR-4510, Focused Photonics Inc, China) from 1600
to 1000 nm (6400 to 4000 cm−1). For each sample, the measurements
were made every 30 s, then choosing 10 spectra with a deviation of less
than 5 parts per 10,000. The 10 scans were made with a spectral re-
solution of 6 cm−1 and then averaged to minimize interferences.
Samples were temperature equilibrated at 35 °C in the constant tem-
perature drying oven before scanning.
The samples were divided into two groups randomly, training set
(80 % of the entire data set) and test set (20 % of the entire data set).
The quantitative models were established by chemometrics methods
based on the training set, and their predictive ability were evaluated by
the test set as external independent samples that were excluded from
the modeling procedure.
2.2. The percentages content of PIONA
The PIONA analysis including the estimation of hydrocarbons was
carried out on the GC-FID (ASTM D5134-98 r03). The GC system con-
sisted of a 6890 GC system (Agilent Technologies, USA). GC analysis
was performed on a 19091S-001 HP-PONA capillary chromatographic
column (50 m × 20 μm × 0.5 μm; Agilent Technologies, USA). The in-
jection volume was 1 μL. The programmed temperature was adopted.
The initial temperature was 35 °C–200 °C in 1 °C/min.
Gas chromatographic data was processed by the software PONA
(E.05.02). The data are analyzed qualitatively and quantitatively by
comparing the correction table. If the chromatographic peak has shift
caused by other chemical bonds, make appropriate correction. The re-
producibility of the method was evaluated by analyzing standard
sample of naphtha. The method showed satisfactory results for quan-
titative purposes with the relative standard deviations (RSDs) ranging
from 0.02 % to 0.03 %.
The 26 PIONA percentages contents in 101 naphtha samples were
listed in Table 1.
2.3. Modeling and evaluation
2.3.1. Tchebichef curve moments
Tchebichef curve moment (TCM) had been defined in the reference
[26]. Here, a brief description is provided as follows:
N −1
1
Tn =
ρ˜ (n, N )
∑ t͠n (x ) f (x )
x=0
n = 0, 1, 2, … N − 1 (1)
When the values of n are increased to a certain point (nN), the
significant information in the curve can be extracted adequately by the
set of calculated TCMs according to the reconstruction error.
The calculated TCMs were regard as independent variables and the
concentrations of target compounds were denoted by response vari-
ables, stepwise regression was employed to establish linear quantitative
models.
2.3.2. PLS algorithm
With regression by partial least squares, the arrays X and y are de-
composed into smaller matrices that contain relevant information about
the samples (called scores) and the original variables (loadings).
L. Zhu, et al. Vibrational Spectroscopy 109 (2020) 103071

Table 1
Mean, range, and standard deviation (SD) of percentages concentrations of the
PIONA.
No. Chemical Mean Range Standard deviation

1 p5 0.24 0−1.15 0.32

2 p6 5.43 3.62−6.53 0.62
3 p7 6.88 5.67−7.84 0.46
4 p8 7.61 5.82−8.55 0.63
5 p9 2.82 0.78−4.12 0.70
6 p10 0.86 0.02−2.62 0.59
7 p11 0.07 0−0.34 0.10
8 i5 0.04 0−0.71 0.23
9 i6 4.44 2.22−6.48 0.83
10 i7 5.78 5.04−7.33 0.54
11 i8 8.00 5.02−9.64 1.12
12 i9 4.44 3.47−7.01 0.88
13 i10 1.78 0.54−3.65 0.64 Fig. 1. The raw NIR spectra of the naphtha samples for dataset.
14 i11 0.16 0−0.56 0.15
15 n5 0.26 0.04−0.90 0.24
16 n6 7.82 5.92−10.65 1.03 excellent (RPD > 2.5), very good (RPD = 2.5–2.0), good (RPD =
17 n7 14.40 11.47−17.18 0.99 2.0–1.8), fair (RPD = 1.8–1.4), poor (RPD = 1.4–1.0), and very poor
18 n8 10.52 8.16−13.33 0.94
model (RPD < 1.0). Generally, models with good performance should
19 n9 6.56 4.90−8.60 0.83
20 n10 0.44 0.01−1.48 0.36
have higher R2p and RPD values, lower RMSEP values.
21 n11 0.06 0−1.21 0.39 All calculation programs were written in M-file based on MATLAB
22 a6 2.98 1.74−4.80 0.66 7.0 and carried out with a PC (CPU 4.00 GHZ, RAM 32.0 GB).
23 a7 3.44 2.07−5.59 0.71
24 a8 3.66 2.65−4.71 0.42
25 a9 1.01 0.28−2.16 0.39 3. Results and discussions
26 a10 0.27 0.01−0.99 0.25

3.1. NIR spectral characteristics of naphtha

The PLS regression algorithm was employed to build quantitative
calibration models for hydrocarbon composition of naphtha. The ma-
trices containing the data provided by the NIR spectra, denominated by
X, and the vector Y containing the percent concentration of hydro-
carbon composition (PIONA), were employed to build the regression
model. During the established PLS models, the appropriate number of
latent variables (LVs) was selected according to the cumulative con-
tribution rate exceeded 85 %.
2.3.3. Spectral pretreatment
To eliminate the effects of the disturbing information such as noisy
signal, light scattering, baseline drift and so on, some preprocessing
methods were used in this research: Normalization (NOR),
Standardization (SD), Detrending (DT), Meancenter (MC) [27], Moving
window smoothing (MW), Savitzky-Golay smoothing (SG), Multi-
plicative scatter correction (MSC), Standard normal variate transfor-
mation (SNV) [28], First derivative (1D), Second derivative (2D) [29].
The results of TCM and PLS models based on these pretreatment
methods were used to evaluate the performances of these pretreat-
ments.
2.3.4. Evaluation of the obtained models
The robustness of the TCM and PLS models were evaluated based on
the correlation coefficient of prediction (R2p), the root mean square error
of prediction (RMSEp) and the ratio of performance to deviation (RPD):
n
∑i = 1 (yi, exp − yi, pred )2
RMSEp =
n (2)
SD
RPD =
RMSEp
where n is the number of samples in the validation test set, yi,exp and yi,
pred are the hydrocarbon composition measured by the GC experiment
and calculated with NIR models, respectively. y is the average of the
experimental values. SD stands for the standard deviation of predicted
samples.
Viscarra Rossel et al. [30] classified the RPD values into six classes:
The raw NIR absorbance spectra of naphtha which was character-
istic of the entire samples molecule were shown in Fig. 1. As can be seen
in Fig. 1, there exists the seriously overlapping and drift of peaks, and
the different colors of samples with different components affect their
NIR spectra, which are usually troublesome in analysis. A group of
atoms in a molecule may have multiple modes of oscillation caused by
stretching and bending motions of the naphtha group. The NIR spectra
of naphtha present major peaks at around 1153 nm, 1193 nm, 1208 nm,
1390 nm, 1411 nm and 1432 nm. NIR spectra present combination
bands of CeH and CeC bonds (typically from aliphatic hydrocarbons)
in the range from 1125 to 1280 nm, and first overtone bands of CeH
bonds in the range from 1340 to 1550 nm. The bands around 1192 nm
correspond to the second overtone, around 1390 nm to the 1 st overtone
combination.
3.2. Performance of obtained TCM models
The curve moment can be directly applied to the analysis of the
conventional spectrum, which makes the work simpler and easier. As
the same as TIM, TCM not only possess powerful multi-resolution as
well as the inherent invariance properties, but also do not involve any
numerical approximation in the computational process [26]. Therefore,
the information in the raw NIR spectra (including the target compo-
nents and interference components) can be represented by TCM with
different orders and separated automatically.
The obtained linear models are listed in supplementary materials.
The performance and predictive quality of the established linear
models are summarized in Tables 2. From Table 2, the values of R2p for
the 24 components are greater than 0.8, in which the R2p values of the
18 obtained models are more than 0.91. By the classification of RPD of
(3)
Table 2, the predictive quality of the 23 TCM models are excellent (RPD
＞2.5). The most of the established models have the high values of R2p,
RPD and the lower values of RMSEp, which shows that the proposed
models possess better prediction and generalization abilities.
The relationship between the experimental concentrations and cal-
culated concentrations by TCM of the 26 target components are illu-
strated in supplementary materials.

3
L. Zhu, et al. Vibrational Spectroscopy 109 (2020) 103071

Table 2
The parameters of TCM and PLS (with spectral pretreatment) models.
Chemical TCM PLS with spectral pretreatment

R2p RMSEp RPD Predictive Quality Method R2p RMSEp RPD Predictive Quality

p5 0.66 0.02 6.13 Excellent DT 0.64 0.14 1.32 Poor

p6 0.92 0.03 15.57 Excellent SD 0.94 0.16 2.68 Excellent
p7 0.96 0.02 23.80 Excellent NOR 0.90 0.17 2.90 Excellent
p8 0.92 0.08 8.42 Excellent MW 0.92 0.21 2.91 Excellent
p9 0.49 0.34 2.17 Very good SNV 0.48 0.63 1.08 Poor
p10 0.94 0.07 9.32 Excellent SNV 0.92 0.18 2.60 Excellent
p11 0.90 0.01 149.93 Excellent MC 0.92 0.02 3.45 Excellent
i5 0.56 0.01 3.09 Excellent 2D 0.12 0.14 0.37 Very poor
i6 0.86 0.12 6.75 Excellent 2D 0.90 0.27 3.16 Excellent
i7 0.79 0.05 7.20 Excellent 1D 0.94 0.16 3.21 Excellent
i8 0.85 0.59 1.82 Good 2D 0.86 0.46 2.37 Very good
i9 0.28 0.58 0.69 Very poor MSC 0.61 0.63 0.66 Very poor
i10 0.92 0.06 12.57 Excellent 2D 0.92 0.19 3.16 Excellent
i11 0.79 0.01 33.49 Excellent DT 0.83 0.05 2.35 Very good
n5 0.71 0.01 23.53 Excellent DT 0.77 0.04 2.07 Poor
n6 0.98 0.02 49.19 Excellent DT 0.92 0.35 3.23 Excellent
n7 0.98 0.03 36.30 Excellent MSC、SNV 0.90 0.33 2.53 Excellent
n8 0.88 0.23 4.80 Excellent DT 0.81 0.46 2.47 Very good
n9 0.94 0.14 6.18 Excellent SD 0.83 0.41 2.26 Very good
n10 0.86 0.01 45.37 Excellent DT 0.86 0.10 3.71 Excellent
n11 0.83 0.01 123.50 Excellent MSC 0.85 0.02 2.66 Excellent
a6 0.92 0.04 17.38 Excellent 2D 0.92 0.19 3.74 Excellent
a7 0.98 0.01 78.54 Excellent DT 0.96 0.13 5.11 Excellent
a8 0.66 0.07 3.75 Excellent 2D 0.61 0.22 1.83 Good
a9 0.94 0.01 49.41 Excellent MSC、SNV 0.88 0.14 2.35 Very good
a10 0.92 0.01 43.58 Excellent SNV 0.85 0.08 2.78 Excellent

Note: (1) Values listed are related only to the optimal results for each pretreatment method.
(2) Abbreviation: Normalization (NOR), Standardization (SD), Detrending (DT), Meancenter (MC), Savitzky-Golay smoothing (SG), Moving window smoothing
(MW), Multiplicative scatter correcction (MSC), Standard normal variate transformation (SNV), First derivative (1D), Second derivative (2D).

The spectral preprocessing methods were also used to TCM mod- suitable preprocessing methods can effectively improve the perfor-
eling. The results of preprocessing don't make too much difference ex- mance of PLS models, because there are various interference factors on
cept for i8 and i9 (Details are listed in supplementary materials). For raw NIR spectra.
TCM models, the RPD of i8 and i9 are less than 2.0 (RPDi8 = 1.83,
RPDi9 = 0.69), so the results present a little worse prediction ability
with respect to the other studied targets. Compared with other hydro- 3.4. Comparison of TCM method and traditional PLS method
carbon compounds, the NIR spectra of isoparaffins has more inter-
ference such as overlapping peaks, unknown interfering substances, From Table 2, the most R2p values of the obtained TCM models are
noise and drifts. So for excellent model (RPD＞2.5) of TCM, there is no higher than or near to the PLS models. All the values of RMSEp calcu-
need to do the spectral preprocessing. When RPD＜2.5, proper pre- lated by TCM are lower than PLS. At the same time, all the values of
treatment methods can be done to improve the performance and pre- RPD calculated by TCM models are higher than that of PLS models. For
dictive quality of the established models. TCM, 23 models of the predictive quality meet “excellent”. But for PLS
modeling with spectral pretreatment, only 15 models of the predictive
quality meet “excellent”. In supplementary data, the value of pre-
3.3. Performance of PLS models
processing methods doesn't make too much difference for TCM models,
but spectral pretreatment before PLS modeling can greatly improve the
PLS regression was carried out based on the same dataset, and the
accuracy of the models. Therefore, all the results mean that the per-
26 PLS models for the target components were established, respec-
formance of the TCM models are superior to that of PLS models with
tively. PLS models without preprocessing data are listed in supple-
spectral pretreatment.
mentary data, most of the PLS models without spectral pretreatment are
The main reasons are that the different unknown interferences in
not ideal. Only four models of the predictive quality meet “excellent”.
real samples severely affect the distributions in data, which leads to the
Four models are “very poor”, and seven models are “poor”.
poorer performance of the PLS models established based on standard
The optimal results of the obtained PLS models by pretreatment
samples. However, the TCM with different orders can separate the
methods are listed in Tables 2. Models with good performance should
target and interference components. The important features of target
have higher R2p and lower RMSEP values, then choose respectively the
components can be extracted effectively to establish models, mean-
more optimal model. In Table 2, if the subtractive value before and
while, the interference components can be eliminated.
after processing is greater than 0.1, the parameters are bold.
The TCM can be used entire raw NIR spectra without spectral pre-
For most of PLS models, spectral preprocessing is commonly used to
treatment to predict molecular composition of naphtha. It can be con-
correct measurements and noisy spectra. We use multiple processing
sidered an excellent model and an effective, rapid approach to build the
methods to enhance the more chemically relevant peaks in the spectra.
model to predict molecular composition. Therefore, the proposed TCM
There has been a lot of literature which reported that each processing
method is expected to be applied for the quantitative analysis of mul-
method has its own advantages and disadvantages, so selection of the
tiple target components based on conventional NIR spectra.
most optimal model process by relevant parameters is needed. After
preprocessing, the results have marked improvement that 15 models of
the predictive quality meet “excellent”. It can be concluded that

4
L. Zhu, et al.
4. Conclusions
In the present contribution, a Tchebichef curve moment (TCM)
approach was applied for the quantitative analysis of 26 hydrocarbons
(PIONA) with different carbon numbers and components in naphtha
samples based on the raw NIR spectra determination. Compared with
similar work in the literature, our advantages are as follows: (1) The
prediction models of PIONA components in naphtha were obtained
with TCM method based on full NIR spectra without any spectra pre-
processing. (2) More detailed molecular composition information can
be obtained; (3) Compared with the traditional PLS models with spec-
tral pretreatment, the TCM models present higher anti-interference
ability especially for complex spectral signals; (4) All the results of
molecular composition can be got just for a few seconds; (5) This simple
and convenient method is expected to be a rapid and reliable analytical
technology applied to the quality assessment of refining products.
CRediT authorship contribution statement
Ling Zhu: Methodology, Data curation, Software, Writing - original
draft. Shao Hua Lu: Software. Yao Heng Zhang: Validation. Hong Lin
Zhai: Conceptualization, Writing - review & editing, Supervision. Bo
Yin: Visualization. Jia Ying Mi: Visualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.vibspec.2020.103071.
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