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Muller 2013
Muller 2013
Analytical Letters
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To cite this article: Aline L. H. Muller , Rochele S. Picoloto , Regina C. L. Guimaraes , Ricardo A.
Guarnieri , Bianca M. S. Ferreira , Julio C. M. Dias , Maria F. P. Santos , Erico M. M. Flores & Edson I.
Muller (2013) Determination of Basic Nitrogen in Residues of Crude Oil Distillation Using ATR-FTIR and
Chemometric Methods, Analytical Letters, 46:18, 2879-2889, DOI: 10.1080/00032719.2013.828299
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Analytical Letters, 46: 2879–2889, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2013.828299
Chemometrics
A method for basic nitrogen determination in residues of crude oil distillation using infrared
spectroscopy and chemometrics algorithms was developed. Interval partial least squares, syn-
ergy interval partial least squares, and backward interval partial least squares were evaluated
for calibration model construction. The samples were divided into a calibration and prediction
set containing 40 and 15 samples, respectively. The first derivative with a Savitzky-Golay fil-
ter and the mean centered data showed the best results and were used in all calibration mod-
els. The backward interval partial least squares algorithm with spectra divided in 60 intervals
and combinations of 4 intervals (1407 to 1372; 1117 to 1082; 971 to 936; 914 to 879 cm1)
showed the best root mean square error of prediction of 0.016 wt%. This calibration model
displayed a suitable correlation coefficient between reference and predicted values.
Keywords: ATR-FTIR; Backward iPLS; Basic nitrogen; Chemometrics; Crude oil residues; Interval PLS;
Synergy iPLS
INTRODUCTION
Nitrogen compounds are present in crude oil and their concentration generally
ranges from 0.1 to 0.9%. Despite this relatively low concentration, the presence of
2879
2880 A. L. H. MULLER ET AL.
nitrogen compounds can affect many of the important petroleum refining processes
(Speight 2001). Due to high polarity and basicity, nitrogen species, even at very
low concentration levels (mg kg1), may poison the catalysts used in cracking and
hydrocracking reforming process (Mills, Boedeker, and Oblad 1950). Compounds
containing nitrogen also reduce the stability of refined products due to gum forma-
tion (Batts and Fathoni 1991). Basic and neutral nitrogen compounds can be found
in the products of the distillation of petroleum. The basic nitrogen content in crude
oil ranges from 12 to 35% of the total nitrogen, depending on boiling point of the
derivative and crude oil origin. Moreover, basic nitrogen compounds have been
found in higher boiling fractions of crude oil and do not seem to be degraded by heat-
ing process during the atmospheric and vacuum distillation (Boduszynski 1987;
Merdrignac et al. 1998; Simon et al. 2010). The main basic nitrogen compounds present
in residues of crude oil distillation were the pyridine homologues (Speight 2001).
The classical method to measure basic nitrogen in crude oil is the UOP 269-10
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The application of variable selection methods has been performed for total acid
number (TAN) (Parisotto et al. 2010) and total sulfur determination in residues of
crude oil distillation using ATR-FTIR (Müller et al. 2012). In the first application,
the best results for TAN determination were obtained using the biPLS algorithm
with the spectrum split in twenty intervals which allowed obtaining the equivalent
root mean square error of prediction (RMSEP) in comparison with the full-spectrum
PLS model. In this case, the biPLS model used only 25% of the original variables
present in the full spectrum and it was possible to minimize the noise contribution
in the model (Parisotto et al. 2010). On the other hand, for total sulfur determi-
nation, significantly lower RMSEP was obtained using siPLS algorithm with spec-
trum divided into 20 intervals and combination of three intervals (Müller et al. 2012).
In the proposed method, the determination of basic nitrogen in residues from
crude oil distillation process was evaluated using ATR-FTIR and iPLS, siPLS,
and biPLS as algorithms for variable selection and subsequent calibration model
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construction.
EXPERIMENTAL
Materials and Sample Preparation
Fifty five samples of crude oil distillation residues (17 and 38 residues of atmos-
pheric distillation and of vacuum distillation, respectively) with basic nitrogen values
ranging from 0.047 to 0.430 wt% were used. Basic nitrogen was determined in resi-
dues of crude oil distillation using the UOP 269-10 method (UOP Method 269-10
2010). Toluene, acetic acid, acetone, and perchloric acid of analytical grade were
purchased from Merck (Germany).
Previously, the residues of crude oil distillation samples were heated up to 180 C
to promote the melt and then the heated samples were placed on top of ATR surface
to obtain the infrared spectrum. After analysis, the ATR crystal was cleaned using
toluene in a fume-hood.
Figure 1. Spectra of samples with different basic nitrogen values. Black line sample with basic nitrogen ¼
0.047 wt%; and gray line sample with basic nitrogen ¼ 0.380 wt%.
Model Construction
First, the average spectrum of three replicates was obtained for each sample
and calibration models were constructed using the PLS algorithm and spectra
information without excluded regions (called all variables model, 2150 variables).
Multiplicative scatter correction (Geladi, MacDougall, and Martens 1985) (MSC)
and first derivative with a Savitzky-Golay filter (D) (Savitzky and Golay 1964) were
used as treatment. Autoscaling (A) and mean centered data (MC) were evaluated as
pre-processing algorithms for the models construction.
The suitable number of latent variables was selected using the root mean
square error of cross-validation (RMSECV). In addition, the predictive ability of
the models was compared using the root mean square error of prediction (RMSEP)
that was calculated using the samples of the predictive set. Finally, the accuracy was
evaluated using weighted least square (WLS) (González, Herador, and Asuero 1999).
For the iPLS, siPLS, and biPLS algorithms, the spectra set was split into 10,
20, 40, and 60 intervals and all possible combination of two and three intervals were
evaluated using the siPLS algorithm. Finally, biPLS models were obtained with each
interval left out.
Table 1. Results for basic nitrogen PLS calibration models using all variables
a
VN, total variables numbers.
b
LVs, latent variables.
2884 A. L. H. MULLER ET AL.
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Figure 2. First derivative spectrum split in 60 different intervals. The horizontal black line represents the
RMSECV value for the full spectrum PLS model. Numbers inside the rectangles are the optimal number
of latent variables.
first derivative spectra divided in 60 different intervals. The RMSECV values of the
model with all variables are plotted in Figure 2 as a horizontal black line in order to
facilitate the comparison with RMSECV value of each interval. Models with each of
these regions were obtained and some of these models (constructed with 14, 16, and
27 interval) showed RMSECV values lower than the RMSECV value for all vari-
ables (spectra without excluded regions). However, improvement in predictive ability
was not observed for iPLS models constructed with spectra split in 10, 20, 40, and 60
intervals because significant differences were not observed in RMSEP values
obtained for this models. Probably, the spectral information correlated with the con-
tent of basic nitrogen may be located in different regions of the spectrum and iPLS
was not suitable as the interval selection algorithm.
a
VN, total variables numbers.
b
LVs, latent variables.
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1300 cm1, probably corresponding to ring stretching vibration of C-C and C-N of
the heteroaromatic nitrogen compounds) showed reduction in th RMSEP value of
about 60% in comparison with RMSEP value of PLS model (Table 2). Therefore,
the biPLS algorithm was also evaluated in order to obtain RMSEP values signifi-
cantly lower than those obtained by the PLS model with all variables.
biPLS Models
Models using the backward interval PLS algorithm also proposed the use of
spectral interval combinations to decrease the RMSEP value. Table 3 shows the
results for the best biPLS calibration models for basic nitrogen determination.
RMSECV and RMSEP values of biPLS40 and biPLS60 were significantly lower
when compared to RMSECV of PLS model with all variables (F test, 95% confidence
level). However, biPLS60 was selected as the best model for basic nitrogen determi-
nation because it was simpler and allowed a reduction of total variable numbers when
compared to the PLS model with all variables (from 2150 to 144). The biPLS60 model
was obtained when the spectra set was split into 60 intervals and the interval numbers
35, 46, 50, and 52 were used (Table 3). The selected intervals included the regions from
1407 to 1372 cm1 (interval 35) and probably corresponds to ring stretching vibration
of C-C and C-N of the heteroaromatic nitrogen compounds. The intervals 46 (1117 to
1082 cm1), 50 (971 to 936 cm1), and 52 (914-879 cm1) probably corresponded to
the bending of C-H of heteroaromatic nitrogen compounds (Silverstein et al. 1991).
a
VN: total variables numbers.
b
LVs: latent variables.
2886 A. L. H. MULLER ET AL.
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Figure 3. Errors for the prediction samples using the biPLS60 model.
The biPLS60 model showed an error lower than 10% for all prediction samples
(Figure 3).
The WLS method was also carried out with the results obtained with the
biPLS60 model for predictive sample set. The WLS results include the theoretical
expected value (1, 0), indicating that the proposed methodology is accurate and free
of systematic errors.
Figure 4 shows the values of basic N obtained for AR and VR samples obtained
by UOP 269-10 (2010) reference method and predicted values using ATR-FTIR and
the selected biPLS60 model. A correlation equal to 0.99 was obtained when the UOP
269-10 method and biPLS60 model values were compared.
Figure 4. Calibration graph obtained for the biPLS60 model using 35, 46, 50, and 52 intervals and 9 latent
variables.
DETERMINATION OF BASIC NITROGEN 2887
CONCLUSIONS
A backward interval PLS algorithm with ATR-FTIR data provided a suitable
model for basic nitrogen determination in crude oil residues. Moreover, the RMSEP
values obtained using the best model (biPLS60) was significantly lower in compari-
son with RMSEP values of the model constructed using all variables. A relative error
lower than 10% was obtained in comparison between results of reference method
(UOP 269-10 2010) and those obtained using biPLS60 model. The proposed method
is easy to use, needs short time for analysis, uses instruments that are easy to handle,
and has low operational costs.
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