Article: Daniel Molina-V., Roika Angulo, Fay Zuly Dueñez, and Alexander Guzman

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Article
Partial Least Squares (PLS) and Multiple Linear Correlations between Heithaus
Stability Parameters (Po) and the Colloidal Instability Indices (CII) with the
1H Nuclear Magnetic Resonance (NMR) Spectra of Colombian Crude Oils.
Daniel Molina-V., Roika Angulo, Fay Zuly Dueez, and Alexander Guzman
Energy Fuels, Just Accepted Manuscript DOI: 10.1021/ef4022224 Publication Date (Web): 11 Feb 2014
Downloaded from http://pubs.acs.org on February 12, 2014
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Page 1 of 34 Energy & Fuels
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Partial Least Squares (PLS) and Multiple Linear Correlations between
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6 Heithaus Stability Parameters (Po) and the Colloidal Instability Indices
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9 (CII) with the 1H Nuclear Magnetic Resonance (NMR) Spectra of
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12 Colombian Crude Oils
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15 Daniel Molina V.,*,, Roika Angulo, Fay Zuly Dueez, Alexander Guzmn
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18 Laboratorio de Resonancia Magntica Nuclear, Universidad Industrial de Santander,
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20 Apartado Areo 678, Bucaramanga, Colombia,
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Ecopetrol-Instituto Colombiano del Petrleo, Piedecuesta, Colombia
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29 ABSTRACT
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32 Various methods were developed to predict the stability of Colombian crude oils, in which
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34 the integral areas of the resonance signals from 12 regions of 1H nuclear magnetic
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37 resonance (NMR) spectra of 29 widely different crudes oils were correlated with the
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39 stability parameter of Heithaus (Po) and the colloidal instability index (CII). Correlations
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between the NMR spectra and properties were obtained using partial least squares (PLS)
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44 regression and multiple linear regression (MLR). The prediction models for Po and CII by
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46 PLS had coefficients of determination (R-squared) of R2>98% and R2>99%, respectively,
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49 while the cross-validation values CV-q2 ranged from 89% to 90%, respectively. The models
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51 obtained from MLR showed a high (adjusted R-Squared) R2ad for Po and a lower R2ad for
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53 CII. The R2 values of the prediction models for Po ranged from 97% to 98%. The use of
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56 these predictive methods is faster, more environmentally friendly and less expensive than
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ACS Paragon Plus Environment
Energy & Fuels Page 2 of 34
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3 conventional methods. Of the set of crudes used in this study, it was observed that the
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6 crudes with low tendency to precipitate asphaltenes are those with high aromatic content
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8 and low paraffin content because they exhibited a very low CII and a very high peptizing
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power for asphaltenes, Po. Considering the relationship between the asphaltene content and
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13 the peptizing power Po and the colloidal stability index CII, asphaltenes cannot be
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15 considered negative factors for the stability of some crude oils.
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22 1. INTRODUCTION
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25 Crude oils are complex colloidal systems that possess a dispersed phase composed of
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27 asphaltenes and resins whose stability is one of the most important factors in the petroleum
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30 industry.The term stability can be understood as a measure of the tendency of the
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32 asphaltenes to precipitate in relation to the oil.1 Asphaltenes, the most heavy fraction of the
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34 oils, have a tendency for precipitation, flocculation and sedimentation under specific
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37 temperature, pressure and composition (SARA: saturates, aromatics, resins and
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39 asphaltenes) conditions.2, 3, 4 Asphaltene precipitation is an indication of stability loss, and
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41 their precipitation in the petroleum reservoir, in the wells, during crude transportation and
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44 during refining causes a significant number of severe technological problems. Crude oils
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46 are classified as stable under conditions in which the oil does not have a tendency to
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precipitate the asphaltenes.5
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52 An evaluation of the colloidal stability of crude oils involves determining the solubility
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54 profile or solubility distribution of the asphaltenes in these materials, and this evaluation
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can be described by different models and indices. Some of these indices involve the
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60 2
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3 experimental determination of the precipitation of the asphaltenes by the addition of a non-
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6 solvent to the oils or solutions of oils in aromatic solvents, e.g., the Heithaus titration (P-
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8 index or Po). Other indices use the SARA composition, e.g., the colloidal instability index
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(CII). 6 Some include the toluene equivalence (TE) and the Bureau of Mines correlation
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13 indextoluene equivalence (BMCITE), which represents some of the parameters initially
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15 developed for the prediction of asphalts stability, and also the oil compatibility model that
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was developed for the prediction of the compatibilities of mixtures of oils and is also
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20 applicable to the evaluation of stability.1 The filter drop spreading method allows the
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22 accurate and rapid determination of the flocculation point of asphaltenes, which is
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25 measured in terms of the proportion of n-alkane added to the crude oil.7 With the exception
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27 of the CII, these indices require the experimental determination of the onset of precipitation
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29 of the asphaltenes.
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33 Heithaus results have been modified to generate a coke index, as the presence of coke
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35 appears to coincide with the depletion of resins, which are components that play a crucial
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37 role in the dispersion of asphaltenes. The Heithaus titration is a one-dimensional titration,
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40 and it has been replaced by a three-dimensional turbidimetric titration to determinate the
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42 structural stability of mixtures of old and new bituminous binders. The three dimensions
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are a visualization of the Hansen solubility parameters, displaying the dispersive, polar, and
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47 hydrogen-bonding components. The results from the three-dimensional titration
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49 demonstrated that it provides more detailed information regarding structural stability
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compared to the one-dimensional Heithaus titration.8
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55 A separate model to evaluate the colloidal stability of crude oils and related products uses
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57 an on-column precipitation coupled with an evaporative light scattering detector (ELSD).
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60 3
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3 On-column precipitated asphaltenes typically have bimodal distributions, where the
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6 separation between the peaks is related to the colloidal stability of the asphaltenes. In
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8 general, asphaltenes from unstable materials are characterized by wider solubility profile
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distributions than asphaltenes from stable materials.9
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14 Various methods have been reported to determine the stability of crude oils. Some of these
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16 have used light transmission, such as the microscopic examinations of solutions, 10
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18 refractive index,11 light scattering by particles,9 a solvent titration method with near-infrared
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21 (NIR) solid detection,12 and fluorescence spectroscopy. However, when the transmission is
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23 low, methods such as viscosimetry, conductivity, heat transfer analysis,16 critical voltage,13
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electric field, 14 zeta potential, 15 filtration and other similar procedures are the only
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28 options.16
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31 Another way to determine the stability of crude oils is with prediction models using
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spectroscopy data in conjunction with chemometric techniques, e.g., NIR spectroscopy in
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36 the range of 11002250 nm, together with a latent-variable regression technique,13 NIR and
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38 PLS.17
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Multiple linear regression (MLR), partial least-squares (PLS), and principal component
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44 analysis (PCA) and artificial neural networks (ANN) are multivariable data analysis
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46 methods that allow the construction of models to predict properties of crude oils and/or
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their fractions from NMR spectra. PLS regression combines characteristics from principal
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51 component analysis and multiple regression, and these methods were used to predict sulfur
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53 (% wt), N (ppm), waxes (% wt), MCR (% wt) insolubles in nC-7(% wt), vanadium (ppm)
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56 and nickel (ppm) in Colombian crude oils.18 Additionally, the combination of standard 1H
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60 4
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3 NMR spectroscopy and PLS analysis was employed for the rapid and accurate extraction of
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6 parameters pertaining to the physical and chemical properties of heavy fuel, and good
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8 prediction models were obtained for the calculated aromaticity index, the density, gross and
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net calorific values, and water and sulfur contents, as well as micro-carbon residue (MCR).
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13 The coefficients calculated by the PLS procedure revealed which parts of the NMR
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15 spectrum are important for the prediction of the various chemical and physical parameters.
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The MCR parameter is related to the oil stability, and the important regions of the NMR
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20 spectrum to predict this parameter is the region from 4.7 to 6.2 ppm, as well as small
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22 contributions from the 3.2-3.7 region and small negative effects from the aliphatic region
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25 near 1 ppm.19 The correlations between physicochemical properties and SARA components
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27 with the 1H NMR spectra of vacuum residues, represented by chemical shift regions, were
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29 determined using the MLR method. The MLR model for predicting SARA components is
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32 excellent for saturates, aromatics and resins; while the model for the asphaltene content is
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34 quite reasonable and is dependent on the chemical shift region from 6.0 to 8.9 ppm.20
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37 In summary, chemometrics is the statistical processing of analytical chemistry data with
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40 various numerical techniques to extract information. A series of mathematical
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42 manipulations of the data are used with a previously developed calibration model to predict
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the property of interest: RAW DATA, X Chemometrics: f(X) fuel property. The
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47 following calibration model was used in this work: NMR data, chemical shifts MLR (or
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PLS): f(1H-NMR chemical shifts) CII, or Po of crude oils. Based on the calibration
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52 model the fuel property of a new unknown sample can be determined.
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55 The goal of this study was to develop models to predict the stabilities of Colombian crude
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58 oils using partial least squares (PLS) and multiple linear regressions (MLR), in which the
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3 integral areas of the resonance signals of 1H-NMR spectra of 29 crudes oils were correlated
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6 with the stability parameter of Heithaus (Po) and the colloidal instability index (CII). The
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8 chemometric models accurately predicted the stabilities of asphaltenes, making possible a
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molecular approach for the description of the stability of crude in terms of the proportion of
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13 the different protons provided by the high-resolution 1H NMR spectrum. Coefficients,
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15 calculated by the multivariate algorithms MLR and PLS, indicated which protons influence
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positively and negatively the stability of crude oils and therefore providing a tool to blend
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20 crudes based on their contributions to the type of protons that are determinant of
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22 compatibility. This approach not only permits a quick and easy estimation of crude
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25 stability but also makes possible to develop or formulate additives with specific chemical
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27 structure to control crude oils stability.
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30 2. EXPERIMENTAL SECTION
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To investigate a very wide range of chemical compositions, 29 Colombian crude oils were
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36 used in this study. The SARA fractionation and the stability parameter of Heithaus (Po)
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38 were determined at the Instituto Colombiano del Petrleo (ECOPETROL-ICP).
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41 The parameter Po described in the ASTM D7112 standard method was used to determine
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44 the peptizer power of the maltenes. This method covers an automated procedure involving
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46 titration and optical detection of precipitated asphaltenes for determining the stability and
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compatibility parameters of crude oils. Using this method, the solubility power of the
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51 medium increases as the value of Po increases.
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54 The SARA procedure described in the ASTM-2007 standard method was used to determine
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the compositions of the oils. The colloidal instability index (CII) was calculated using eq. 1,
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60 6
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3 which is defined as the mass ratio between the sum of the asphaltenes and saturates and the
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6 sum of the peptizer agents (aromatics and resins).12
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9 %
%
Eq. 1
10 %%
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13 Table 1 shows the maximum and minimum values of the SARA components and the Po and
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15 CII data for the set of crude oils used in this study. The SARA components of 29
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18 Colombian crude oils and theirs CII and Po values are shown in Fig. 1 and 2, respectively.
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21 The 1H NMR spectra of the crudes were obtained using a Bruker Avance III 400 MHz
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23 spectrometer in 5% (wt) solutions in CDCl3 containing tetramethylsilane (TMS) as internal
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26 reference. This concentration was found to be optimal for avoiding a concentration
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28 dependence of the chemical shifts, and it also provided an excellent signal-to-noise ratio.
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The 30 pulses (Bruker zg30 pulse sequence) had a pre-scan delay of 10.0 s and the delay
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33 time between the scans was 10 s. The sweep width was 6000.0 Hz, the acquisition time
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35 was 5.45 s and 16 scans were averaged for each spectrum used in the correlations. The
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38 phase and baseline of the resulting spectra were manually adjusted and corrected after using
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40 a very large expansion of the y-axis. The integration was performed within each of these
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42 spectral segments, minimizing the small shifts observed between samples. This was
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45 achieved by carefully setting the TMS signal to 0 ppm, and the resulting integrals of the
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47 different segments of the spectrum were normalized. Figure 3 shows the 1H NMR spectra
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of three crude oils with different asphaltene content.
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53 The 1H NMR spectrum of crudes is very complex and contains a large number of signals
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55 because of the large distribution of chemical complexity. These are highly overlapped and
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57 dense; therefore, it is not possible to make an assignment of each of the lines with respect to
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3 specific molecular structural types, but a reasonable demarcation exists between methyl
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6 (0.5-1.10 ppm), methylene (1.10 1.65 ppm), methine (1.65 2.3 ppm) protons, and for
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8 the aromatic fractions (6.7 8.5 ppm).
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11 Protons of cycloalkanes produce signals inconsistent with the CH3, CH2 and CH 1H spectral
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14 regions characteristic of normal and branched alkanes.21 Additionally, various authors have
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16 reported different chemical shifts for the same type of proton, e.g.,proton of paraffins CH3
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type in positions to the aromatic ring: (1.0 2.0),22 (1.01.85),23 (1.0 1.4),24 (1.0 1.5),25
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21 (1.1 2.1),26 (0.3 2.0),27 (1.01.85),30and (1.85 2.1).28 Thus, for this study, the spectrum
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23 was divided in twelve chemical shift regions, and these regions were selected from different
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26 authors,29, 30, 31, 32, 33, 34, 35, 36, 37as shown in Table 2.
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29 The signal induced in the radio frequency receiver of a NMR spectrometer is detected as a
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31 time-dependent oscillating voltage, the free induction decay (FID). In high resolution
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34 NMR, we need to transfer the time domain data into the frequency domain and this way we
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36 convert the FID into the spectrum. Frequency analysis of the FID by Fourier
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38 Transformation (FT) produces the NMR spectrum (intensity vs. frequency, ppm). The full
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41 processing of the data, in summary, is: FT calculation, phase adjusting, baseline adjusting,
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43 scale setting and the integration. The most important of them to assure the quantitative
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results is the right adjustment of the phase.
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49 After the FT transformation, the phase of the spectrum needs to be corrected if the baseline
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51 around the peaks is not flat. In this point, the autophase routine does a pretty good job, but
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53 it is likely that the spectrum will still need a little manual phasing to get a really good
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56 phase. Our experience has shown that this automatic mode generally works well when pure
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60 8
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3 compounds are analyzed, but in the case of complex mixtures such as crude oils, the phase
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6 obtained from autophase mode is not good and this must be done manually.
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9 Manual phasing requires two phasing adjustments: the so-called zero and first order phase
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11 parameters. The zero order phase adjustment affects the phasing of all of the peaks in the
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14 spectrum equally. The first order correction varies linearly across the spectrum, so that the
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16 correction affects the peaks differently. The zero order is used by adjusting the phase of one
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18 signal in the spectrum as judged by eye, and the first-order is then used by adjusting the
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21 phase of a signal far away from the first in a similar manner. Therefore, to achieve high
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23 accuracy, to the phase, baseline, ppm scale and integration was conducted six times for
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each spectrum, thus, the area of each chemical shift (A1, A2, ...A12; see Table 2) is the
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28 averaged result of six integrations.
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31 Fig. 4 shows the relative percentage of the chemically different types of hydrogen atoms
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obtained from the 1H NMR spectra of three different crude oils; at each chemical shift
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36 region, the corresponding area of the three crude oils is plotted in the order from lowest to
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38 highest asphaltene content: 0.6, 3.7 and 14.2% wt.
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41 Finally, the averaged integrals were correlated with the stability parameter of Heithaus (Po)
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44 and the colloidal instability index (CII). The average total time required, including
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46 preparation, was 30 min per sample.
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49 Multiple linear regressions
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53 The correlation between the Po and CII data with the 1H NMR spectra of the crude oils
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55 represented by chemical shift regions was determined using the MLR method. With the
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57 MLR method, a linear relationship is assumed to exist between the properties Yi (i.e., Po or
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3 CII) and the 12 chemical shift regions (i.e., Xi1, Xi2,,Xi12). The proposed relationship is
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6 described by Eq. 2:
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9 Eq. 2
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12 where the i is the coefficient that minimizes the square of the difference between the
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15 predicted and measured values (Eq. 3),
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17 Eq. 3
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where i represents the number of measurements of the property of interest, and j is the
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23 number of chemical shift regions of the NMR spectrum. The statistical significance of the
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25 MLR models was evaluated by analysis of the R2 and adjusted R2adj values. The values of
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R2 are known to increase with the number of descriptors (chemical shift regions), thus R2adj
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30 is a much better indicator of the quality of the fitting. Its value takes into account the
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32 relevance of the number of descriptors used in the model, providing a better estimation of
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35 the quality of the MLR model.38
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38 Partial Least Squares Regression
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40 The correlation between the Po and CII data with the 1H NMR spectra of the crude oils was
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43 also determined using partial least squares (PLS) regression.38,39 To select the optimal
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45 model in each case, the predicted residual sum of squares (PRESS) for the cross-validated
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47 models was computed with various numbers of factor h. A leave-one-out cross validation
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50 (CV) regression method was employed to estimate the prediction statistics.39 This is a strict
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52 validation tool, and it easily selects the best models. According to this procedure, the best
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54 prediction model is the one that has the largest CV-q2value.39 Further information regarding
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3 the application of the MLR and PLS methods can be found in Molina et al., 2007,18
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6 Montgomery and Runger, 2003,38 Otto, 1999,39 and Molina et al., 2010.40
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11 3. RESULTS AND DISCUSSION
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The data exhibited in Table 1 indicate that the crudes in this study possessed a wide range
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17 of SARA values; therefore, they were considered a reasonable representation of Colombian
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19 crude oils.
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Fig. 3 shows the 1H NMR spectra of only 3 of the 29 crude oils used in this study, but with
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25 different asphaltene contents: 0.6; 3.7 and 14.2% wt. These have the same peaks in the
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27 same chemical shift, which indicates that the crude oils have the same proton types, but the
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30 difference in the values of the physicochemical properties of the crudes is due to the
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32 difference in the relative amount of these proton types.
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35 Fig. 4 shows the relative percentage of the chemically different types of Hydrogen atoms
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that are obtained from the 1H NMR spectra and are present in the same three crude oils
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40 shown in Fig 3. In each chemical shift frequency, the corresponding area (relative
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42 percentage) of the three crude oils is plotted in the order of low (left) to high (right)
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45 asphaltene content. It is readily observable from Fig. 4 that there are significant differences
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47 in the relative amount of Hydrogen atoms of the crude oil with different asphaltene content
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49 in most of the chemical shift regions. This is clearly observed in areas A2, A3, A4 and A6,
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52 where a clear trend is observed from Crudes 1 to 3. For the other areas, no definite trend
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54 was found because the size of the fluctuations within each set of the chemical shift regions
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prevented the determination of a clear trend. These results showed that differences in the
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60 11
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3 chemical composition of the crude oils may be easily detected by 1H NMR spectroscopy in
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6 most chemical shift regions, and the differences can be used to distinguish their chemical
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8 differences with high accuracy, which is a valuable tool in their characterization.
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11 As shown in Fig. 1 and Fig. 2, among the set of crudes used in this study, the crudes with
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14 low tendency to precipitate asphaltenes are those with high of aromatic and low paraffin
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16 content, and they have been shown to exhibit a very low CII and a very high peptizing
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18 power for asphaltenes, Po. The tendency curves and their R2 values indicate a clear
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21 relationship between the saturates (R2 = 0.92) and the CII; an acceptable correlation with
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23 the aromatic (R2 = 0.81) and a low correlation with the resins (R2 = 0.65) was observed, but
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this relationship was not clear with the asphaltene content because the R2 is very low (0.20).
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29 According to the CII, when CII0.9, the asphaltenes are unstable in the medium; when
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31 0.7CII<0.9, there is uncertainty about the stability; and if CII<0.7, the asphaltenes are
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stable in the oil.12 The most unstable crude, with the lowest Po (0.31), showed a
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36 consistently high CII value (2.5). However, none of the crudes in the set indicated CII
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38 values lower than 0.7 based on the CII classification corresponding to the most stable crude
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oils. On the contrary, the most stable crude, with the highest Po (0.93) exhibited a CII value
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43 of 1.1 that should correspond to an unstable crude and not to most stable forms. For the set
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45 used in this study, we observed that some crudes with low asphaltene contenthad low
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48 peptizing power and that some crudes with high asphaltene content showed high peptizing
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50 power. Considering the relationship between the asphaltene content and the peptizing
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52 power Po of the crudes of this study, asphaltene content cannot be considered as a negative
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55 factor for crude stability (see Fig. 2); e.g., crude 3 with 14.2% wt asphaltenes contains Po =
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57 0.77, and the crude oil with Po= 0.31 only contains 1.1% wt asphaltenes.
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60 12
1
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3 Because asphaltenes appear in the numerator of the ratio for calculating CII, it is expected
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6 that crudes with high asphaltene content would lead to a higher CII and would be more
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8 unstable. However, as shown in Fig. 2 for the crudes in this study, some crudes with high
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10
asphaltene content have resulted in more stable crudes (higher Po). Based on these results, it
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12
13 is proposed that in the colloidal stability index calculation, asphaltenes should not be
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15 considered as a negative factor for stability, but instead the most determining factor should
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be the amounts of saturates and aromatics present in a crude. A small increase in the value
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20 of saturates, that is caused by crude blending for example, can lead to asphaltene
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22 precipitation.
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26
Nellensteyn was the first researcher to suggest that asphaltene stability is likely associated
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28 with the presence of resins. Because resins have an intermediate polarity between
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30 asphaltenes and the remainder of the crude oil, they are likely to adsorb on the surface of
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33 the asphaltene colloidal particles and act as a steric dispersant.41
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36 When resins and asphaltenes are present together, hydrogen bonding may be one of the
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38 mechanisms by which resin-asphaltene interactions are achieved, and resin-asphaltene
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41
interactions are preferred over asphaltene-asphaltene interactions. Thus, if the same
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43 intermolecular forces are present in petroleums, it would not be surprising if the asphaltenes
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45 exist not as the more cumbersome agglomerations but rather as single entities that are
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48 peptized and effectively dispersed by the resins. The general indications are that the degree
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50 of aromaticity of, and the proportion of hetero elements in, the resins appear to play an
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52 important role in the ability of these materials to effect the solubility of the asphaltenes in
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55 an oil. It is presumed that the resins associate with the asphaltenes in the manner of an
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57 electron donor-acceptor and that there could well be several points of structural similarity
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60 13
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3 between the asphaltenes and resins that would have an adverse effect on the ability of the
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6 resins to associate with asphaltenes from different crude oil.42
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9 However, as shown in Fig. 1 and Fig. 2, CII and Po tendency curves and their R2 values
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11 indicate low correlation with the resins with values of 0.65 and 0.64, respectively.
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14 Different experimental and theoretical studies of resins from different crude oils have
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16 shown that the Nellensteyn hypothetical model, in which asphaltenes are sterically
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18 stabilized by resins, is not entirely valid. Additionally, resins are reported to be able to
19
20
21 contribute to the stabilization and destabilization of asphaltenes.
22
23
24 From the variations of the direct-current (DC) conductivity of solutions of asphaltenes in
25
26 toluene, it was demonstrated that the asphaltene nanoaggregates begin to form at low
27
28
29 concentrations and that their aggregation number is rather small (less than 10). The amount
30
31 of resins in asphaltene nanoaggregates is not high enough to increase their drag; thus, resins
32
33
are unlikely to coat asphaltenes. This study shows that the Nellensteyn hypothetical model
34
35
36 is not valid within the concentration range investigated. In heptane/toluene mixtures (30:70,
37
38 vol/vol), the least soluble resins tend to aggregate with asphaltenes to enhance their
39
40
41
stability.43
42
43
44 Resin adsorption isotherms were carried out on different substrates such as silica particles
45
46 or asphaltenes and silica-asphaltene extracted from different Venezuelan crude oils,
47
48
49
suggesting a correlation between the resin adsorption behavior and asphaltene
50
51 stability/instability phenomena in crude oil. Moreover, it appears that the resin molecular
52
53 self-interaction intensity plays a key role in the asphaltene stability/instability issue. Resins
54
55
56 with weak self-interaction exhibit a low adsorption tendency and tend to stabilize
57
58
59
60 14
1
2
3 asphaltenes against flocculation by the conventional peptization mechanism. In contrast,
4
5
6 resins that strongly self-interact exhibit high adsorption and produce a thick and sticky
7
8 adsorbed layer, which favors the flocculation of contacting asphaltene particles.44
9
10
11 Molecular mechanical calculations of resins and a highly aromatic model asphaltene
12
13
14 extracted from the spectroscopic data of a 510 C residue of a Venezuelan crude showed
15
16 that the driving interaction in micelle formation is the attraction between their aromatic
17
18 planes. The molecular recognition process is completed by the interactions produced by the
19
20
21 alkyl and cycloalkyl groups present in these molecules. The complex three-dimensional
22
23 shape of the alkyl parts of this model asphaltene limits the growth of its micelles through
24
25
26
steric interference. The shape of these asphaltene molecules allows the aggregation of only
27
28 those resins that fit their aromatic regions and show the lowest steric interference with their
29
30 alkyl groups. This type of molecular recognition may explain why only some resins are
31
32
33 able to solubilize specific types of asphaltenes through the formation of stable aggregates. It
34
35 was found also that the steric interference of the alkyl groups may limit the number of
36
37 available sites for H bonding and other directional interactions in this type of model
38
39
40 asphaltene.45
41
42
43
44
45
46 3.1 Prediction models
47
48
49
Different models were obtained by MLR and PLS, but only the best are shown in this
50
51 study, i.e., those with the highest R2 and CV-q2 values. Eq. 4 and 5 show the resulting
52
53 polynomials for the prediction of Po and CII obtained from the PLS correlation of the 1H
54
55
56 NMR data and the equations (for details see Appendix 1). More details about how to
57
58
59
60 15
1
2
3 calculate these equations are reported in Molina et al. 2010. 46 Fig. 5 and 6 show the
4
5
6 experimental and predicted Po and CII values with the PLS and MLR correlations,
7
8 respectively, for the 29 crudes used in this study. Fig. 7 and 8 show the coefficients for the
9
10
Po and CII models from MLR, respectively. Table 3 shows the statistical parameters (R2
11
12
13 and CV-q2) for the prediction models for Po and CII from the PLS and MLR methods.
14
15
16 Po(PLS) = -8,895 + 1,019*C2 + 1,448*C3 - 0,607*C4 + 1,915*C5 + 8,418*C7 - 0,652*C10 - 0,015*C1*C1 -
17 1,371*C7*C7 + 2,506*C8*C8 + 1,816*C9*C9 + 0,086*C1*C2 + 0,132*C4*C5 + 0,992*C6*C7 -
18 2,605*C7*C8 Eq. 4
19
20
CII (PLS) = -286,926 - 13,051*C2 - 10,176*C3 - 3,797*C4 - 24,327*C5 - 60,646*C6 + 34,117*C7 +
21
410,531*C8 - 87,153*C9 - 12,101*C10 + 0,144*C1*C1 + 36,376*C5*C5 + 89,635*C6*C6 + 3,463*C7*C7 -
22 153,373*C8*C8 - 2,924*C10*C10 - 0,418*C1*C2 + 1,075*C2*C3 + 1,781*C3*C4 - 3,909*C4*C5 +
23
105,463*C5*C6 - 32,941*C7*C8 + 67,682*C8*C9 Eq. 5
24
25 Po (PLS) = predicted Po with PLS correlations.
26 CII (PLS) = predicted CII with PLS correlations.
27
28
29
30 From Table 3, the PLS R2 values showed that the prediction of Po (R2>98%) and CII
31
32
33
(R2>99%) and that the values of CV-q2>89.9% were good for Po and CII, while the models
34
35 from the MLR method, with R2 values >97% and CV-q2>93%, were also very good. The
36
37 values of CV-q2 for CII (for MLR) were very close to one, showing that this model had the
38
39
40 highest the quality. Figure 5 shows the predicted and measured values of CII (PLS). The
41
42 PLS model exhibited a good fit (R-squared adjusted for d.f. = 98.2 ).The correlations of the
43
44 other models were slightly less accurate than the former models, although they were still of
45
46
47 high quality. All of these models showed that high-quality correlations between the Po, CII
48
49 and the 1H NMR spectra can be obtained for Colombian crude oils using the PLS and MLR
50
51
52
methods.
53
54
55 The relationship of fuel composition to fuel property is very complex and often requires a
56
57 complex solution, and the stability (CII or Po) is not an exception. The Po and CII values
58
59
60 16
1
2
3 depend on the chemical composition of that fuel (in this work, the SARA components and
4
5
6 the relative composition of different types of protons were determined by 1H NMR).
7
8 Chemometric techniques such as MLR provide a means for extracting information about
9
10
the property (Po or CII) from subtle variations in the NMR fuel spectrum that arise from
11
12
13 variations in the relative compositions of the chemical constituents present in the fuel
14
15 sample.
16
17
18
19
20 Because crude oils with high values of Po are more stable, further investigation of the
21
22 coefficients calculated by the MLR procedure (Fig. 7) revealed which part of the spectrum
23
24 (or which protons) influence (positively and negatively) the stability of crude oils. Protons
25
26
27 of CH3 of paraffins (n- and iso), paraffinic hydrogen and more to aromatic systems (A1),
28
29 -CH3 to aromatic carbons (A5), and CH, CH2 of olefins (A8) tend to decrease the
30
31
32 stability. It is known that paraffins and isoparaffins help to precipitate asphaltenes. The
33
34 interaction A2*A2 is similar to the multiplier effect of the CH2 protons that are present in
35
36 this organic compound.
37
38
39
40
Protons in di-ring aromatics and some tri- and tetra- ring aromatics (A10) tend to decrease
41
42 the stability. These protons are present in molecules of asphaltenes (with aromatic carbons
43
44 peri- and cata-condensed);therefore, if the asphaltene content increases, the instability also
45
46
47 increases. This is also confirmed with the A11*A11 coefficient (aromatic protons, CH of
48
49 some tri- and tetra-ring aromatics) with the highest negative value.
50
51
52 Protons in mono-ring aromatics (A9) tend to increase the stability. It is known that toluene
53
54
55 and benzene dissolve the asphaltenes;i.e., crude oils with high benzene and toluene contents
56
57
58
59
60 17
1
2
3 are more stable. Furthermore, the positive coefficient A3*A10 can be understood to
4
5
6 represent protons present in polyaromatic compounds with naphthene rings.
7
8
9
10
Aromatic protons present in di-rings and some aromatic tri- and tetra-rings (A10) tend to
11
12
13 decrease the stability. These protons are likely present in asphaltene molecules that contain
14
15 peri-aromatic carbons and that are cata-condensed. If the asphaltene content also increases
16
17
18
the instability, this occurrence is also confirmed with the coefficient A11 * A11 (aromatic
19
20 protons CH containing some tri and tetra-aromatic) rings.
21
22
23
Crude oils with low values of CII are more stable, and further investigation of the
24
25
26 coefficients calculated by the MLR procedure (Fig. 8) indicated that protons with positive
27
28 coefficients are associated with molecules that cause instability in the asphaltenes as
29
30
31 follows:-CH3 to aromatic carbons (A5), CH of di-ring aromatics and some tri- and tetra-
32
33 ring aromatics (A10),and CH of some tetra- ring aromatics (the highest, A12). This is also
34
35
confirmed with the interaction A11*A11, protons in some tri- and tetra-ring aromatics as
36
37
38 well as with protons in paraffinic compounds (A3*A4).
39
40
41
42
43
Protons associated with compounds that give stability to the oil are those with negative
44
45 coefficients: A2, A7, A11, A3*A3, A4*A4, A8*A8, i.e., protons that are present are in
46
47 aliphatic compounds, but these results are contradictory because it is well known that
48
49
50 asphaltenes are unstable in their presence.
51
52
53
54 Comparing the common protons obtained in the models for predicting CII and Po (Figs. 7
55
56
57 and 8) using A5, A10, A2*A2 and A11*A11, the results are consistent because the sign of
58
59
60 18
1
2
3 the coefficients of Po (negatives) are opposite to the sign of the coefficients of CII
4
5
6 (positives); that is, if a crude oil is more stable, then the Po will be greater and the CII will
7
8 be smaller.
9
10
11 After the basic correlations using these well-known crudes is established, the prediction of
12
13
14 Po and CII will require the determination of the 1H NMR spectrum of the new crudes under
15
16 investigation. The total time required for this analysis is approximately 30 min.
17
18
19
20
21
22 CONCLUSION
23
24
25 The use of the 1H NMR spectra provided a very rapid method to predict the stability
26
27 parameters of Heithaus (Po) and colloidal instability indices (CII) for a wide variety of
28
29
30 Colombian crude oils using different regression methods. The Po and CII were more
31
32 accurately predicted using the PLS method. Considering the relationship between the
33
34 asphaltene content and the peptizing power Po and the colloidal stability index CII,
35
36
37 asphaltenes cannot be considered as a negative factor for the stability of crude oils. Among
38
39 the set of crudes used in this study, it was observed that the crudes with low tendency to
40
41 precipitate asphaltenes are those with high of aromatic content and low paraffin content
42
43
44 because they have shown a very low CII and a very high peptizing power for asphaltenes,
45
46 Po.
47
48
49 AUTHOR INFORMATION
50
51
52
53 Corresponding Author
54
55
56 * E-mail: dmolina@uis.edu.co
57
58
59
60 19
1
2
3 ACKNOWLEDGEMENTS
4
5
6
7 The authors would like to thank ECOPETROL S.A.-InstitutoColombiano del Petrleo for
8
9 allowing the publication of this paper and for generous financial support (Convenio No.
10
11 003, 2007) and Universidad Industrial de Santander.
12
13
14
15
16
17
18
19
20
21 REFERENCES
22
23
24
25 (1) Moura, L. G. M.; Santos, M. F. P.; Zilio, E. L.; Rolemberg, M. P.; Ramos, A. C. S.
26
27
Journal of Petroleum Science and Engineering 2010, 74, 77-87.
28
29 (2) Spiecker, P. M.; Gawrys, K. L.; Trail, C. B.; Kilpatrick, P. K. Colloids Surfaces A:
30 Physicochem. Eng. Aspects 2003, 220, 9-27.
31
32 (3) D. Espinat, D.; Fenistein, D.; Barre, L.; Frot, D.; Briolant, Y. Energy & Fuels 2004, 18,
33
34
1243-1249.
35
36 (4) Evdokimov, I. N.; Eliseev, N. Y. Energy & Fuels 2006, 20, 682-687.
37
38 (5) Holmes, J. W.; Bullin, J. A. Hydrocarbon Processing 1983, September, 101-103.
39
40
41 (6) Heithaus, J.J. J. Inst. Petrol.1962, 48, 4553.
42
43 (7) Carnahan, N. F.; Salager, J-L.; Antn, R.; Dvila, A. Energy & Fuels 1999, 13, 309 -
44
314.
45
46
47 (8) Karlsson, R.; Isacsson, U. Energy & Fuels 2003, 17, 1407-1415.
48
49 (9) Rogel, E.; Ovalles, C.; Moir, M. Energy & Fuels, 2010, 24, 4369 4374.
50
51 (10) Buckley, J. S. Fuel Sci. Technol. Int. 1996, 14, 55-74.
52
53
(11) Wang, J.; Buckley, J. Energy & Fuels 2003, 17, 1445-1451.
54
55
56 (12) Asomaning, S. Petroleum Science and Technology 2003, 21,581-590.
57
58
59
60 20
1
2
3
4
5
(13) Kallevik, H.; Kvalheim, O. M.; Sjblom, J. Journal of Colloid and Interface Science
6 2000, 225, 494504.
7
8 (14) Aske,N.; Kallevik, H.; Sjblom, J. Journal of Petroleum Science and Engineering
9
2002, 36, 1 17.
10
11
12 (15) Parra, H.; Hernndez, D.; Lizard, J.; Hernndez, J.; Herrera, R.; Urbina, M.; Valdez,
13 A. Fuel 2003, 82, 869874.
14
15 (16) Andersen, S. I. Energy & Fuels 1999, 13, 315 -322.
16
17
18 (17) Macho, S.; Larrechi, M.S. Trends in Analytical Chemistry 2002, 21, 799-806.
19
20 (18) Molina, D.; Navarro, U.; Murgich, J. Energy & Fuels 2007, 21, 1674-1680
21
22 (19) Nielsen, K. E.; Dittmer, J.; Malmendal, A.; Nielsen, N. C. Energy & Fuels 2008, 22,
23 40704076.
24
25
26 (20) Molina, D.; Navarro, U.; Murgich, J. Fuel 2010, 89, 185-192.
27
28 (21) Haw, J. F.; Glass, T. E.; Dorn, H. C. Anal.Chem. 1983, 55, 22-29.
29
30 (22) Gupta, P. L.; Dogra, P. V.; Kuchnal, R. K.; Kumar, P. Fuel 1986, 65, 515519.
31
32
33
(23) Delpuech , J .- J.; Nicole, D .; Daubenfel d, J. -M.; Boudel, J .-C. Fuel 1985, 64, 325
34 334.
35
36 (24) Winschel, R. A.; Robbins, G. A.; Burke, F. P. Fuel 1986, 65, 526 532.
37
38
(25) Rousseau, B.; Funchs, A. H. Fuel 1989, 68, 1158 1165.
39
40
41 (26) O'Donnell, D. J., Sigle, S. O., Berlin, K. D., Sturm, G. P., Vogh, J. W. Fuel 1980, 59,
42 166 174.
43
44 (27) Cantor, D. M. Anal. Chem. 1978, 50, 11851187.
45
46
47 (28) Meussinger, R.; Moros, R. Fuel 2001, 80, 613 621.
48
49 (29) Gillet, S.; Rubini, P.; Delpuech, J. J.; Escalier, J-C.; Valentin, P. Anal. Chem. 1980,
50 52, 813-817.
51
52
53 (30) Gillet, S.; Rubini, P.; Delpuech, J. J.; Escalier, J-C.; Valentin, P. Fuel 1981, 60, 221-
54 225.
55
56 (31) Brown, J. K.; Ladner, W. R. Fuel 1960, 39, 87-96.
57
58
59
60 21
1
2
3
4
5
(32) Rongbao, L.; Zengmin, S.; Bailing, L. Fuel 1988, 67, 565-569.
6
7 (33) Kapur, G. S.; Singh, A. P.; Sarpal, A. S. Fuel 2000, 79, 1023-1029.
8
9 (34) Sarpal, A. S.; Kapur, G. S.; Mukherjee, S.; Tiwari, A. K. Fuel 2001, 80, 521-528.
10
11
12 (35) Hue, Z.; Ring, Z.; Liu, S. Energy & Fuels 2005, 19, 152-163.
13
14 (36) Kapur, G. S.; Ecker, A.; Meusinger, R. Energy & Fuels 2001, 15, 943-948.
15
16 (37) Meusinger, R. Fuel 1996, 75, 1235-1243.
17
18
19 (38) Montgomery, D. C.; Runger, G. C. Applied statistics and probability for engineers;
20 John Wiley and Sons, 3rd ed. New York, 2003.
21
22 (39) Otto, M. Chemometrics, Wiley-VCH, New York, 1999.
23
24
25 (40) Molina, D.; Parra, M.; Murgich, J. Petroleum Science and Technology, 2011, 29, 640-
26 648.
27
28 (41) Nellensteyn, F. J. The colloidal structure of bitumen. In The Science of Petroleum,;
29 Oxford University Press: London, U.K., 1938; Vol. 4, p 2760.
30
31
32 ( 42 ) Speight J. The Chemistry and Technology of Petroleum; second edition. Marcel
33 Dekker, Inc. New York, 1991.
34
35 (43) Sedghi, M.; Goual, L. Energy & Fuels 2010,24,2275 2280.
36
37 (44) Pereira, J.; Lpez, I.; Salas, R.; Silva, F.; Fernndez, C.; Urbina, C.; Lpez, J. Energy
38 & Fuels 2007, 21, 1317-1321.
39
40
41 (45) Murgich, J.; Rodrguez, J.; Aray, Y. Energy & Fuels 1996, 10, 68-76.
42
43 (46) Molina, D.; Navarro, U.; Murgich, J., Fuel 2010, 89, 185-192.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 22
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Table 1. Maximal and minimal composition (%wt) of the SARA fractions, stability
24
25
26 parameter of Heithaus (Po) and colloidal instability index (CII) of the set of Colombian
27
28 crude oil samples.
29
30
31
32
33
34
35 Property range Saturates Aromatics Resins Asphaltenes Po CII
36
37 Minimum
37.9 21.3 3.7 0.6 0.31 0,86
38
39
40 Maximum
70.8 40.2 14,7 14,2 0,93 2.62
41
42
43 Average
57.3 30.5 9.2 3.1 0.59 1.62
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 23
1
2
3
4
5 80
wt %
6
7 R = 0.92
8 70 crude 1
9
10
11 60
12 crude 2
13 crude 3
14
15 50
16 Saturates
17
18 40 Aromatics
19 Resins
20
21 Asphaltenes
30
22
23 R = 0.81
24
20
25
26
27
28 10
R = 0.65
29
30 R = 0.20
31 0
32 0.7 1.2 1.7 2.2 2.7 CII
33
34
35 Figure 1. Tendency of CII from SARA components of Colombian crude oils. Crude 1 (%
36
37 wt asphaltenes = 0.6); Crude 2 (% wt asphaltenes = 3.7); Crude 3 (% wt asphaltenes =14.2).
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 24
1
2
3
4
5 wt %
80
6
7
8 70
9
10
11 crude 1
60
12
13 R = 0.69
14
50
15 crude 2
16 Saturates
17
crude 3
18 40 Aromatics
R = 0.49
19 Resins
20
Asphaltenes
21 30
22
23
24 20
25 R = 0.65
26
27
10
28
29 R = 0.27
30
31 0
32 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P0
33
34
35 Figure 2. Tendency of Po from SARA components of Colombian crude oils. Crude 1 (% wt
36
37 asphaltenes = 0.6); Crude 2 (% wt asphaltenes = 3.7); Crude 3 (% wt asphaltenes =14.2).
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 25
1
2
3
4
5
Table 2. Chemical shift regions in the 1H NMR spectra of crude oils and structural
6
7 assignments.
8
9
10 Chemical shift Nomenclature Hydrogen type
11
12 (ppm)
13
14
0.5-1.0 A1 CH3 of paraffins (n- and iso). Paraffinic hydrogen
15
16
17 and more to aromatic systems.
18
19 1.0-1.7 A2 CH2 of paraffins (n- and iso), CH of iso-paraffins,
20
21 CH and CH2 of naphthenes. Paraffinic hydrogen
22
23 to aromatic systems.
24
25 1.7-1.9 A3 CH and CH2 of naphthenes. Mostly -CH and -
26
27
28 CH2 to aromatic systems
29
30 1.9-2.1 A4 -CH2 to olefins
31
32 2.1-2.4 A5 -CH3 to aromatic carbons
33
34 2.4-3.5 A6 -CH and -CH2 to aromatic carbons
35
36
37 3.5-4.5 A7 Bridged CH2 or CH
38
39 4.5-6.0 A8 CH and CH2 of olefins
40
41 6.0-7.2 A9 CH of mono-ring aromatics,
42
43 7.2-8.3 A10 CH of di-ring aromatics and some tri- and tetra- ring
44
45 aromatics
46
47
48
8.3-8.9 A11 CH of some tri- and tetra-ring aromatics
49
50 8.9-9.3 A12 CH of some tetra- ring aromatics
51
52
53
54
55
56
57
58
59
60 26
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 3. Typical 1H NMR spectra of Colombian crude oil. Crude 1 (red, % wt asphaltenes
33
34 = 0.6); Crude 2 (green, % wt asphaltenes = 3.7); Crude 3 (blue; % wt asphaltenes = 14.2).
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 27
1
2
3
4
5 60
6
7
H%
8 50
9
10
11
40
12
13
14 Crude 1
15 30
Crude 2
16
17 Crude 3
18 20
19
20
21
10
22
23
24
25 0
26 A12 A11 A10 A9 A8 A7 A6 A5 A4 A3 A2 A1
27
28
29 Figure 4. Relative percentage of chemically different hydrogen atoms obtained from 1H
30
31 NMR spectra of three crude oils. Crude 1 (red, % wt asphaltenes = 0.6); Crude 2 (green, %
32
33 wt asphaltenes = 3.7); Crude 3 (blue; % wt asphaltenes = 14.2).
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 28
1
2
3
4
5
6
7
1,1 2,8
8
9 2,4
10 0,9
11
observed
observed
2
12 0,7
13 1,6
14
0,5
15 1,2
16
17 0,3 0,8
18 0,3 0,5 0,7 0,9 1,1 0,8 1,2 1,6 2 2,4 2,8
19 predicted Po (PLS) predicted CII (PLS)
20
21
22 Figure 5. Experimental and predicted Po (eq. 4) and CII (eq. 5) for Colombian crude oils.
23
24
25
PLS correlation.
26
27
28
29
30 1 2,8
31
32 0,8
2,4
33
observed
observed
34 2
35 0,6
36 1,6
37 0,4
1,2
38
39 0,2 0,8
40 0,2 0,4 0,6 0,8 1 0,8 1,2 1,6 2 2,4 2,8
41 predicted Po (MLR) predicted CII (MLR)
42
43
44
45 Figure 6. Experimental and predicted Po and CII for Colombian crude oils. MLR
46
47 correlation.
48
49
50
51
52
53
54
55
56
57
58
59
60 29
1
2
3
4
5
6
7
8 4
9
10
2
11
12
13 0
A10
A2*A2
A11*A11
A3*A9
A4*A9
A5*A9
A1
A5
A8
A9
A3*A10
A4*A10
A5*A11
14
15
-2
16
17
18 -4
19
20
-6
21
22
23 -8
24
25
-10
26
27
28 -12
29
30
31 -14
32
33 -16
34
35
36
37 Figure 7. Coefficients of model Po (MLR model).
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 30
1
2
3
4
5 150
6
7
8
9 100
10
11
12
13 50
14
15
16
17 0
18
A10
A11
A12
A2*A2
A3*A3
A4*A4
A5*A5
A6*A6
A7*A7
A8*A8
A9*A9
A1*A2
A2*A3
A3*A4
A8*A9
A2
A5
A7
A10*A10
A11*A11
19
20
21
22 -50
23
24
25
26 -100
27
28
29
30 -150
31
32
33
34 -200
35
36
37 Figure 8. Coefficients of model CII (MLR model).
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 31
1
2
3
4
5
Table 3. R2 and CV-q2 values for prediction models of Po and CII using PLS and MLR.
6
7
8 PLS MLR
9
10 Po CII Po CII
11
12 98.6 99.6 97.6 98.8
13 R2 (%)
14 (%) -adjusted for d.f. 97.2 98.2 95.6 95.8
15
16
Cv q2(%) 90.5 89.9 78.1 96.0
17
18
19 Standard error of the estimate 0.03 0.07 0.03 0.11
20
21 Absolute error 0,02 0.02 0.02 0.04
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 32
1
2
3
4
5
6 Appendix 1.
7
8
9 The procedure for a particular property (CII) will be outlined here to describe the different
10
11
12 steps involved in the correlation between the areas of the NMR signals and properties. The
13
14 notation employed is such that the NMR1 (H1) area of Crude 1 is 1H1, while area 2 for the
15
16 same Crude is 1H2, while the area for Crude 2 and H1will be 2H1. These values formed
17
18
19 matrix x,while the different properties generated matrix q as shown in Eq. 1A.
20
21
22 1H1 1H2 1H3 1H4 1H5 1H6 1H7 1H8 1H9 1H10 1H11 1H12 2,048
23 2H1 2H2 .... 2H12 2,436
24
3H1 ; 0,934 (1A)
25
26 x = ..... q = .....
27 ...... ........
28
...... .......
29 29H1 .. ....
29H12 1,898

30
31
32
33 The application of PLS produces the weights (W) for the different areas. In the present
34
35 case, the results are shown in Table A1.
36
37
38 Table A1. Weight of variables in Matrix X
39
40
41
42 Weight H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12
43 W1 -0.0755 -0.4210 0.4423 . . . . . . . . 0.0060
44 W2 0.2374 -0.1815 0.4404 . . . . . . . . -0.1576
45
46 W3 0.1747 -0.0070 0.1278 . . . . . . . . 0.4916
47 . . . . . . . . . . . . .
48 . . . . . . . . . . . . .
49
W10 0.0460 -0.1458 0.3824 . . . . . . . . 0.0301
50
51
52
53 For Table A1 and matrix X, the factors (Ci) were calculated as follows:
54
55 C1 of crude 1= (-0.0755 x 1H1)+(-0.4210 x 1H2)+ ..(0.0060 x 1H12)= -22.0437
56
57 C1 of crude 2= (-0.0755 x 2H1)+(-0.4210 x 2H2)+ ..(0.0060 x 2H12)=-20.6640
58 C10 of crude 29 = (0.0460 x 29H1)+(-0.1458 x 29H2)+ .(0.0301 x 29H12)= -5.2625
59
60 33
1
2
3
4
5
6 The values for the Ci for each crude are shown in Table 1B
7
8
9
10 Table 1B.Cis factors
11
12
13 Cis Factors
Crude
14 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 CII
15
16 1 -22.0437 -1.9368 3.0551 . . . . . . -5.6494 2.0488
17 2 -20.6641 -1.4004 3.4342 . . . . . . -5.0495 2.4364
18 3 -14.4837 1.6622 2.9321 . . . . . . . .
19
. . . . . . . . . . .
20
21 . . . . . . . . . . .
22 . . . . . . . . . . .
23 29 -21.4436 -0.7297 3.5990 . . . . . . -5.2625 1.8986
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 34

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