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Petroleum Science and Technology

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Manuscript ID:

Complete List of Authors:

Murgich, Juan; IVIC, C. de Quimica


V., Daniel; Universidad Industrial de Santander, Esc. de Quimica
Parra, Martha; ECOPETROL-Instituto Colombiano del Petroleo

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Keywords:

Original Papers

Date Submitted by the


Author:

LPET-2009-0188.R1

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Manuscript Type:

Petroleum Science and Technology

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Journal:

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MRL and PLS Correlations Between the 1H NMR Spectra of


Vacuum Residues and the deasphalting conditions with the
DMO yields

vacuum residue, NMR, DEMEX, yield, correlation, PLS, MLR

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MRL and PLS Correlations Between the 1H


NMR Spectra of Vacuum Residues and the
deasphalting conditions with the DMO yields.

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Daniel Molina V.a*, Martha Parrab, and Juan Murgichc
Escuela de Qumica, Universidad Industrial de Santander, Apartado Areo 678,
Bucaramanga, Colombia
b
ECOPETROL-Instituto Colombiano del Petrleo, Piedecuesta, Colombia.
c
Centro de Qumica, IVIC, Apartado 21827, Caracas1020A, Venezuela

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*dmolina@uis.edu.co

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Abstract

The areas of signals present in 12 consecutive frequency bins of the 1H NMR


spectra of different vacuum residues VRs were correlated with the yield of the
deasphalting/ demetallization process (DEMEX) under fixed and variable conditions

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(Antisolvent/load ratio and rectification temperature). Prediction models for the


demetallized oil DMO obtained under variable process conditions generated by partial
least square PLS had R2= 0.950 while the CV-q2 was 0.943. Models obtained with
multiple linear regression MLR for the same process was R2= 0.93 but with a significant

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lower CV-q2 (0.608) value. The prediction models for the DMO yield under a set of fixed

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conditions was such that R2 = 0.930 for the PLS while for the MRL method it was 0.970.
Again, the CV-q2 value was higher for the PLS (0.998) than for the MRL method (0.610).

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The proposed correlation methods are much faster and significantly less costly than the
conventional ones used in predicting the yield of the DMO process.

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Introduction.

Vacuum residues VRs are the main byproducts of oil refining that require
extensive processing to convert them in more valuable products (Speight and zm,
2002). This is especially important in the case of heavy oils that produce large quantities

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of VRs. This problem is enhanced by the historical decrease in light oils production and
the simultaneous increase in the production of heavy ones. One of the conversion
processes required in the generation of valuables product from the VRs is their
demetallization/ deasphalting prior to thermal cracking and/or visbreaking. To predict the

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amount of the demetallized oil DMO obtained using different operational conditions for a

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set of residues or for different VRs under fixed conditions, it is necessary to determine
the yield in each case. These measurements are expensive and include several long

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tedious operations (Speight and zm, 2002). Faster and less expensive methods to
predict the yields of these residues using spectroscopic method such as 1H NMR are thus

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of interest to optimize valuable refinery production in shorter times. NMR spectroscopy

is a powerful technique for the investigation of properties in highly complex mixtures

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(Alam and Alam, 2005). NMR provides a fast and efficient way of obtaining valuable
molecular structural information even if the components are part of a highly complex

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Petroleum Science and Technology

mixture such as the VRs. An advantage of NMR over other techniques is that the
spectrum is just the sum of those corresponding to the pure compounds if simple
conditions are met (Molina et al., 2007). This allows the simultaneous identification and
the quantitative determination of resonant nuclei belonging to chemically different groups
present in these complex mixtures (Alam and Alam, 2005). All these properties led to

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application of NMR to the study of the complex mixtures such as petroleum and a
significant number of its byproducts. Both 1H and 13C NMR has been applied to the study
of different fractions of crude oils in order to correlate different properties with the
molecular structural information obtained by means of NMR (Hue, et al., 2005; Kapur et
al., 2001; Kapur et al., 2000; Meusinger and Moros, 2001, and Meusinger, 1996).

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Recently, selected physicochemical properties and the refined product yields of different
type of crudes were obtained by means of PLS correlation with their 1H NMR spectra
(Molina et al., 2007).

In this work, we have obtained predictive models based in the correlation of the
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H NMR spectra of the VRs with their DMO yield for different types of residues under a

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set of fixed operational conditions and the same but using in this case different conditions
(i.e. antisolvent solvent/load ratio, etc.) under which the deasphalting takes place for a

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fixed set of VRs. The models obtained from the correlations allow the prediction of the
yield of the deasphalting processes of the residues in a very short time. In this way, costly

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studies and refinery or pilot plant trial runs may be avoided or minimized with the

corresponding savings in cost and time. In this work, the deasphalting method used was

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DEMEX (Speight and zm, 2002). Nevertheless, the procedure developed in this work
can be easily extended to any other deasphalting processes.

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Experimental
The deasphalting process was generated by the controlled addition of the
antisolvent LPG (Liquefied Petroleum Gas) in a model pilot plant. The antisolvent
composition is shown in Table 1.
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Table 1. Composition (%w) of LPG


C3

i-C4

n-C4

Olefins

C5+

IS

4.42

22.82

68.47

0.86

3.24

2.51

where IS designates other types of unsaturated compounds present in the

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antisolvent. In order to have a wide set of samples, 14 different vacuum residues VR


were used. They were the residues of blends of crudes or different crudes as received
from the refinery of ECOPETROL, in Barrancabermeja, Colombia.
In the second part of this work, the condition of the deasphalting process were

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changed by using different antisolvent to load ratios and rectification temperatures while

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using a fixed set of VRs. The values employed in the deasphalting process are shown in
Table 2

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The pilot plant was designed to closely simulate the full-scale DEMEX process
used in the refineries of ECOPETROL (see Fig. 1).

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Fig. 1. Schematic of the pilot plant used for the DEMEX process.

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The glass vessel with 1l of the residue is located on the upper left side of Fig. 1 while that
of mixture and precipitation (4.5l) one is on the upper right. In Fig. 1, M is a pneumatic
motor that drives a mechanical stirrer (480-500 rpm), T is a calibrated thermometer, TB
is a thermostatic bath that controls the temperature of the residue and separation vessels
at 0.2C, P is a variable speed pump, SM is a static mixer, and VF is the vacuum

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filtering system. The antisolvent vessel contained up to 5l of LPG. The process started
with the mixing of a solution of 1 part of residue to 5 of LPG for 1 hour at 50C to
facilitate the transfer to the separation vessel. The flow transfer rate was of 1l/min to the
mixing vessel. The second mixing step with LPG was done in two parts: the first one

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occurred in the static mixer SD and a second one in the separation vessel. In the latter

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step, additional mixing and contact was achieved with the stirrer (480-500 rpm) and using
a much longer contact time (2 hours). The solution and precipitated solid were left in the

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vessel for 15 hours to assure proper sedimentation. The separation was done in three
steps: first the supernatant liquid part was filtrated. Then, the solid cake was vacuum

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filtered in a Buchner funnel (150 mm in diameter). After that, the precipitated solid was

extracted and washed with 1l of LPG. In the last step, the solid was again washed until

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the LPG flowed colorless and then the sample was dried and collected for weighting. The
deasphalting process was done at atmospheric pressure.

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The NMR spectrometers settings were optimized to obtain a high signal-to-noise ratio.
The final settings have been applied throughout this work and were such that the 1H
NMR spectra of the VRs before deasphalting were obtained with a Bruker ACP-400MHz
spectrometer in 5%w solutions in CDCl3 at room temperature. The 30-degree pulses
(Bruker zg30 pulse sequence) were of 9.6s and the delay time between scans was 4s.

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Table 1. Deasphalting conditions used in the DEMEX process.


Exp.
Number
1

Load DEMEX AS/L


382H
5.0

Trect. [C]
100

Exp.
Number
13

Load
DEMEX
384H

AS/L
6.5

Trect. [C]
115

382H

6.5

100

14

397H

6.5

115

382H

8.5

100

15

363H

6.5

115

382H

5.0

115

16

396H

6.5

115

6.5

115

17

398H

6.5

115

382H

8.5

115

18

276H

6.5

115

382H

5.0

120

19

277H

6.5

115

382H

6.5

120

20

278H

6.5

115

328H

8.5

120

21

280H

6.5

115

10

375H

5.0

115

22

285H

6.5

115

11

375H

6.5

23

287H

6.5

115

12

375H

8.5

6
7
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382H

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115
115

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Trect. is the rectification temperature and AS/L is the antisolvent to load ratio
employed.

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(Sweep width: 3937.0, Dwell Time: 254sec, Offset Frequency: 1814.8, Number

of points: 16384, Line Broadening: 0.1Hz), TMS was used as reference and 16 scans

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were averaged for each spectrum employed in the correlations. The phase and base line
of the resulting spectra was manually adjusted (Molina et al., 2007)

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The NMR spectrum was divided in 12 consecutive frequency bins to facilitate the
model construction (Molina et al., 2007) (see Table 2). The integration was performed
within each of these spectral segments minimizing the small shifts found between
samples. This was achieved by carefully setting the TMS signal at 0 ppm in each case.

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Petroleum Science and Technology

The integrals of the bins were normalized, and to have high accuracy, 6 integrations were
averaged per each segment and were performed on the same spectrum.
Table 1. Spectral range, frequency bins and Hydrogen types present in the NMR spectra
of vacuum residues.
Spectral
range (ppm)

Frequency bin

Hydrogen Type

H12

CH3, some naphthenic CH and


CH2s

1.0-1.7

H11

CH2, and some CHs.

1.7-1.9

H10

Most CH, CH2 in positions.

1-9-2.1

H9

CH3 in olefins

2.1-2.4

H8

CH3 in aromatic carbons.

H7

CH, CH2 in aromatic carbons

H6

Bridging CH2

4.5-6.0

H5

Olefins

6.0-7.2

H4

Mono-aromatics

0.5-1.0

2.4-3.5

H3

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7.2-8.3

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3.5-4.5

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Di-aromatics and some tri- and tetraaromatics

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8.3-8.9

H2

Some tri and tetra-aromatics

8.9-9.3

H1

Some tetra-aromatics

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The assignment of the frequency bins shown in Table 1 was based on that used
previously in (Molina et al, 2007). Four blind tests were performed to assure that

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variations due to spectrometers conditions and/or operator skills were kept to a minimum.
The correlation between % DMO with DEMEX conditions data and the 1H NMR
spectra of VRs, represented by frequency bins, was determined using the MLR method.
In it, a linear relationship is assumed to exist between the properties Yi with the
frequency bins Xi1, Xi2,, Xi12. The proposed relationship was such that
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Yi=

X
j

ij

Eq. 1

+ i

where the j are the coefficients that minimize the square of the difference between
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predicted values and the measured ones, i , while i represents the number of
i

measurements of the property of interest while j is the number of frequency bins of the

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NMR spectrum.

The correlation between the % DMO with DEMEX conditions data and the 1H
NMR spectra of the VRs were also determined using the Partial Least Square Regression
PLS (Otto, 1999 and Montgomery and Runger, 2003). To select the optimal model in

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each case, were computed the Predicted Residual Sum of Squares PRESS for cross-

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validated models with various numbers of factors h. In order to estimate prediction


statistics, a Leave-one-out cross validation (CV) regression method was employed (Otto,

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1999). This is a strict validation tool and easily discriminates the best models. According
to this method, the best prediction model is then the one that has the larger CV-q2 value

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(Otto, 1999). Further information regarding the application of the MLR and PLS methods

may be found in (Molina et al., 2007, Molina et al., 2009, Montgomery and Runger, 2003
and Otto, 1999)

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Results and Discussion

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H NMR spectrum of each of the VRs was taken and the integrals calculated.

MRL was used to model the DEMEX process using the integrals of the frequency bins of
the NMR spectrum (H1 to H12) and the deasphalting conditions (S/L, Trect) as

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independent variables and the %w DMO (and %w DEMEX residue) as dependent. Table
3 shows the 1H NMR results, the deasphalting conditions and the %wDMO yield
obtained
Table 3. Areas of the frequency bins of the 1H NMR spectra, solvent to load ratio S/L
and DMO yield %w for different process conditions.
H1

H4

H5

H10

H11

H12
S/L

0.79
0.79
0.79
0.79
0.79
0.79
0.79
0.79
0.79
0.78
0.78
0.78
0.72
0.80
1.22
0.73
0.85
1.20
1.07
1.05
1.03
1.16
1.14

4.80
4.80
4.80
4.80
4.80
4.80
4.80
4.80
4.80
4.54
4.54
4.54
4.06
4.80
5.09
4.56
4.90
5.20
4.89
4.79
4.80
5.01
4.99

3.84
3.84
3.84
3.84
3.84
3.84
3.84
3.84
3.84
3.68
3.68
3.68
3.32
3.93
3.86
3.66
4.06
3.97
3.76
3.66
3.74
3.87
3.80

3.30
3.30
3.30
3.30
3.30
3.30
3.30
3.30
3.30
3.20
3.20
3.20
2.82
3.31
3.41
3.16
3.52
3.61
3.42
3.36
3.38
3.50
3.44

15.22
15.22
15.22
15.22
15.22
15.22
15.22
15.22
15.22
14.67
14.67
14.67
14.29
15.14
14.53
15.02
15.64
14.01
13.46
13.71
13.11
13.46
13.42

45.49
45.49
45.49
45.49
45.49
45.49
45.49
45.49
45.49
46.17
46.17
46.17
48.86
44.88
43.92
46.25
43.45
42.35
44.23
44.48
45.08
44.33
43.98

19.85
19.85
19.85
19.85
19.85
19.85
19.85
19.85
19.85
20.77
20.77
20.77
19.99
19.94
19.18
20.17
20.85
19.54
19.91
19.77
20.56
19.65
19.24

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0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.05
0.05
0.05
0.07
0.05
0.61
0.05
0.07
0.71
0.58
0.61
0.50
0.65
0.73

H9

2.02
2.02
2.02
2.02
2.02
2.02
2.02
2.02
2.02
1.96
1.96
1.96
1.71
2.13
3.17
1.99
2.11
3.96
3.83
3.82
3.49
3.66
3.81

H8

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4.00
4.00
4.00
4.00
4.00
4.00
4.00
4.00
4.00
3.57
3.57
3.57
3.54
4.33
4.27
3.79
3.93
4.60
4.14
4.12
3.69
4.00
4.50

H7

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0.55
0.55
0.55
0.55
0.55
0.55
0.55
0.55
0.55
0.50
0.50
0.50
0.51
0.58
0.58
0.50
0.51
0.67
0.55
0.50
0.50
0.56
0.74

H6

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0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.10
0.10
0.10
0.11
0.12
0.16
0.10
0.10
0.18
0.15
0.12
0.12
0.15
0.20

H3

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H2

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5.0
6.5
8.5
5.0
6.5
8.5
5.0
6.5
8.5
5.0
6.5
8.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5

DMO
Trect. yield
[C] [%w]
100
43
100
48
100
49
115
38
115
44
115
44
120
34
120
43
120
44
115
53
115
54
115
56
115
56
115
49
115
48
115
54
115
54
115
37
115
51
115
53
115
53
115
44
115
34

Equations 3 and 4 show the best models obtained by the MLR and PLS methods
(Statistica 6.0, 2001).

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DMO yield (MLR)= -2554.52+ 63.48*H3+ 68.28*H4+ 99.57*H6+ 30.15*H10+


22.27*H11+ 38.04*H12+ 1.69*solv/load- 0.29*Trect- 9.63*H3*H4

Eq. 3

DMO yield (PLS)= -79.2165- 22.5471*C1+ 26.7119*C2- 51.4457*C3+ 83.6256*C4

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- 8.74693*C7+ 124.288*C8- 57.3382*C9+ 276.487*C10+ 181.602*C11-177.397*C12


Eq. 4
Figure 2. Predicted (MRL) and measured DMO yield from the 1H-NMR spectra and
different antisolvent/ load ratios and rectification temperatures.

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Figure 3. Predicted (MRL) and measured DMO yield from the 1H-NMR spectra and
different antisolvent/load ratios and rectification temperatures.

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Petroleum Science and Technology

The MLR method showed a R2 value of 0.930 while PLS gave 0.950. Statistically, the
CV-q2 values clearly showed that the PLS method provided a significantly better model
(0.943) than the MLR one (0.608).
In Table 4 are shown the results obtained for the DMO yield for the different VRs
under the same DEMEX process conditions.

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Table 4. Areas of the 1H NMR frequency bins, DMO yield %w and the Residue of the
DEMEX process.

ee
H4

H5

H6

H7

H8

H9

H10

H11

DMO
yield R.DX
H12 [%w] [%w]

VR

H1

H2

H3

0.12

0.55

4.00 2.02 0.04 0.79 4.80 3.84 3.30 15.22 45.49 19.85

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56

0.10

0.50

3.57 1.96 0.05 0.78 4.54 3.68 3.20 14.67 46.17 20.77

54

46

0.11

0.51

3.54 1.71 0.07 0.72 4.06 3.32 2.82 14.29 48.86 19.99

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44

0.12

0.58

4.33 2.13 0.05 0.80 4.80 3.93 3.31 15.14 44.88 19.94

49

51

0.32

1.05

5.70 3.74 1.08 1.89 6.63 4.64 4.17 15.47 38.13 17.18

48

52

0.16

0.58

4.27 3.17 0.61 1.22 5.09 3.86 3.41 14.53 43.92 19.18

48

53

0.10

0.50

3.79 1.99 0.05 0.73 4.56 3.66 3.16 15.02 46.25 20.17

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0.10

0.51

3.93 2.11 0.07 0.85 4.90 4.06 3.52 15.64 43.45 20.85

54

46

0.18

0.67

4.60 3.96 0.71 1.20 5.20 3.97 3.61 14.01 42.35 19.54

51

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10

0.15

0.55

4.14 3.83 0.58 1.07 4.89 3.76 3.42 13.46 44.23 19.91

37

63

11

0.12

0.50

4.12 3.82 0.61 1.05 4.79 3.66 3.36 13.71 44.48 19.77

51

49

12

0.12

0.50

3.69 3.49 0.50 1.03 4.80 3.74 3.38 13.11 45.08 20.56

53

47

13

0.15

0.56

4.00 3.66 0.65 1.16 5.01 3.87 3.50 13.46 44.33 19.65

53

47

0.20

0.74

4.50 3.81 0.73 1.14 4.99 3.80 3.44 13.42 43.98 19.24

44

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The best models from MLR and PLS for this case were (Eq.5 and eq.6, respectively):

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DMO yield (MLR)= 334.608 + 26.988*H3 486.143*H2 + 108.223*H2*H8


- 1.3393*H8*H11 9.26052*H9*H3

Eq. 5

DMO yield (PLS) = -16.82+ 64.43*C1- 33.32*C2+ 511.31*C3- 22.31*C4- 0.83*C5 +


9.02*C6- 36.60*C7- 127.9*C8+ 144.93*C9- 5.65*C1*C1+ 2.39*C1*C2 32.89*C1*C3
Eq. 6
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Figure 4. Predicted (MLR) and measured DMO yield from the 1H-NMR data with fixed
antisolvet/load ratio= 6.5 and Rectification Temperature=115C

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Figure 5. Predicted (PLS) and measured DMO yield from the 1H-NMR data with fixed
antisolvet/load ratio= 6.5 and Rectification Temperature=115C

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The R2 values for the MRL model was 0.93 and its P-value 0.0005 showed that the model
was in the 95% confidence level. The MRL method provides a good fit although the PSL
gave again a much better one with R2= 0.970 but with a CV-q2 value of 0.998 instead of
0.610.

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Conclusions

It was found that the combined use of 1H NMR spectra of the VRs and
Chemometrics provides a fast and convenient way of determining the yield of the

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deasphalting/demetallization processes for different types of VRs and processes

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conditions. The PLS method provided better models than the MRL one in every case.

Acknowledgements

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The authors would like to thank for allowing the publication of this paper to the

Unidad de Investigacin of Ecopetrol-Instituto Colombiano del Petrleo and for generous

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financial support (Convenio No. 004 2003) and to Dr. Uriel Navarro. To Drs. Winston
Quionez from Univ. de Antioquia for the NMR spectra and to Jairo Ren Martnez from

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Univ. Industrial de Santander for acting as the University Coordinator of the Convenio
004 with Ecopetrol-ICP.

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References

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Kapur, G.S., Singh, A.P. and Sarpal, A.S. (2000). Determination of aromatics and
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nuclear magnetic resonance (NMR) spectra of colombian crude oils, Energy & Fuels,
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Statistica 6.0, (2001) StatSoft, Inc., Tulsa, OK 74104, USA.

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