spectroscopy based crude assays for ... based crude assays for laboratory, at-line, and on-line...
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SPECTROSCOPY BASED CRUDE ASSAYS FOR LABORATORY, AT-LINE, AND ON-LINE
APPLICATIONSPaul J. Giammatteo and John C. Edwards
Process NMR Associates, LLC
Danbury, Connecticut
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
• True Boiling Point which accurately measures product yields • Water Content • API Gravity • Metals and Inorganic Content (nickel, vanadium, sulfur, sodium, chlorine) • Corrosivity
• Full distillation yields (True boiling point vol% and wt%) by NMR • Water content (Microwave water cut and NMR) • API Gravity (NMR) • Carbon distribution (aromatics, olefins, naphthenics, paraffins) (NMR) • Metals (nickel, vanadium) (ESR) • Acidity/Corrosivity (ESR / Microwave)
Traditional
Spectroscopic
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
• NMR – Nuclear Magnetic Resonance» Time-Domain/Low Resolution» High Resolution
• ESR – Electron Spin Resonance
• FTIR – Fourier Transform Infra–Red with Diamond ATR» Mid-infra-red region (4000 – 650)
• LIBS - Laser Induced Breakdown Spectroscopy
1. Can be applied in a variety of laboratory, at-line, and/or online configurations.2. Offer rapid, cost effective and simultaneous multi-parameter analyses.3. Measurement of both bulk and trace properties.4. Ideal for use in combination with software planning tools.
Crude Oil Chemistry: Alkanes, cycloalkanes (naphthenes), aromatics,polycyclic aromatics, S-containing compounds, etc. Gasoline: branched alkanesDiesel: linear alkanes
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Polycyclic Aromatics and Asphaltene “Precursors”
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Oil Refining, one of the most complicated manufacturing operations in all industry, taking extremely diverse feed stocks to make products of consistent quality worldwide.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
0
5
10
15
20
10 8 6 4 2 0
NMR Spectra Showing Spectral Variability of 6 Crudes
ppm
CH
CH2
CH3CH3
CH3
0
5
10
15
20
10 8 6 4 2 0
NMR Spectra Showing Spectral Variability of 6 Crudes
ppm
CH
CH2
CH3CH3
CH3
0
5
10
15
10 8 67 4 2 0
0
5
10
15
10 8 67 4 2 0
All Diesels: (Data date range 1999 to present)
Atmospheric Crude Straight Run
Vacuum Crude Straight Run
Coker Diesel
FCC Diesel
Diesel Hydro Cracker Feed
Diesel Hydro Cracker Product
Mild, Moderate and Severely Hydro Treated Diesel
Blend Header Diesel
R R R
CH 3
CH2
R
CH3
RH
RH
RH
HR
RR
HH
0
5
10
15
10 8 67 4 2 0
0
5
10
15
10 8 67 4 2 0
All Diesels: (Data date range 1999 to present)
Atmospheric Crude Straight Run
Vacuum Crude Straight Run
Coker Diesel
FCC Diesel
Diesel Hydro Cracker Feed
Diesel Hydro Cracker Product
Mild, Moderate and Severely Hydro Treated Diesel
Blend Header Diesel
R R RR R R
CH 3
CH2
CH 3
CH2
R
CH3
R
CH3
RH
RH
RH
HR
RR
HH
RH
RH
RH
HR
RH
HR
RR
HH
Gasolines
0
5
10
15
20
10 8 6 4 2 0
NMR Spectra Showing Spectral Variability of 6 Crudes
ppm
CH
CH2
CH3CH3
CH3
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Table 1: Initial Study Crude Oils - 2003 to 2008 Alaskan North Slope Forties Nile Blend Amna Fosterton Odudu Arab Heavy Gos Mix Oily Rock Arab Medium Grand Isle Qatar Marine Arab X-light High Island Qua Iboe Bach Ho Kerapu Rang Dong Badak Khafji Ras Garib Basra Kiame Ratawi (Neutral Zone) Basra Light Kirkuk Ross Bay Marchand Kuwait Ruby Bay Marchand Lago Medio Schiehallion BCF-17 Lavan Blend Shell Delta Belayim (Egypt) Light Louisiana Sweet South Arne Brent Liverpool BlendStag Cheleken Loyal Syrian Light Cuisiana Lu Feng Tantawan Cupiago Mandji Tapis Blend Cupiagua Marib light Tengiz Curlew Mars Torcados (Nigeria) Didon Masa Upper Zakum Dubai Masila Wafra (Neutral Zone) Dulang Maui Condensate Walio Dulang Maya West Texas Intermediate Duri Minas Xi Xiang Es Sahara Mudi YME Flotta Nemba Zafiro Blend
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
TBP Weight Percent Cut Point (Actual versus NMR Predicted) Partial Least Squares results for Table 1Crude oils. Graphs are for (clockwise) 50 deg C, 200 deg C, 700 deg C, and, 500 deg C. CorrelationCoefficients (R2) for each plot are greater than 0.96
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
TBP at 50C (Wt%)
Actual
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
TBP at 500C (Wt%)
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
TBP at 700C (Wt%)
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
TBP at 200C (Wt%)N
MR
Pre
dict
ed
-10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
TBP at 50C (Wt%)
Actual
NM
RPr
edic
ted
-1
2
5
8
11
-1 2 5 8 11 14
-1
2
5
8
11
-1 2 5 8 11 14
1
2
3 45
6
7
8
9
10
11
1213
1415
16
17
18
20
21
22
23
24
25
26
28
2930
31 32
33
34
35
36
37
38
39
40
41
42
43 44
4546
47
4850
5152
53
54
55
56
57
58
59
60
-1
2
5
8
11
-1 2 5 8 11 14
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
Actual
NM
RPr
edic
ted
45
60
75
90
105
50 65 80 95
45
60
75
90
105
50 65 80 95
1
34
56 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
2324
25
26
27
28
29
3031
32
33
34
3536
37
38
39
40
414243
44
4546
47
48
49
50
5152
53
54
55
56
57
5859
60
45
60
75
90
105
50 65 80 95
TBP at 500C (Wt%)
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
TBP at 700C (Wt%)
Actual
NM
R P
redi
cted
74
80
86
92
98
76 82 88 94 100 74
80
86
92
98
76 82 88 94 100
1
34
56
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 24
2526
2728
29
3031
32
33
34
3536
37
38
39
40
414243 44
45 46
47
48
49
50
5152
53
54
55
56
57
5859
60
74
80
86
92
98
76 82 88 94 100
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
Actual
10 25 40 55 70 10 25 40 55 70
1
234
56
78
9
10
11 12
13
1415
16
17
18
19
20212223
24
25
262829
30
3132
33
34
3536
37
38
39
40
4142
43 44
4546
47
48
49515253 54
55
56
57
5859
60
10 25 40 55 70
TBP at 200C (Wt%)N
MR
Pre
dict
ed
-10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5 -10
20
50
80
-5 -10
20
50
80
-5
27
-10
20
50
80
-5
Actual Crude TBP Curves
0
10
20
30
40
50
60
70
80
90
100
30 130 230 330
Temperature (C)
Cum
ulat
ive
Wei
ght L
oss
( Wt%
)
KuwaitMarib LightNembaGOS MixDulangBacho
Actual Crude TBP Curves
0
10
20
30
40
50
60
70
80
90
100
30 130 230 330
Temperature (C)
Cum
ulat
ive
Wei
ght L
oss
( Wt%
)
KuwaitMarib LightNembaGOS MixDulangBacho
NMR Predicted TBP Curves for Crudes
0102030405060708090
100
30 130 230 330Temperature (C)
Cum
ulat
ive
Wei
ght L
oss
(Wt%
)
NMR Predicted TBP Curves for Crudes
0102030405060708090
100
30 130 230 330Temperature (C)
Cum
ulat
ive
Wei
ght L
oss
(Wt%
)
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
pna-15-95.tdf,9 (R² = 0.892837573)pna-15-95.tdf,9 (R² = 0.892837573)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
20
35
50
18 24 30 36 42 48
20
35
50
18 24 30 36 42 48
1
2
3 4
5
6
7
8
10
11
12
13
1415
1617
18
19
20
22
23
24
25
27
28
29
31
32
33
34
3637
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 53
54
55
56
57
58
5961
62
63
64
65
66
67
68
69
70
71
72
73
74 75
7677
78
79
81
82
83
84
8586
87
88
89
90
91
93
94
95
96
98
99
100
102
103
104
105
107108
110
111
112
113
114
115
116117
118
119 120
121
122
123
124
125
126
127
128
129130
132
133
134
135
136
137
138
139
140
141
142
20
35
50
18 24 30 36 42 48
Normal-Paraffins of 15-95C Cut
pna-15-95.tdf,9 (R² = 0.892837573)pna-15-95.tdf,9 (R² = 0.892837573)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
20
35
50
18 24 30 36 42 48
20
35
50
18 24 30 36 42 48
1
2
3 4
5
6
7
8
10
11
12
13
1415
1617
18
19
20
22
23
24
25
27
28
29
31
32
33
34
3637
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 53
54
55
56
57
58
5961
62
63
64
65
66
67
68
69
70
71
72
73
74 75
7677
78
79
81
82
83
84
8586
87
88
89
90
91
93
94
95
96
98
99
100
102
103
104
105
107108
110
111
112
113
114
115
116117
118
119 120
121
122
123
124
125
126
127
128
129130
132
133
134
135
136
137
138
139
140
141
142
20
35
50
18 24 30 36 42 48
Normal-Paraffins of 15-95C Cut
pna-15-95.tdf,5 (R² = 0.914837471)pna-15-95.tdf,5 (R² = 0.914837471)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F15
C1
)P
redi
cted
Con
cent
ratio
n ( F
15 C
1 )
24
30
36
42
48
54
24 30 36 42 48 54 60
24
30
36
42
48
54
24 30 36 42 48 54 60
1
3
4
5
6
7
8
9
10
11
12
1314
15
16
17
18
19
20
21
22
24
25
27
28
29
30
3132
3334
35
36
38 40
42
43
44
45
4647
48
51
5354
55
56
58
59
61
62
64
66
67
69
70
71
72
74
75
76
77
78
79
80
8182
83
84
85
86
87
88
89
90
91
92
93
9697
98
99
100
101
102103
104
105
106
107
109
111113
114
116
117118
119
124
125
126
127129
130
132
133
135
137
138
140
141
142
24
30
36
42
48
54
24 30 36 42 48 54 60
Iso-Paraffins of 15-95C Cut
pna-15-95.tdf,5 (R² = 0.914837471)pna-15-95.tdf,5 (R² = 0.914837471)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F15
C1
)P
redi
cted
Con
cent
ratio
n ( F
15 C
1 )
24
30
36
42
48
54
24 30 36 42 48 54 60
24
30
36
42
48
54
24 30 36 42 48 54 60
1
3
4
5
6
7
8
9
10
11
12
1314
15
16
17
18
19
20
21
22
24
25
27
28
29
30
3132
3334
35
36
38 40
42
43
44
45
4647
48
51
5354
55
56
58
59
61
62
64
66
67
69
70
71
72
74
75
76
77
78
79
80
8182
83
84
85
86
87
88
89
90
91
92
93
9697
98
99
100
101
102103
104
105
106
107
109
111113
114
116
117118
119
124
125
126
127129
130
132
133
135
137
138
140
141
142
24
30
36
42
48
54
24 30 36 42 48 54 60
Iso-Paraffins of 15-95C Cut
pna-15-95.tdf,14 (R² = 0.845575799)pna-15-95.tdf,14 (R² = 0.845575799)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F14
C1
)P
redi
cted
Con
cent
ratio
n ( F
14 C
1 )
10
25
40
6 12 18 24 30 36 42
10
25
40
6 12 18 24 30 36 42
1
2
3
4
5
7
81011
12
13
14
15
17
18
19
20
21
22
23
24
25
27
28
29
30
31
32
33
34
35
3638
39
40
41
42
43 44
4546
47
48
4950
51
53
54
55
58
59
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
8182
83
84
85
86
88
89
90
91
9293
94
95 96
98
99
100101
102
103 104
105
106
107
109
111
112
113
114 115
116117
118
119
120
121
122124
125
126
127
129
130
132
133
134
135
136
137
138
139
141
142
10
25
40
8 14 20 26 32 38
Naphthenes of 15-95C Cut
pna-15-95.tdf,14 (R² = 0.845575799)pna-15-95.tdf,14 (R² = 0.845575799)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F14
C1
)P
redi
cted
Con
cent
ratio
n ( F
14 C
1 )
10
25
40
6 12 18 24 30 36 42
10
25
40
6 12 18 24 30 36 42
1
2
3
4
5
7
81011
12
13
14
15
17
18
19
20
21
22
23
24
25
27
28
29
30
31
32
33
34
35
3638
39
40
41
42
43 44
4546
47
48
4950
51
53
54
55
58
59
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
8182
83
84
85
86
88
89
90
91
9293
94
95 96
98
99
100101
102
103 104
105
106
107
109
111
112
113
114 115
116117
118
119
120
121
122124
125
126
127
129
130
132
133
134
135
136
137
138
139
141
142
10
25
40
8 14 20 26 32 38
Naphthenes of 15-95C Cut
pna-15-95.tdf,19 (R² = 0.917781604)pna-15-95.tdf,19 (R² = 0.917781604)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
-1
2
5
8
11
14
-1 2 5 8 11 14
-1
2
5
8
11
14
-1 2 5 8 11 14
1
2
34
5 67
891011
12
13
14
15
1617
19
21
22
23
2425
26
27
2829
30
31
32
33
34
35
36
37
38
40
42
43
44
45
46
4748
50
51
52
53
54
5556
59
60
61
63 64
65
66
68
69
70
71
72
73
74
75
76 77
7879
8081
82
83
84
85
86
87
88
90
92
93
94
95
9697
98
99100
101
102
103
104
105
106
107
108
109111
113
114
115116
117
119
121
122
123
124
125
126127 130
131
132
134135
136
137
139
140
141
142
-1
2
5
8
11
14
-1 2 5 8 11 14
Aromatics of 15-95C Cut
pna-15-95.tdf,19 (R² = 0.917781604)pna-15-95.tdf,19 (R² = 0.917781604)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
-1
2
5
8
11
14
-1 2 5 8 11 14
-1
2
5
8
11
14
-1 2 5 8 11 14
1
2
34
5 67
891011
12
13
14
15
1617
19
21
22
23
2425
26
27
2829
30
31
32
33
34
35
36
37
38
40
42
43
44
45
46
4748
50
51
52
53
54
5556
59
60
61
63 64
65
66
68
69
70
71
72
73
74
75
76 77
7879
8081
82
83
84
85
86
87
88
90
92
93
94
95
9697
98
99100
101
102
103
104
105
106
107
108
109111
113
114
115116
117
119
121
122
123
124
125
126127 130
131
132
134135
136
137
139
140
141
142
-1
2
5
8
11
14
-1 2 5 8 11 14
Aromatics of 15-95C Cut
pna-15-95.tdf,9 (R² = 0.892837573)pna-15-95.tdf,9 (R² = 0.892837573)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
20
35
50
18 24 30 36 42 48
20
35
50
18 24 30 36 42 48
1
2
3 4
5
6
7
8
10
11
12
13
1415
1617
18
19
20
22
23
24
25
27
28
29
31
32
33
34
3637
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 53
54
55
56
57
58
5961
62
63
64
65
66
67
68
69
70
71
72
73
74 75
7677
78
79
81
82
83
84
8586
87
88
89
90
91
93
94
95
96
98
99
100
102
103
104
105
107108
110
111
112
113
114
115
116117
118
119 120
121
122
123
124
125
126
127
128
129130
132
133
134
135
136
137
138
139
140
141
142
20
35
50
18 24 30 36 42 48
Normal-Paraffins of 15-95C Cut
pna-15-95.tdf,9 (R² = 0.892837573)pna-15-95.tdf,9 (R² = 0.892837573)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
20
35
50
18 24 30 36 42 48
20
35
50
18 24 30 36 42 48
1
2
3 4
5
6
7
8
10
11
12
13
1415
1617
18
19
20
22
23
24
25
27
28
29
31
32
33
34
3637
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 53
54
55
56
57
58
5961
62
63
64
65
66
67
68
69
70
71
72
73
74 75
7677
78
79
81
82
83
84
8586
87
88
89
90
91
93
94
95
96
98
99
100
102
103
104
105
107108
110
111
112
113
114
115
116117
118
119 120
121
122
123
124
125
126
127
128
129130
132
133
134
135
136
137
138
139
140
141
142
20
35
50
18 24 30 36 42 48
Normal-Paraffins of 15-95C Cut
pna-15-95.tdf,5 (R² = 0.914837471)pna-15-95.tdf,5 (R² = 0.914837471)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F15
C1
)P
redi
cted
Con
cent
ratio
n ( F
15 C
1 )
24
30
36
42
48
54
24 30 36 42 48 54 60
24
30
36
42
48
54
24 30 36 42 48 54 60
1
3
4
5
6
7
8
9
10
11
12
1314
15
16
17
18
19
20
21
22
24
25
27
28
29
30
3132
3334
35
36
38 40
42
43
44
45
4647
48
51
5354
55
56
58
59
61
62
64
66
67
69
70
71
72
74
75
76
77
78
79
80
8182
83
84
85
86
87
88
89
90
91
92
93
9697
98
99
100
101
102103
104
105
106
107
109
111113
114
116
117118
119
124
125
126
127129
130
132
133
135
137
138
140
141
142
24
30
36
42
48
54
24 30 36 42 48 54 60
Iso-Paraffins of 15-95C Cut
pna-15-95.tdf,5 (R² = 0.914837471)pna-15-95.tdf,5 (R² = 0.914837471)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F15
C1
)P
redi
cted
Con
cent
ratio
n ( F
15 C
1 )
24
30
36
42
48
54
24 30 36 42 48 54 60
24
30
36
42
48
54
24 30 36 42 48 54 60
1
3
4
5
6
7
8
9
10
11
12
1314
15
16
17
18
19
20
21
22
24
25
27
28
29
30
3132
3334
35
36
38 40
42
43
44
45
4647
48
51
5354
55
56
58
59
61
62
64
66
67
69
70
71
72
74
75
76
77
78
79
80
8182
83
84
85
86
87
88
89
90
91
92
93
9697
98
99
100
101
102103
104
105
106
107
109
111113
114
116
117118
119
124
125
126
127129
130
132
133
135
137
138
140
141
142
24
30
36
42
48
54
24 30 36 42 48 54 60
Iso-Paraffins of 15-95C Cut
pna-15-95.tdf,14 (R² = 0.845575799)pna-15-95.tdf,14 (R² = 0.845575799)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F14
C1
)P
redi
cted
Con
cent
ratio
n ( F
14 C
1 )
10
25
40
6 12 18 24 30 36 42
10
25
40
6 12 18 24 30 36 42
1
2
3
4
5
7
81011
12
13
14
15
17
18
19
20
21
22
23
24
25
27
28
29
30
31
32
33
34
35
3638
39
40
41
42
43 44
4546
47
48
4950
51
53
54
55
58
59
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
8182
83
84
85
86
88
89
90
91
9293
94
95 96
98
99
100101
102
103 104
105
106
107
109
111
112
113
114 115
116117
118
119
120
121
122124
125
126
127
129
130
132
133
134
135
136
137
138
139
141
142
10
25
40
8 14 20 26 32 38
Naphthenes of 15-95C Cut
pna-15-95.tdf,14 (R² = 0.845575799)pna-15-95.tdf,14 (R² = 0.845575799)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F14
C1
)P
redi
cted
Con
cent
ratio
n ( F
14 C
1 )
10
25
40
6 12 18 24 30 36 42
10
25
40
6 12 18 24 30 36 42
1
2
3
4
5
7
81011
12
13
14
15
17
18
19
20
21
22
23
24
25
27
28
29
30
31
32
33
34
35
3638
39
40
41
42
43 44
4546
47
48
4950
51
53
54
55
58
59
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
8182
83
84
85
86
88
89
90
91
9293
94
95 96
98
99
100101
102
103 104
105
106
107
109
111
112
113
114 115
116117
118
119
120
121
122124
125
126
127
129
130
132
133
134
135
136
137
138
139
141
142
10
25
40
8 14 20 26 32 38
Naphthenes of 15-95C Cut
pna-15-95.tdf,19 (R² = 0.917781604)pna-15-95.tdf,19 (R² = 0.917781604)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
-1
2
5
8
11
14
-1 2 5 8 11 14
-1
2
5
8
11
14
-1 2 5 8 11 14
1
2
34
5 67
891011
12
13
14
15
1617
19
21
22
23
2425
26
27
2829
30
31
32
33
34
35
36
37
38
40
42
43
44
45
46
4748
50
51
52
53
54
5556
59
60
61
63 64
65
66
68
69
70
71
72
73
74
75
76 77
7879
8081
82
83
84
85
86
87
88
90
92
93
94
95
9697
98
99100
101
102
103
104
105
106
107
108
109111
113
114
115116
117
119
121
122
123
124
125
126127 130
131
132
134135
136
137
139
140
141
142
-1
2
5
8
11
14
-1 2 5 8 11 14
Aromatics of 15-95C Cut
pna-15-95.tdf,19 (R² = 0.917781604)pna-15-95.tdf,19 (R² = 0.917781604)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F17
C1
)P
redi
cted
Con
cent
ratio
n ( F
17 C
1 )
-1
2
5
8
11
14
-1 2 5 8 11 14
-1
2
5
8
11
14
-1 2 5 8 11 14
1
2
34
5 67
891011
12
13
14
15
1617
19
21
22
23
2425
26
27
2829
30
31
32
33
34
35
36
37
38
40
42
43
44
45
46
4748
50
51
52
53
54
5556
59
60
61
63 64
65
66
68
69
70
71
72
73
74
75
76 77
7879
8081
82
83
84
85
86
87
88
90
92
93
94
95
9697
98
99100
101
102
103
104
105
106
107
108
109111
113
114
115116
117
119
121
122
123
124
125
126127 130
131
132
134135
136
137
139
140
141
142
-1
2
5
8
11
14
-1 2 5 8 11 14
Aromatics of 15-95C Cut
density-api-s.tdf,12 (R² = 0.971960511)density-api-s.tdf,12 (R² = 0.971960511)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
15
30
45
15 30 45
15
30
45
15 30 45
1
2
34
56 7
8
9
1011
12 13
1415
16
17
18
1920
21
22
2324
25
26
27
28
29
3031
32
33
35
36
373839
40
41
42
43
45
46
47
48
5054
55
56
57
59
60
61
62
63
65
66
67
68
69
70
7274
75
7677
78
79
80
81
82
8384
8586
8788
89
90
91
9293
94
95
96
97
98
99
100
101
102
103104
105 106
107
108
109
110111112
113
114
115
116118119
120
121
123128
129
130
132
133
134135
136
138
139
140
141142 143
144
145
15
30
45
15 30 45
API Gravity
density-api-s.tdf,12 (R² = 0.971960511)density-api-s.tdf,12 (R² = 0.971960511)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
15
30
45
15 30 45
15
30
45
15 30 45
1
2
34
56 7
8
9
1011
12 13
1415
16
17
18
1920
21
22
2324
25
26
27
28
29
3031
32
33
35
36
373839
40
41
42
43
45
46
47
48
5054
55
56
57
59
60
61
62
63
65
66
67
68
69
70
7274
75
7677
78
79
80
81
82
8384
8586
8788
89
90
91
9293
94
95
96
97
98
99
100
101
102
103104
105 106
107
108
109
110111112
113
114
115
116118119
120
121
123128
129
130
132
133
134135
136
138
139
140
141142 143
144
145
15
30
45
15 30 45
API Gravity
con res-asphaltenes.tdf,2 (R² = 0.97418733)con res-asphaltenes.tdf,2 (R² = 0.97418733)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
-1
2
5
8
11
-1 2 5 8 11
-1
2
5
8
11
-1 2 5 8 11
1
2
34
5 6
7
8
9
1011
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
2728
2930
31
3233
3435
36
3738
39
40
41
42
4344
4546
47
48
51
5254
55
56
57
58
59
60
61
6264
65
66
67
68 69
70
71
72
7374
75
76
77
787980
81
82
8384
85
86
88
89
90
91
92
93
94
95
96
97
98
99
100101
102
103
104
105
106
107108
109
110111
112
113
114
115
116117
118
119
120
121
124125
126
127
128
129
130
131
132
133
134
135137
138
139
140
141142
143
144
145146
-1
2
5
8
11
-1 2 5 8 11
Carbon Residue
con res-asphaltenes.tdf,2 (R² = 0.97418733)con res-asphaltenes.tdf,2 (R² = 0.97418733)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
-1
2
5
8
11
-1 2 5 8 11
-1
2
5
8
11
-1 2 5 8 11
1
2
34
5 6
7
8
9
1011
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
2728
2930
31
3233
3435
36
3738
39
40
41
42
4344
4546
47
48
51
5254
55
56
57
58
59
60
61
6264
65
66
67
68 69
70
71
72
7374
75
76
77
787980
81
82
8384
85
86
88
89
90
91
92
93
94
95
96
97
98
99
100101
102
103
104
105
106
107108
109
110111
112
113
114
115
116117
118
119
120
121
124125
126
127
128
129
130
131
132
133
134
135137
138
139
140
141142
143
144
145146
-1
2
5
8
11
-1 2 5 8 11
Carbon Residue
density-api-s.tdf,12 (R² = 0.971960511)density-api-s.tdf,12 (R² = 0.971960511)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
15
30
45
15 30 45
15
30
45
15 30 45
1
2
34
56 7
8
9
1011
12 13
1415
16
17
18
1920
21
22
2324
25
26
27
28
29
3031
32
33
35
36
373839
40
41
42
43
45
46
47
48
5054
55
56
57
59
60
61
62
63
65
66
67
68
69
70
7274
75
7677
78
79
80
81
82
8384
8586
8788
89
90
91
9293
94
95
96
97
98
99
100
101
102
103104
105 106
107
108
109
110111112
113
114
115
116118119
120
121
123128
129
130
132
133
134135
136
138
139
140
141142 143
144
145
15
30
45
15 30 45
API Gravity
density-api-s.tdf,12 (R² = 0.971960511)density-api-s.tdf,12 (R² = 0.971960511)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
15
30
45
15 30 45
15
30
45
15 30 45
1
2
34
56 7
8
9
1011
12 13
1415
16
17
18
1920
21
22
2324
25
26
27
28
29
3031
32
33
35
36
373839
40
41
42
43
45
46
47
48
5054
55
56
57
59
60
61
62
63
65
66
67
68
69
70
7274
75
7677
78
79
80
81
82
8384
8586
8788
89
90
91
9293
94
95
96
97
98
99
100
101
102
103104
105 106
107
108
109
110111112
113
114
115
116118119
120
121
123128
129
130
132
133
134135
136
138
139
140
141142 143
144
145
15
30
45
15 30 45
API Gravity
con res-asphaltenes.tdf,2 (R² = 0.97418733)con res-asphaltenes.tdf,2 (R² = 0.97418733)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
-1
2
5
8
11
-1 2 5 8 11
-1
2
5
8
11
-1 2 5 8 11
1
2
34
5 6
7
8
9
1011
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
2728
2930
31
3233
3435
36
3738
39
40
41
42
4344
4546
47
48
51
5254
55
56
57
58
59
60
61
6264
65
66
67
68 69
70
71
72
7374
75
76
77
787980
81
82
8384
85
86
88
89
90
91
92
93
94
95
96
97
98
99
100101
102
103
104
105
106
107108
109
110111
112
113
114
115
116117
118
119
120
121
124125
126
127
128
129
130
131
132
133
134
135137
138
139
140
141142
143
144
145146
-1
2
5
8
11
-1 2 5 8 11
Carbon Residue
con res-asphaltenes.tdf,2 (R² = 0.97418733)con res-asphaltenes.tdf,2 (R² = 0.97418733)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F16
C1
)P
redi
cted
Con
cent
ratio
n ( F
16 C
1 )
-1
2
5
8
11
-1 2 5 8 11
-1
2
5
8
11
-1 2 5 8 11
1
2
34
5 6
7
8
9
1011
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
2728
2930
31
3233
3435
36
3738
39
40
41
42
4344
4546
47
48
51
5254
55
56
57
58
59
60
61
6264
65
66
67
68 69
70
71
72
7374
75
76
77
787980
81
82
8384
85
86
88
89
90
91
92
93
94
95
96
97
98
99
100101
102
103
104
105
106
107108
109
110111
112
113
114
115
116117
118
119
120
121
124125
126
127
128
129
130
131
132
133
134
135137
138
139
140
141142
143
144
145146
-1
2
5
8
11
-1 2 5 8 11
Carbon Residue
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
R² = 0.9982rmsd=0.11 Wt%
Actual Water Content (Wt%)
Pred
icte
d W
ater
Con
tent
(Wt%
)
123
45
6
78
910
11
12
1617
1920
21
2224
25
26
27
2829
303132
34
350
3
6
9
0 3 6 9
R² = 0.9982rmsd=0.11 Wt%
Actual Water Content (Wt%)
Pred
icte
d W
ater
Con
tent
(Wt%
)
123
45
6
78
910
11
12
1617
1920
21
2224
25
26
27
2829
303132
34
350
3
6
9
0 3 6 9
Water in Crude By Process 1H NMR
0 Wt%
1.7
3.5
7.1
9.4
19.8
30 40 50 60 70 80 90 100 110 120
0 Wt%
1.7
3.5
7.1
9.4
19.8
0 Wt%
1.7
3.5
7.1
9.4
19.8
30 40 50 60 70 80 90 100 110 120
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Crude Analysis
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Lagomar/Basrah 71/29GP(Lagotreco/DZO/Boscan) 95/4/1GP(Lagotreco/DZO/Boscan/Slops) 90/4/1/5GP(Lagotreco/DZO) 95/5GP(Lagotreco/Oriente/DZO/Slops) 68/23/4/5GP(Lagotreco/Oriente/DZO) 92/3/5GP(Lagotreco/Oriente/mesa/DZO) 74/14/7/5GP(Lagotreco/Oriente/mesa/DZO/slops) 51/11/28/5/5GP(Lagotreco/LagotrcoMediano/Oriente/mesa/DZO/Slops) 37/2/24/28/4/5GP(DZO/MESA/Lagotreco/LagotrcoMediano/Orientae/Slops) 5/27/42/6/12/3
GP = General Purpose Crude. Slops = refinery slop re-blends of unknown composition and quality.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050
Cut Point Deg C
WT%
Yie
ld
LPReconNMR
Blue line represents the predicted curve using only an off-line LP program based on historical crude properties of the blend.
Magenta line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050
Cut Point Deg C
WT%
Yie
ld
LPReconNMR
Blue line represents the predicted curve using only an off-line LP program based on historical crude properties of the blend.
Magenta line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050
Cut Point Deg C
WT%
Yie
ld
LPReconNMR
Blue line represents the predicted curve using only an off-line LP program based on historical crude properties of the blend.
Magenta line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050
Cut Point Deg C
WT%
Yie
ld
LPReconNMR
Blue line represents the predicted curve using only an off-line LP program based on historical crude properties of the blend.
Magenta line is the actual yield curve for the same crude blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NMR predicted yield curve demonstrating the NMR accuracy compared to the LP.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Crude API 8/25-9/6/01
2526272829303132333435
0:03
:38
15:1
6:27
6:29
:22
21:4
2:25
12:5
5:32
4:08
:17
19:2
1:02
10:3
3:52
1:46
:49
18:4
9:43
10:1
0:13
1:30
:48
16:5
1:30
8:12
:22
23:3
2:13
14:5
3:09
6:14
:16
5:48
:57
21:0
7:14
12:2
5:33
Crude Switch
Tank Switch
Feed change
causing CDU
upset.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
0
5
10
15
20 40 60 80 100 120 140
60 MHz NMR of on-line and laboratory analyzed crude samples. Red Spectrum is ASTM 0903 (Cushing) run in PNA lab.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
0
.1
.2
.3
.4
.5
.6
.7
30 40 50 60 70 80
Olefins from coker diesel for reference
Olefins in crude are typically from the blending of cracked stocks found in refinery slops, condensate, etc, or from thermal cracking in enhanced recovery processes.
2 distinct water peaks are observed, some centered at 74 and most centered at 78. Water peak position is indicator of polarity of crude matrix.
0
.1
.2
.3
.4
.5
.6
.7
30 40 50 60 70 80
0
.1
.2
.3
.4
.5
.6
.7
30 40 50 60 70 80
Olefins from coker diesel for reference
Olefins in crude are typically from the blending of cracked stocks found in refinery slops, condensate, etc, or from thermal cracking in enhanced recovery processes.
2 distinct water peaks are observed, some centered at 74 and most centered at 78. Water peak position is indicator of polarity of crude matrix.
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
0
.2
.4
.6
.8
30 40 50 60 70 80
0
.2
.4
.6
.8
30 40 50 60 70 80
0
.2
.4
.6
.8
Aromatic and Water Region Expansion Red Spectrum is ASTM 0903
On-line spectra showing two distinct water peaks. Crude spectra are after pre-heaters and desalters. Water position is indicator of crude polarity.
combined crude simdis t10(f) 060209.tdf,6 (R² = 0.95281493)combined crude simdis t10(f) 060209.tdf,6 (R² = 0.95281493)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F8
C1
)
160
220
280
340
160 220 280 340
160
220
280
340
160 220 280 340
36
78
10
121314
15
1620
2122 23
24
2526
27
303233
373941 4243
45 46
474849505152
565758
596061656667 68
6970
747576
777879
808182
8384858687
88
899091
929394959697
9899100101102103104105106107108109110111112113114115116117118
119120121122123124 125126127
128129130132137138139
143146
149150151
155
156157
159
161163
164
165167168169170
171
173
174175176
180181182
183
191
192193
195196 197
198
201203
211212
213
216
218220221222223
224225226
227228229230231232
236237238
239240
241242243
247248
160
220
280
340
160 220 280 340
combined crude simdis t30(f) 060209.tdf,5 (R² = 0.935901615)combined crude simdis t30(f) 060209.tdf,5 (R² = 0.935901615)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F8
C1
)
320
380
440
500
560
620
320 380 440 500 560 620
320
380
440
500
560
620
320 380 440 500 560 620
35
6
78
9
1112
14 1516
17
18
1923
2425
2627 28
2930
31
32
333537
38
39
4041
42
44
4547
48
74
75
76
77
78
79
83848586
87
89
909192
969798102
103 107
108109110
111112
113114
117118119
127128129
132
134136
137138139
140141142
143144145146147148152153154
155156157159
160161162
163164
165
167168
169170171172
173174178
179180
184185186
187
188189 190
191
192
193194
195196197198199200201
202203204206207
211212213
214215216
217218219
220221222 223
224
225
226227228
232233234
235236237238239240241242243
244245246247248249250
251252253254255 256257258
259260
261262263264
320
380
440
500
560
620
320 380 440 500 560 620
combined crude simdis t50 (f) 060209.tdf,5 (R² = 0.933545027)
Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F8
C1
)
500
650
800
500 560 620 680 740 800
500
650
800
500 560 620 680 740 800
1
34
6
7
8
910
1213
151617
18
19
20
2223
25
2627 28 293031
3233
3436
373839
4142 4344
4546
47
4849
50
51
52
53
54
555761
626364
65
6667 686970
7172
73
747576
777879
82
899091
9293
959697
98
99
100
101
102103
104105
106
107108109110111112
113114115116117118
119120121 122123
124125126127128129130
131132133134135136137
138
139 140141142
143144145146
147148
176
177
178
182183184185186
187
188
192193194 207
208
209
210211212213 216
217218
226227228
233235236237238
239240241
242243244
245246247248249250
251
252
253254255
256257258259260261
262263
264
266267
500
650
800
500 560 620 680 740 800
combined crude simdis t70 (f) 060209.tdf,6 (R² = 0.94056458)
Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F8
C1
)
650
800
950
1100
700 850 1000 650
800
950
1100
700 850 1000
13 4
567
9 10
1112
1314
1516
17
18
2021
222324
2526 27
28
29303132
33 34353637
3839
40
4142
43
44
4546
535455
59
6061
63
65
66
67
717273
7475
76
77818283
848586
90
91
979899100101102
103104105106107
108109
115116
117
120
121122124
125126127
128129130
131132133
134135136137138139
140
141
142143144
145146147148149150
151152
153
154
155156
157158159161162
172173174
175
176177178179180
182
184185186
187188189
190192
199200
205206
208
209210
211
212213
217218219
220221222
223224225226227228
229230231
232233
234
235236237238239240
241242243
244245246247248
249250251252
650
800
950
1100
700 850 1000
SimDis T10
SimDis T70SimDis T50
SimDis T30
Process NMR Associates, LLC www.process-nmr.com
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combined crude simdis t90 (f) 060209.tdf,7 (R² = 0.938801011)
Actual Concentration ( C1 )
Pre
dict
ed C
once
ntra
tion
( F7
C1
)
950
1100
1250
940 1000 1060 1120 1180 1240 1300
950
1100
1250
940 1000 1060 1120 1180 1240 1300
1
34
56
7
12
14
15
1617
18
19
20
21
2223
24
2526
3132
36
37
41
45
47
5455
606162
636465
69
70
71
757677
787980818283
848586
878889
9192
939495
99100101102
103
104105106107
108109110
126
129
130131134136
137
139
147149151
173
174177178
179 181182183
193
198
199
200201202203
204205206
207208209
210211212
216
217
218219220221222223
227228
229
230
231232
950
1100
1250
940 1000 1060 1120 1180 1240 1300
3 day API GravitySame model - two crude feeds
2526272829303132333435
Fraction 1 (Vol%)
2022242628303234363840
Fraction 2 (Vol%)
30
32
34
36
38
40
42
44
SimDis T90
Process NMR Associates, LLC www.process-nmr.com
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0
2
4
6
8
10
20 40 60 80 100 120 140
Bitumen
Asphaltenes
Comparison of Bitumen And Precipitated Asphaltenes
4 ring+
Process NMR Associates, LLC www.process-nmr.com
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An electron spin resonance (ESR) spectrometer detects the concentration and composition of chemical species with unpaired electrons that are present in a sample. Typical chemical species are free radicals and many transition metal ions, depending on their valence state. The sample is loaded into a high frequency resonant cavity in a magnetic field. Free radicals irradiated with microwave radiation will undergo transitions at a characteristic frequency
Sample Number
Location Vanadium Content (ppm) – Original Assay
1 Vasconia, Magdalena Basin, Columbia 39 2 Merey, Eastern Venezuela Basin, Venezuela 303 3 Oriente, Oriente Basin, Ecuador 65 4 Qua Iboe, Agbada Formation, Niger Delta 2 5 Basrah Light, Zubair Zone, Iraq 29
Process NMR Associates, LLC www.process-nmr.com
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-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
1.95
1.95
1.96
1.96
1.96
1.97
1.97
1.97
1.98
1.98
1.98
1.99
1.99
1.99
1.99 2 2 2
2.01
2.01
2.01
2.02
2.02
2.02
2.03
2.03
2.03
2.04
2.04
2.04
2.05
2.05
2.05
2.06
206
Kero Blnk BasLt Merey Oriente QuaIboe Vasconia
Process NMR Associates, LLC www.process-nmr.com
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-0.01
-0.005
0
0.005
0.01
0.015
0.02
2.1
2.1
2.11
2.11
2.11
2.11
2.12
2.12
2.12
2.13
2.13
2.13
2.13
2.14
2.14
2.14
2.15
2.15
2.15
2.16
2.16
2.16
2.16
2.17
2.17
2.17
2.18
2.18
Kero Blnk BasLt Merey Oriente QuaIboe Vasconia
0
5
10
15
10 8 67 4 2 0
0
5
10
15
10 8 67 4 2 0
All Diesels: (Data date range 1999 to present)
Atmospheric Crude Straight Run
Vacuum Crude Straight Run
Coker Diesel
FCC Diesel
Diesel Hydro Cracker Feed
Diesel Hydro Cracker Product
Mild, Moderate and Severely Hydro Treated Diesel
Blend Header Diesel
R R R
CH 3
CH 2
R
CH3
RH
RH
RH
HR
RR HH
Process NMR Associates, LLC www.process-nmr.com
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SAMPLING and TESTING
Process NMR Associates, LLC www.process-nmr.com
NMR Process Systems, Inc www.nmr-automation.com
Crude Diesel 124733
200225250275300325350375400425450475500525550575600625650675700725750
IBP1% O ff2% O ff3% O ff4% O ff5% O ff
1 0% O ff1 5% O ff2 0% O ff2 5% O ff3 0% O ff3 5% O ff4 0% O ff4 5% O ff5 0% O ff5 5% O ff6 0% O ff6 5% O ff7 0% O ff7 5% O ff8 0% O ff8 5% O ff9 0% O ff9 5% O ff9 6% O ff9 7% O ff9 8% O ff9 9% O ffF BP
SimDis D86
200
300
400
500
600
700
800
900
10 D S L T 5 T 50 T 95910 L C GO
T 5 T 50 T 95H C U C H GT
5 T 50 T 9510 D S L T 5 T 50 T 95LAD T 5 T 50 T 95
R R B /M A DT 5 T 50 T 95
C AR B D ST 5 T 50 T 95
SimDis (actual) Corr D86 Actual D86
Numerous factors (especially aromatics) are responsible for deviations between distillation methods.
200
300
400
500
600
700
800
900
10 D
SL T5 T50
T95
910
LCGO T5 T50
T95
HCU
CHG
T5 T50
T95
10 D
SL T5 T50
T95
LAD T5 T50
T95
RRB/
MAD T5 T50
T95
CARB
DSL T5 T50
T95
SimDis (actual) Corr D86 Actual D86
Numerous factors (especially aromatics) are responsible for deviations between distillation methods.
Process NMR Associates, LLC www.process-nmr.com
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ISSUES Traditional and Spectroscopic
• Sampling, Sampling, Sampling
• Representative Sample
• Time and Money
• Accuracy
• Value of the Information
Questions?