on-line analyses of crude feeds and distillation products unit control... · crude reconcilation...
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OnOn--Line Analyses of Crude Feeds and Distillation Products:Line Analyses of Crude Feeds and Distillation Products:Utilization of OnUtilization of On--Line NMR on a RefineryLine NMR on a Refinery’’s Crude Distillation Units Crude Distillation Unit
Paul J. GiammatteoPaul J. Giammatteo** and John C. Edwardsand John C. EdwardsProcess NMR Associates, LLCProcess NMR Associates, LLC
Danbury, ConnecticutDanbury, Connecticutwww.processwww.process--nmrnmr.com.com
Process NMR Associates
NMR Lösungsfertig für Raffinerien
LPG
Gasoline
Aromatics
Kerosene / Diesel
Fuel Oil
Lubricant Oils
Bitumen
VGO
Gas
Lt. Naphtha
Hy. Naphtha
AGO
Crude Oil
Residue
Olefins
iC4
Reformate
FCC Gasoline
Naphtha
Cat. Cracker
Alkylate
VacuumTower
Atmospheric Tower
Kero.Crude Oil -Preparation
Crude Oil Blending
Hydrocracker
Alky. Plant
Poly. Plant
Cat. Reformer Aromatic Extraction
Gas Plant
Coker
Distillate Blending
Process NMR Solutions in Refining
Process NMR Associates
Process NMR Associates
Process NMR Associates
Basic Measurement PrincipleBasic Measurement Principle
Process NMR Associates
10 8 6 4 2 0
R R R
CH3
CH2
R
H2O
PPM
CH3
Crude Oils – on-line spectra
Process NMR Associates
Actual API Gravity (Degrees)
Pred
icte
d AP
I Gra
vity
(Deg
rees
)
20
35
50
16 22 28 34 40 46 52
API GravityR2=0.963SECV=1.2o
20
35
50
16 22 28 34 40 46 52
1
2
34
57
8
9
10
12
13
14
15
16
19
20
22
23
24
27
28
2930
31 32
3435
36
37
38
39
4243
4546
48
5152
56
59
6061
62
6364
65
67
68
69
70
72
73
74
75
76
79
80
82
83
84
87
88
8990
91 92
9496
97
98
99
100
103104
106107
109
112113
117
120
121
122123
126
127129130131132
137
139140
141144
145
147
149
150
154155156
157
159160161162
163
164165166167 169
170171172173174
175176177178179
180181183184185186187188189
190191192193
194195196197198
199
200201202203
204205206207208
209210211212213
214215216217
218219220221
222229230232233234
235236237238239
240
241242243
244245246247
248249250251252253
254255256257
258259260261262263264265266267268271272273274275276277278
279
20
35
50
16 22 28 34 40 46 52
Process NMR Associates
Actual TBP @ 365C (Wt%)
Pred
icte
d TB
P @
365
C (W
t%)
20
50
80
25 40 55 70 85 100
TBP @ 365C (Wt%)R2=0.972SECV=1.8 Wt%
20
50
80
25 40 55 70 85 100
1
3
4
7
8
10
12
13
14
15
16
17
1920
21
22
23
24
2528
29
30
31
32
36
37
39
40
41
42
43
50
54
58
61
62
63
6568
70
71
72
73
74
76
77
80
81
83
85
86
87
88
89
9092
93
94
95
96
97
98101
102
103
104
105
109
110
112
113
114
115
116
123
127
131
134
135
138141
143
144
145
146
149150
154155156
157158
159
160
162
163166
167168
169170
171
172173174175177
178179180181182
183184185186187
188189191192193194195196197198200
202203204205206
207208209210211
212213214215216
217218219220221
222223224225
226228229230
231232233234235236237238239240241242
243244245247248
249250251252
253254255256257258
20
50
80
25 40 55 70 85 100
Process NMR Associates
Zafiro Blend
0.00
20.00
40.00
60.00
80.00
100.00
0 200 400 600 800
temp (C)
wt% Zafiro Blend p
Zafiro Blend
Basra
0.00
20.00
40.00
60.00
80.00
100.00
0 200 400 600 800
temp(c)
wt% Basra p
Basra
Maui Condensate
0.00
20.00
40.00
60.00
80.00
100.00
120.00
0 200 400 600 800
Temp (C)
Wt% Maui Condensate p
Maui Condensate
Odudu TBP
0.00
20.00
40.00
60.00
80.00
100.00
120.00
0 200 400 600 800
Temp (C)
Wt% Odudu p
Odudu
Process NMR Associates
-20
0
20
40
60
80
100
120
0 100 200 300 400 500 600 700 800
Temp (C)
Zafiro Blend
Badak
Didon
Basra
Maui Condensate
Odudu
Kirkuk
Bay Marchand
Alaskan North Slope
Schiehallion
Arab X-light
South Arne
Stag
Ross
Actual NMR TBP Curves
Process NMR Associates
10
15
20
25
30
35
40
45
50
55
API c165wt c365wt Sulfur*10
3 Day On3 Day On--line Crude Feed Analyses showing real time results for API Graviline Crude Feed Analyses showing real time results for API Gravity, ty, two TBP cut points (wt%, deg C), and sulfur. Crude 1 and Crude two TBP cut points (wt%, deg C), and sulfur. Crude 1 and Crude 2 are actually 2 are actually
crude blends of 3crude blends of 3--4 individual 4 individual crudes crudes plus refinery slops (2plus refinery slops (2--5% of blend).5% of blend).
Crude Adjustment
0
10
20
30
40
50
60
70
80
90
100
-150 50 250 450 650 850 1050CutPoint Deg C
WT%
Yie
ld
BeforeAfterNMR
Crude Reconcilation
•Crude Assay Data may be old. Crude Composition has changed over time.
•Every Crude Tank has a heel of mixed Crudes received earlier. Crude in a Tank will settle.
•A Crude Switch (normally 7 to 8 hours) leaves you with an unknown Blend of the old and new Crude
in the Pipeline
Benefit with on-line analyses - $3 million/year
NMR Lösungsfertig für Raffinerien
LPG
Gasoline
Aromatics
Kerosene / Diesel
Fuel Oil
Lubricant Oils
Bitumen
VGO
Gas
Lt. Naphtha
Hy. Naphtha
AGO
Crude Oil
Residue
Olefins
iC4
Reformate
FCC Gasoline
Naphtha
Cat. Cracker
Alkylate
VacuumTower
Atmospheric Tower
Kero.Crude Oil-Preparation
Crude Oil Blending
Hydrocracker
Alky. Plant
Poly. Plant
Cat. Reformer Aromatic Extraction
Gas Plant
Coker
Distillate Blending
Process NMR Solutions in Refining
Process NMR Associates
0
2
4
6
8
10
12
20 40 60 80 100 120 140
Arbitrary Y / Arbitrary X
File # 1 = LGO000~1
Foxboro NMR SPC File.
Naphtha
Kerosene
Heavy Gas Oil
Process NMR Associates
Distillation Parameters on CDU
0
100
200
300
400
500
600
700
800
900
0:00
5:54
11:4
7
17:4
1
23:3
5
5:49
11:4
2
17:3
6
23:3
0
5:04
10:5
8
16:5
2
22:4
6
4:42
10:3
6
16:3
0
22:2
4
4:22
10:1
6
16:1
0
22:0
3
Flash T10 T50 T90
Process NMR Associates
360
370
380
390
400
410
420
430
440
450
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
KERO PRODUCT 50% Lab KERO PRODUCT 50% NMR
Process NMR Associates
Naphthenes5/
17
5/24
5/31 6/7
6/14
6/21
6/28 7/5
7/12
7/19
7/26 8/2
8/9
8/16
8/23
8/30 9/6
Date
Wt% GC
NMR
Process NMR Associates
NMR Lösungsfertig für Raffinerien
LPG
Gasoline
Aromatics
Kerosene / Diesel
Fuel Oil
Lubricant Oils
Bitumen
VGO
Gas
Lt. Naphtha
Hy. Naphtha
AGO
Crude Oil
Residue
Olefins
iC4
Reformate
FCC Gasoline
Naphtha
Cat. Cracker
Alkylate
VacuumTower
Atmospheric Tower
Kero.Crude Oil-Preparation
Crude Oil Blending
Hydrocracker
Alky. Plant
Poly. Plant
Cat. Reformer Aromatic Extraction
Gas Plant
Coker
Distillate Blending
Process NMR Solutions in Refining
Process NMR Associates
05
101520253035404550
1.4000 1.4500 1.5000 1.5500 1.6000
Refractive Index
Car
bon
Aro
mat
icity
Correlation Between Carbon Aromaticity and Refractive Index
Why Measure Refractive Index When NMR Allows the Carbon Aromaticity to be Obtained Directly?
1.00
3.03
SF: 75.43 MHz SW: 50000.00 Hz AQ: 0.48 seconds TD: 65536 points Scale units: ppm
13C NMR Spectrum
Aromatics Paraffins
Area under aromatic peaks corresponds to carbon aromaticity
Correlate to 60 MHz Foxboro NMR Using PLS
00 15 30 45
0
15
0 15 30 45
12
345 6
7
8
9
10
1112
13
141516
1718
19
2021
22
232425
26
27
2829303132
333435
36373839
40
41
42
43
44
45464748
4950
51
52
5354
55
56
5758
5960
6162
63
64
6566
676869
70
71
72
73
7475
76
0
30
45
0 15 30 45
Actual Aromaticity (13C)
Pred
icte
d A
rom
atic
ity (1 H
)
0
2
4
6
8
10
12
0 20 40 60 80 100 120 140 160 180
PLSModel
arom.tdf,5 (R² = 0.996772359)arom.tdf,5 (R² = 0.996772359)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pred
icte
d C
once
ntra
tion
( F7
C1
)Pr
edic
ted
Con
cent
ratio
n ( F
7 C
1 )
0
15
30
45
0 15 30 45
0
15
30
45
0 15 30 45
1
2345
6
78
9 10
11
12
13
14
15
1617
18
19
20
21
22
23242526
27
28
2930
31
323334
35
36 3738
39
40
41
42
43
44
45464748
49
50
52
53
54
55
575859
606162
63
64
6667
68
70
7172 737475
7677
78
7980 8182
83
85
87
8889 9091
93
94
0
15
30
45
0 15 30 45
Actual 13C NMR Result (At% C)
1 H N
MR
Pre
dict
ed R
esul
t (A
t% C
) R2=0.997SECV=0.6 atomic % Carbon
Base Oil and VGO Carbon Aromaticity by 1H NMR and PLS in One Model
Process NMR Associates
Process NMR Associates
Process NMR Associates
SummarySummaryHigh Resolution NMR is now possible in a wide variety of onHigh Resolution NMR is now possible in a wide variety of on--line, line,
process environments.process environments.Simultaneous, multiSimultaneous, multi--parameter analyses can be performed using parameter analyses can be performed using
either direct measurements or either direct measurements or chemometric chemometric based correlations.based correlations.The hardware has been proven stable, robust, and available.The hardware has been proven stable, robust, and available.Economic paybacks, especially when linked to advanced process Economic paybacks, especially when linked to advanced process
control applications are substantial.control applications are substantial.
Process NMR Associates
AcknowledgementsAcknowledgements
J. Cijntje and S. Ranganathan, Isla Refinery, CuracaoT. Cohen, Foxboro NMR Ltd, Israel
Invensys
Process NMR Associates
Process NMR Associates