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Process NMR Associates
Detailed Hydrocarbon Analyses of Naphthaby On-Line NMR
Integration of Real-Time NMR Feed AnalysisWith Advanced Process Control and Optimization
Presented ByJohn Edwards, Ph.D.
Process NMR Associates, LLCDanbury, Connecticut
November 21, 2002Eastern Analytical Symposium, Somerset, New Jersey
Process NMR Associates
Presentation Overview
• Process NMR Associates, LLC – Business Profile
• NMR Basics – Very Briefly
• Advantages/Disadvantages of NMR as a Process Spectroscopy
• Applications
1. Naphtha Steam Cracking Control and Optimization
2. Reformer Unit Control
• Conclusion
Process NMR Associates
Company: Process NMR Associates, LLC
Founded : 1997
Personnel: 2 Ph.D. Chemists
Background: Analytical and Process Spectroscopy in Petroleum and Petrochemical (Texaco Inc.)
Facilities: 2 Invensys 58 MHz Process MRA Units300 MHz NMR (Liquids)200 MHz NMR (Solids)
Business: Application Development for Invensys Process MRAAnalytical NMR Services for Commercial and AcademicCustomers
Process NMR Associates
Process NMR Associates
Process NMR Associates
NMR Innovations Developed to Bring NMR On-Line
• Permanent Magnet Stability and Design
• Shimming Protocols
• Flow-Through Probe Technology
• Post Processing Developments
Robust auto-phasing routines
Frequency Domain Averaging
Post-processing monitoring of each constituent spectrumfor heavy stream analyses where sediment/rust may be present.
Process NMR Associates
Advantages and Disadvantages of NMR Applied to ProcessAdvantages:Non-optical spectroscopyNo spectral temperature dependence under optimal conditionsMinimal sampling requirementsSpectral response to sample chemistry is linearChemical regions of NMR spectra are orthogonalEntire volume is sampled by the NMR experimentWater is in distinct region and can be digitally removedDetailed hydrocarbon information is readily observed.Fundamental chemical information can be derived directly from spectrum.Colored or black samples are readily observed
Disadvantages:Solids cannot be observedIndividual molecular components not observed directly in the spectrum.Low sensitivity to impurities – quantitative > 1000 ppm.Sensitive to ferro-magnetics.Sample viscosity causes resolution changesNon-hydrogen containing species are not observed
Process NMR Associates
H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
RR
HH
R
H
R
H
R
H
HR
CH2CH3
CH3
CH3
PPMOxygenate
H-Types Observed in a Gasoline 1H NMR Spectrum
8 7 6 5 4 3 2 1 0
CH
RR
HH
R
H
R
H
R
H
HR
CH2CH3
CH3
CH3
PPMOxygenate
8 7 6 5 4 3 2 1 0
CH
RR
HH
RR
HH
R
H
R
H
R
H
HR
R
H
R
H
R
H
HR
R
H
HR
CH2CH3
CH3CH3
CH3
PPMOxygenate
Process NMR Associates
H2O
Process NMR Associates
Application: Steam Cracking Optimization
Cracker Facility Capacity: 600,000 Tonnes per Year
Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYROOptimization Package (Technip/KTI) and APC
NMR Analysis: 3-4 Minute Cycle (Single Stream)16 Minute Cycle (4 Feed Streams)
NMR PLS Outputs: Naphtha – Detailed PIONAc4-c10 n-paraffin, c4-C11 i-paraffin, c6-c10 aromatics, c5-c10naphthenes
Other Projects require D86 and D2887 Distillation and Density
Value Added: Unit Optimization - $150K /year 4 Units Now Being Optimized ($600K/year)ROI 6-8 Months
Performance : NMR Available 99%+ Since May 2000Models Updated in a Limited Manner
Plant Issues :
Crackers produce 600,000 tonnes of ethylene per year
365 Days of Production per year with turnaround every third year
Strategic Requirements : Naphtha purchased with widely varying feed specification
Need:
Cracker Feed Characterization for APC and Optimization
APC Requirements: Monitor feed characteristics to minimize lost production due to high number of feed transitions:
Simplistically: 1) Heavier naphtha can violate coil outlet temperatures leading to coking or tube wall damage
2) Lighter naphtha can exceed downstream compressor loading
Optimization Requirements: Detailed PIONA analysis allows conditions to be optimized for optimum ethylene/propylene/butyleneproduction based on market conditions.
Process NMR Associates
Process NMR Associates
Distillate
Furnace
Steam
Separation
C2-C3Fractionator
C4+Fractionator
Light Gas Oils
Naphtha
NMR
Optimizer
APC
Steam Ratio
Feed FlowRate
CoilOutlet Temp
Economic Data : Feed/Product Values
PossibleNMR
Steam Cracking Process
EquistarBASF-Antwerpen
Petrochina
Ethylene
Propylene
Butylene
LN
MN-HN
BASF-Ludwigshaven
Process NMR Associates
38.1937.4633.26Total iso-Paraffin
0.0500.2iso-C11
0.650.11.47iso-C10
1.840.52.45iso-C9
3.602.154.03iso-C8
7.105.335.8iso-C7
13.4813.499.05iso-C6
11.0515.519.86iso-C5
0.420.380.4iso-C4
37.7739.0833.08Total n-Paraffin
0.140.020.46n-C10
1.000.191.7n-C9
2.030.952.9n-C8
4.443.494.7n-C7
10.9210.57.97n-C6
15.9619.3711.73n-C5
3.284.533.46n-C4
Naphtha C
Naphtha B
Naphtha AComponent
0.030.120.3Total Olefins
5.503.3210Total Aromatics
0.0400.11Arom-C10
0.360.041.07Arom-C9
1.330.622.87Xylenes
0.210.070.55Ethyl-Benzene
1.791.233.15Toluene
1.771.362.25Benzene
18.3820.0223.36Total Naphthenes
0.0200.04Nap-C10
1.730.612.92Nap-C9
2.341.823.44Nap-C8
2.783.363.26Other Nap-C7
3.233.064.98Methylcyclohexane
3.133.823.77Cyclohexane
4.015.153.82Methylcyclopentane
1.142.21.13Cyclopentane
Naphtha C
Naphtha B
Naphtha AComponent
TYPICAL NAPHTHA
Process NMR Associates
Naphtha 1 Naphtha 2 Naphtha 3Conversion (%) 81.5 94.2 92.0Outlet Temperature (K) 1053 1073 1073Steam/Feed Ratio 0.5 0.5 0.75
Yields (Wt%)Hydrogen 0.5 0.7 0.7Methane 12.0 15.3 14.2
Ethyne 0.1 0.3 0.3Ethene 19.5 23.5 24.0Ethane 4.0 4.0 3.4
Propene 16.2 16.2 15.5Propane 0.5 0.5 0.5
Butadiene 3.7 4.0 4.3Butenes 7.9 5.4 6.0Butane 2.6 1.4 1.7
C5+ 30.2 26.0 25.8
Fuel Oil 2.5 3.4 3.0
Cracking Process Products
Process NMR Associates
N-Paraffin Variation Over 6 Months
20
25
30
35
40
45
50
55
1 7 13 19 25 31 37 43 49 55 61 67 73 79 85 91 97Naptha Purchase
Tota
l N-P
araf
fin (W
t%)
Process NMR Associates
0
10000
20000
30000
40000
50000
60000
6000 6500 7000 7500 8000
0
10000
20000
30000
40000
50000
60000
6000 6500 7000 7500 8000
Arbitrary / Arbitrary Paged Y-Zoom CURSOR
File # 1 = TEST200002 11/14/2002 6:48 AM Res=None
Foxboro NMR SPC File.
Benzene
Cyclohexane
Process NMR Associates
0
5
10
15
30 40 50 60 70 80 90 100 110
0
5
10
15
30 40 50 60 70 80 90 100 110
Aromatics Alpha-Protons
CH3
CH2
Cyclics
Olefins
Process NMR Associates
0
.2
.4
.6
.8
1
1.2
1.4
38 40 42 44 46 48 50 52
0
.2
.4
.6
.8
1
1.2
1.4
38 40 42 44 46 48 50 52
Aromatic Region
Process NMR Associates
0
5
10
15
85 90 95 100 105 110 115
0
5
10
15
85 90 95 100 105 110 115
Aliphatic Region
Process NMR Associates
Steam Cracker Optimization - Project Timeline
Feasibility Performed (30 Samples) – December 1999
Further Off-Line Model Expansion (90 Samples) – December 1999-March 2000
Online System Installed – April 2000
On-Line Localization and Further Model Expansion (65 Samples)– May to July 2000
Validation Period – 1 Month 100% Availability Within Specified Accuracy Limit - Aug 2000
System Validated and Accepted – September 2000
Add Validation Period Samples to Models – (Models now contain 215 Samples)
NMR Put on Control (Detailed PIONA into SPYRO Model for Unit Optimization) Oct 2000
Models have been performing relatively untouched (6 parameters of 32 updated on 4 occasions) since end of validation period. Models updated in limited manner 5 times in 2 years.
99+% Availability September 2000 – May 2002
March 2002 – Three Further Feed-Streams Added to NMR – No model updates required.
Process NMR Associates
Toluene
Actual Toluene (Wt%)
Pred
icte
d To
luen
e (W
t%) (
F9
C1
)
1
1
23
45
6
7
8
9
10
11
12
1314
15
16
17
18
1920
21
22
2325
26
2728
2930
31
32
33
34
35
36
37
383940
4142
43
44
45
46
4950
51
53
5456
58
59
6263
66
68
69
70
71
73
75
76
77
78
79
80
82
83
84
85
86
87
88
90
91
929394
95
9697
98
99
101
102
103
104
105
106
108
109
110
111
112
113
114
115
116
117
118119120
121
122123
124
125126
127128
129130131132133134135136137
138139140141142143
144145146
147148149
150151152
156157158159160161
162163164
165166167168169170
171172173174175176
177178179180181182183184185186187188
189190191
192193194195196197198199200
201202203
204205206
207208209210211212
213214215
216217218219220221222223224
225226227 228229230
231232233
234235236
237238239240241242243244245246247248249250251252253254
255256257258259260261262263
264265266
267268269270271272273274275
279280281282
283284285
286287288
289290291
292293294
295296297298299300301302303
304305306
307308309
310311312313314315
319320321
322323324325326327
328329330
331332333334335336
337338339
340341342343344345
346347348349350351
352353354
355356357358359360
361362363364365366367368369
370371372
373374375
376377378379380381382383384
385386387
388389390391392393
394395396397398399400401402
403404405
406407408
409410411
412413414
427428429 430431432433434435
436437438
439440441
445446447
448449450
451452453454455456
457458459
460461462
463464
465466467
471472473
477478
481482
483484485489490493494495496
-.5
1
2.5
4
5.5
0 1.5 3 4.5
Spectral Units ( )Be
ta C
oeffi
cien
t ( F
9 C
1 )
-1.5
0
1.5
10 40 70 100 130
-1.5
0
1.5
10 40 70 100 130
Process NMR Associates
Cyclohexane
Beta Coefficients
Spectral Units ( )Spectral Units ( )
Beta
Coe
ffici
ent (
F9
C1
)
-2
-.5
1
2.5
10 40 70 100 130
-2
-.5
1
2.5
10 40 70 100 130
Pred
icte
d C
yclo
hexa
ne( F
9 C
1 )
1
4
7
10
1 4 7 10 1 4 7 10
1
2345
6
78
910
11
12
1314
15
16
17
18
19
2021
22
23
242526
2728
29
30
3132
33
34
35
36
37
3839
4041
42
4346
47
48
49
50
51
52
53
54
55
56
58
596067
68
69
7071
72
73
74
75
76
77
7879
80
81
82
8485
8687
88
89
91
92
93
9495
96
97
98
99
100
101
102103
104
105
106
108109
110111
112
113
115116
117118
119120121
122123124125126127
128129130131132133
134135136
137138139
140141142
143144145146147148149150151152153154
161162163164165166
167168169170171172173174175176177178
179180181182183184
185186187
191192193194195196
197198199
200201202
203204205
206207208
209210211
212213214
215216217
218219220
221222223
224225226
227228229230231232
233234235
236237238239240241
243244
245246247248249250251
252253
254255256
257258259
260261262
263264265
266267268
269270271272
273274275
276277278
279280281
282283284
285286287288289290
291292293294295296
297298299
300301302
303304305
309310311
312313314
315316317
318319320
321322323
324325326
327328329
330331332333334335
336337338339340341
342343
345346347348349350
351352353354355356357358359
360361362
363364365
366367368
369370371372373374375376377
378379380381382383
384385386
387388389390391392
393394395396397398399400401
402403404
405406407408409410
414415416417418419
420421422423424425429430431432433434438439440441442443
444445446447448449
453454455
456457
458459460464465466
482483484485486487488489
1
4
7
10
1 4 7 10
Actual Cyclohexane (Wt%)
Process NMR Associates
Actual Normal-C5
Pred
icte
d n-
C5
( F10
C1
)
4 10 16 22 4 10 16 22
12345
6
7
8
911
12
13
14
15
1617
18
19
20
21
22
23
24
2526
27
28
29
30
3132
333435
36
3738394041
42
44
45
4647
48
49
50
51
525354
55
56
62
63
64
65
67
68
70
72
73
74
75
76
77
78
79
80
81
82
84
85
87
89
90
91
92
93
94
95
96
97
98
99
100101
102103104
105106107108109110
111112113114115116
117118119120121122
123124125
126127128129130131
132133134
138139140
144145146
147148
149
150153
154155
156157158
159160161162163164
168169170
171172173
174175176177178179
180181182
183184185
186187188
189190191
192193194195196197
198199200
201202203
204205207208209210211
212213214215216217218
219220221
222223224225226227228229230
231232233
234235236
237238239240241242
243244245
246
247
248249
250251252
253254255
256257258
259260261
262263264265266267
268269270274275276
277278279
280281282
283284285286287288
289290291
295296297
298299300
301302303
304305306307308309
310311312
313314315
316317318
319320321322
323324325326327
328329330
337338339
343344345
346347348349350351
352353354
355356357358359360
361362363364365366367368369370371372
373374375376377378
379380381
382383384
385386387
388389390391392393
394395396
397398399
406407408
409410411
412413414
415416417
418419
423424425429430431
432433434435436
437438444445446
447448
449450451452453454
4
10
16
22
4 10 16 22 Spectral Units ( )Spectral Units ( )
Beta
Coe
ffici
ent (
F10
C1
)Be
ta C
oeffi
cien
t ( F
10 C
1 )
-8
-2
4
10
10 40 70 100 130
-8
-2
4
10
10 40 70 100 130
Normal-C5
Process NMR Associates
96 Hours of NMR Process Output - PINA
0
5
10
15
20
25
30
35
40
45
1 173 345 517 689 861 1033 1205 1377 1549 1721
Total n-ParaffinTotal iso-ParaffinTotal NaphthenesTotal Aromatics
Process NMR Associates
96 Hours of NMR Process Output – n-Paraffin Components
0
2
4
6
8
10
12
14
16
18
1 143 285 427 569 711 853 995 1137 1279 1421 1563 1705
n-C5n-C6n-C7n-C8
Process NMR Associates
0
2
4
6
8
10
12
14
16
1 147 293 439 585 731 877 1023 1169 1315 1461 1607 1753
iso-C5iso-C6iso-C7iso-C8iso-C9
96 Hours of NMR Process Output – iso-Paraffin Components
Process NMR Associates
0
1
2
3
4
5
6
1 177 353 529 705 881 1057 1233 1409 1585
MethylcyclopentaneCyclohexaneMethylcyclohexaneOther Nap-C7Nap-C8Nap-C9
96 Hours of NMR Process Output – Naphthene Components
Process NMR Associates
0
0.5
1
1.5
2
2.5
3
3.5
4
1 167 333 499 665 831 997 1163 1329 1495 1661
BenzeneTolueneEthyl-BenzeneXylenes
96 Hours of NMR Process Output – Aromatic Components
Process NMR Associates
Process NMR Associates
Process NMR Associates
Cyclopentane
5/17
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
Process NMR Associates
Parameter R Std Dev Mean Devn-c4 0.9340 0.52 0.067n-c5 0.9761 0.73 -0.004n-c6 0.9616 0.73 -0.093n-c7 0.9840 0.33 -0.032n-c8 0.9882 0.29 -0.008n-c9 0.9918 0.18 -0.003n-c10 0.9716 0.13 0.022Total n-paraffin 0.9840 0.81 0.013I-c4 0.8765 0.07 0.001I-c5 0.9834 0.76 0.043i-C6 0.9865 0.59 -0.050i-C7 0.9119 0.46 -0.015i-C8 0.9800 0.42 -0.035i-C9 0.9905 0.26 0.010i-C10 0.9866 0.24 0.013i-C11 0.9613 0.08 -0.007Total I-paraffin 0.9617 0.81 -0.011cyclopentane 0.9821 0.14 -0.004me-cyclopentane 0.9937 0.23 -0.018Cyclohexane 0.9940 0.26 0.034Methylcyclohexane 0.9872 0.29 0.001Other C7-Nap 0.9025 0.32 -0.052c8-Nap 0.9713 0.36 0.002c9-Nap 0.9892 0.28 0.026c10-Nap 0.8950 0.06 -0.001Total Naphthenes 0.9794 0.83 0.019Benzene 0.9950 0.10 0.006Toluene 0.9920 0.17 0.007Ethylbenzene 0.9902 0.04 0.002Xylenes 0.9951 0.14 0.003C9 - Arom 0.9875 0.16 0.006C10-arom 0.9586 0.07 0.001Total Aromatics 0.9967 0.31 0.022
Single PLS Model for Each GC Component
Low Model Maintenance
SPYRO Optimization and APC Utilize Real Time Analysis
4 Crackers Now Covered by 1 NMR
Multiple (12) GC Analyzers Replaced Yielding Reduced Maintenance
Reduced Laboratory Requirements
Other Installations:Expanding Model Base to Cover Gas Oils andMixed Naphtha/Gas Oil Blend OperationModel base to be developed for NMR analyzer on gaseous products of naphtha cracker.
Process NMR Associates
Conclusion
High Resolution FT-NMR has Left the Research
Laboratory…. and is Arriving in a Process Near You!
See Further Information at http://www.process-nmr.com
Process NMR Associates
Acknowledgements
Paul Giammatteo – PNA
Tal Cohen – Foxboro NMR Israel
Tony Van Poyenbroeck – Cardoen Technology, Belgium
Invensys
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