Process NMR Associates
On-Line Applications of 60 MHz High-Resolution NMR Systems in
Industry: Direct Measurements, Chemom...
TTC Labs, Inc.
Process Engineering Excellence
Process NMR Associates
TopNIR Systems
250+ Analytical NMR Customers
Analytic...
Process NMR Associates
High Resolution FT-NMR – Online / in Process
First Generation NMR – 1998
Elbit-ATI/Foxboro NMR Seco...
Lab version On-Line version
New magnet design – 30mm bore size
• The amount of magnetic pieces that assemble the magnet re...
New magnet design solves the problem of:
Long term and short term Stability
Temperature sensitivity
State of the Art elect...
NMR Sample System and Placement
Process NMR Associates
Process NMR Associates
NMR Lock - External 7Li Lock @ 22.5 MHz Shim DACs Built into the Magnet Enclosure
Matrix Shimming P...
Process NMR Associates
Process NMR Associates
p p m1234567
CH3
CH3
CH3
O
OH
A
B
C
D E F
G
H
A
F
B
CG
H
D E
PEG OH
PEG
p p m4 06 08 01 0 01 2 01 4...
60 MHz NMR of Essential Oils
Adhesive Prepolymers
Process NMR Associates
ppm12345678
300 MHz
CH3
CH2
CH
a-CH3
a-CH2
Aromatics
Ethanol
Alkenes
60 MHz
Gasoline 1H NMR
Process NMR Associates
Gasoline Parameters:
Octane Numbers
Distillation Properties (T10, T50, T90)
Benzene Content (wt%)
T...
Process NMR Associates
Application: Closed Loop Reformer Control - Installed 1998
Reformer Capacity: 34,000 Barrels per Da...
Process NMR Associates
Application: Steam Cracking Optimization Installed 2000
Cracker Facility Capacity: 600,000 Tonnes p...
Process NMR Associates
Process NMR Associates
Toluene
Actual Toluene (Wt%)
PredictedToluene(Wt%)(F9C1)
1
1
2
3
45
6
7
8
9
10
11
12
1314
15
16
17
...
Process NMR Associates
Cyclohexane
Beta Coefficients
Spectral Units ( )Spectral Units ( )
BetaCoefficient(F9C1)
-2
-.5
1
2...
Process NMR Associates
Process NMR Associates
Process NMR Associates
Cyclopentane
Date
Wt%
GC
NMR
Process NMR Associates
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-C5
iso-C6
iso-C7
...
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
Benzene
Toluene
Ethyl-Benze...
Process NMR Associates
Online NMR Applications
1995 - BTU Analysis of Refinery Fuel Gas - Texaco
1995 - Sulfuric Acid Stre...
1H NMR Reaction Monitoring – Esterification of t-butanol with acetic anhydride
CH3
CH3
CH3
O
O
CH3
CH3
CH3
CH3
OH
OH
O
CH3
CH3
O
O
O
CH3
A
B
C
D
E
E
B
D
A
C
2.0 1.5 1.0 ppm
Esterification of t-BuOH
Integral Graph
And Integration Plot
AcAn
Acetic Acid
Ac-Ester
1H NMR Zreaction Monitoring –propanol esterified with acetic anhydride
Sucrose
a-glucose
1H NMR – Sucrose Hydrolysis
Microreactor Process Monitoring – 1H NMR – Reaction: Cyclohexene -- Cyclohexane
Process NMR Associates
Process NMR Associates
Process NMR Associates
0
.05
.1
.15
.2
.25
.3
3500 3000 2500 2000 1500 1000
Aromatic Region
15 20 25 30 35
Mono
Di
Tri
Aliphatic Region
CH3
CH2
A...
Process NMR Associates
Acknowledgements
Paul Giammatteo – PNA
Tal Cohen – ASPECT AI and Modcon
John Edwards   Online NMR Presentation - PANIC 2012
John Edwards   Online NMR Presentation - PANIC 2012
John Edwards   Online NMR Presentation - PANIC 2012
John Edwards   Online NMR Presentation - PANIC 2012
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John Edwards Online NMR Presentation - PANIC 2012

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John Edwards Online NMR Presentation - PANIC 2012

  1. 1. Process NMR Associates On-Line Applications of 60 MHz High-Resolution NMR Systems in Industry: Direct Measurements, Chemometric Correlations and Multiple Spectroscopy Data Fusion Presented By John Edwards, Ph.D. Process NMR Associates, LLC Danbury, Connecticut October 16, 2012 PANIC 2012, Schaumburg IL
  2. 2. TTC Labs, Inc. Process Engineering Excellence Process NMR Associates TopNIR Systems 250+ Analytical NMR Customers Analytical Services And Consulting
  3. 3. Process NMR Associates High Resolution FT-NMR – Online / in Process First Generation NMR – 1998 Elbit-ATI/Foxboro NMR Second Generation NMR – 2003 Qualion
  4. 4. Lab version On-Line version New magnet design – 30mm bore size • The amount of magnetic pieces that assemble the magnet reduced from 34 to 10. Reduction in Mechanical Complexity • Bore size of the magnet was increased to 30 mm - improved temperature susceptibility • Improved temperature and shim stability. New Digital Spectrometer Design - reduces footprint, improves signal processing capabilities Probe - Improved Probe Q for Higher Sensitivity. Software – Windows 7 – Improved Chemometric Capabilities Third Generation NMR – Aspect AI NMR System
  5. 5. New magnet design solves the problem of: Long term and short term Stability Temperature sensitivity State of the Art electronics: Smaller foot-print 40 Shim coils on 2 single PCB Integrated PCB for Shim & Heater Control Digital RF & Acquisition – improve SNR New concept of Process Probe: Entire sample pipe through without contact with the system Much better temperature insulation Higher Q (better sensitivity) New Software: Includes new algorithm for standard and global Models Fully automated process capacity Extensive remote diagnostic capabilities New Magnet System Process NMR Associates
  6. 6. NMR Sample System and Placement Process NMR Associates
  7. 7. Process NMR Associates NMR Lock - External 7Li Lock @ 22.5 MHz Shim DACs Built into the Magnet Enclosure Matrix Shimming Performed by Optimizing FID RMS
  8. 8. Process NMR Associates
  9. 9. Process NMR Associates p p m1234567 CH3 CH3 CH3 O OH A B C D E F G H A F B CG H D E PEG OH PEG p p m4 06 08 01 0 01 2 01 4 01 6 0 CH3 CH3 CH3 O OH A B C D E F G H I J H I J D E F A B G C PEG CDCl3 FT-13C FT-1H 300 MHz A F B C G H D E PEG OH PEG 58 MHz
  10. 10. 60 MHz NMR of Essential Oils
  11. 11. Adhesive Prepolymers
  12. 12. Process NMR Associates ppm12345678 300 MHz CH3 CH2 CH a-CH3 a-CH2 Aromatics Ethanol Alkenes 60 MHz Gasoline 1H NMR
  13. 13. Process NMR Associates Gasoline Parameters: Octane Numbers Distillation Properties (T10, T50, T90) Benzene Content (wt%) Total Aromatics (Wt%) Total Olefins (Wt%) Total Saturates (Wt%) Oxygenates (Wt%) Reid Vapor Pressure
  14. 14. Process NMR Associates Application: Closed Loop Reformer Control - Installed 1998 Reformer Capacity: 34,000 Barrels per Day Control Strategy: Control on MON and Benzene Content NMR Analysis: 2 Minute Analysis NMR PLS Outputs: RON, MON, Benzene (Wt%) Total Aromatics (Wt%) RON Validation - April 2001 - April 2002 100 101 102 103 104 105 106 107 108 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 NMR CFR
  15. 15. Process NMR Associates Application: Steam Cracking Optimization Installed 2000 Cracker Facility Capacity: 600,000 Tonnes per Year Control Strategy: Feed Forward Detailed Hydrocarbon Analysis to SPYRO Optimization NMR Analysis: 3-4 Minute Cycle (Single Stream) NMR PLS Outputs: Naphtha – Detailed PIONA C4-C10 normal-paraffin, iso-paraffin, aromatics, naphthenes
  16. 16. Process NMR Associates
  17. 17. Process NMR Associates Toluene Actual Toluene (Wt%) PredictedToluene(Wt%)(F9C1) 1 1 2 3 45 6 7 8 9 10 11 12 1314 15 16 17 18 19 20 21 22 2325 26 2728 29 30 31 32 33 34 35 36 37 383940 41 42 43 44 45 46 49 50 51 53 5456 58 59 62 63 66 68 69 70 71 73 75 76 77 78 79 80 82 83 84 85 86 87 88 90 91 9293 94 95 9697 98 99 101 102 103 104 105 106 108 109 110 111 112 113 114 115 116 117 118 119120 121 122123 124 125126 127 128 129130131132133134135136137 138139140 141142143 144145146 147148149 150151152 156157158 159160161 162163164 165166167168169170 171172173 174175176 177 178179 180181182 183184185 186187188 189190191 192193194 195196197 198199200 201202203 204205206 207208209210211212 213214215 216217218 219220221222223224 225226227 228229230 231232233 234235236 237238 239240241242243244245246247248249250251 252253 254 255256257 258259260261262263 264265266 267268269 270271272 273274275 279280281282 283284285 286287 288 289290291 292293294 295296 297298299300 301302303 304305306 307308309 310311312 313314315 319320321 322323324325326327 328329330 331332333334335336 337338339 340341342343344345 346347348 349350351 352353354 355356357 358359360 361362363 364365366367368369 370371372 373374375 376377378 379380381382383384 385386387 388389390391 392393 394395396 397398399400401402 403404405 406407408 409410411 412413414 427428429 430431432433434435 436437438 439440441 445446447 448449450 451452453454455456 457458 459 460461 462 463464 465 466467 471472473 477478 481482 483484485 489490493494495496 -.5 1 2.5 4 5.5 0 1.5 3 4.5 Spectral Units ( ) BetaCoefficient(F9C1) -1.5 0 1.5 10 40 70 100 130 -1.5 0 1.5 10 40 70 100 130
  18. 18. Process NMR Associates Cyclohexane Beta Coefficients Spectral Units ( )Spectral Units ( ) BetaCoefficient(F9C1) -2 -.5 1 2.5 10 40 70 100 130 -2 -.5 1 2.5 10 40 70 100 130 PredictedCyclohexane(F9C1) 1 4 7 10 1 4 7 101 4 7 10 1 23 45 6 7 8 910 11 12 1314 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 3132 33 34 35 36 37 38 39 4041 42 43 46 47 48 49 50 51 52 53 54 55 56 58 596067 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 84 85 86 87 88 89 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 108109 110111 112 113 115 116 117118 119120121 122123124 125126127 128129130131132133 134135136 137138139 140 141142 143144145146 147148149150151152 153154 161162163 164165166 167168169170171172173 174 175176177178 179180181 182183184 185186187 191192 193 194195 196 197198 199 200201202 203204205 206207208 209210211 212213214 215216 217 218219220 221 222 223 224225226 227 228229 230231232 233234235 236237238239240241 243244 245 246247 248249 250251 252 253 254255256 257258259 260261262 263264 265 266 267 268 269270271272 273 274275 276277 278 279280281 282283284 285286 287 288289290 291292293 294295296 297298299 300 301 302 303304305 309310311 312313314 315316317 318319320 321322323 324 325326 327328329 330 331332333334335 336337338339340341 342343 345346347 348349350 351352353 354355356357358359 360361362 363364365 366367368 369370371 372373374 375376377 378379380 381382383 384385386 387388389 390391392 393394395396397398 399400401 402403404 405 406407408409410 414415416 417418419 420421422423424425429430431 432433434438439440 441442443 444445 446 447448449 453454455 456457 458459460 464465466 482483 484485 486487488489 1 4 7 10 1 4 7 10 Actual Cyclohexane (Wt%)
  19. 19. Process NMR Associates
  20. 20. Process NMR Associates
  21. 21. Process NMR Associates Cyclopentane Date Wt% GC NMR
  22. 22. Process NMR Associates
  23. 23. 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-C5 iso-C6 iso-C7 iso-C8 iso-C9 96 Hours of NMR Process Output – iso-Paraffin Components
  24. 24. 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 Benzene Toluene Ethyl-Benzene Xylenes 96 Hours of NMR Process Output – Aromatic Components
  25. 25. Process NMR Associates Online NMR Applications 1995 - BTU Analysis of Refinery Fuel Gas - Texaco 1995 - Sulfuric Acid Strength in Emulsion Zone of Stratco Acid Alkylation Unit - Texaco 1999 - Diesel Blending System - Motiva 1999 - Reformer Control System – BP, Pertamina 2000 - Naphtha Cracker Feed Analyzer – Full GC PIONA – BASF, Lyondell 2000 - Crude Unit Analyzer – PDVSA, BRC, ConocoPhillips 2000 - Crude Blending System - Reliance 2001 - Gasoline Blending System – Fina, Valero 2001 - Base Oil Manufacturing Analyzer - AGIP 2002 - FCC Unit Analyzer – BP 2002 - At-Line Bitumen and Vacuum Residue Analyzer – ERG
  26. 26. 1H NMR Reaction Monitoring – Esterification of t-butanol with acetic anhydride
  27. 27. CH3 CH3 CH3 O O CH3 CH3 CH3 CH3 OH OH O CH3 CH3 O O O CH3 A B C D E E B D A C
  28. 28. 2.0 1.5 1.0 ppm Esterification of t-BuOH Integral Graph And Integration Plot AcAn Acetic Acid Ac-Ester
  29. 29. 1H NMR Zreaction Monitoring –propanol esterified with acetic anhydride
  30. 30. Sucrose a-glucose 1H NMR – Sucrose Hydrolysis
  31. 31. Microreactor Process Monitoring – 1H NMR – Reaction: Cyclohexene -- Cyclohexane
  32. 32. Process NMR Associates
  33. 33. Process NMR Associates
  34. 34. Process NMR Associates
  35. 35. 0 .05 .1 .15 .2 .25 .3 3500 3000 2500 2000 1500 1000 Aromatic Region 15 20 25 30 35 Mono Di Tri Aliphatic Region CH3 CH2 Alpha-Protons CH+Nap AromaticRegion 40 50 60 70 80 90 140 150 160 170 180 190 AliphaticRegion FTIR-ATR 1H NMR 13C NMR Vacuum Gas Oils - Fluid-Ctalaytic Cracking Application 0 20 40 60 80 0 10 20 30 40 50 60 70 C-Type NMR Parameters Depicted as a “Spectrum” Data Fusion
  36. 36. Process NMR Associates Acknowledgements Paul Giammatteo – PNA Tal Cohen – ASPECT AI and Modcon

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