Process NMR Associates

Process NMR - Latest Technology Developments,
Reaction Monitoring, Process Control Applications
an...
Process NMR Associates

250+ Analytical NMR Customers

TTC Labs, Inc.
Process Engineering Excellence

TopNIR Systems
Process NMR Associates

High Resolution FT-NMR – Online / in Process

First Generation NMR – 1998
Elbit-ATI/Foxboro NMR

S...
Third Generation NMR – Aspect Italia NMR System
New magnet design – 30mm bore size
•

The amount of magnetic pieces that a...
Process NMR Associates
New magnet design solves the problem of:
Long term and short term Stability
Temperature sensitivity...
Process NMR Associates

NMR Sample System and Placement
Process NMR Associates
NMR Lock - External 7Li Lock @ 22.5 MHz

Matrix Shimming Performed
by Optimizing FID RMS

Shim DACs...
Process NMR Associates
Process NMR Associates
PEG
D

F

E

CH3

C

G

A

300 MHz

H
B

H3C

OH

CH 3

O

P OH
EG

FT-13C

FT-1H
D

A

F
E

C

G

...
Process NMR Associates

Gasoline 1H NMR

CH3

60 MHz
a-CH3

300 MHz
8

Aromatics

Ethanol
Alkenes

7

6

5

4

CH

a-CH2
3...
Process NMR Associates

Gasoline Parameters:
Octane Numbers
Distillation Properties (T10, T50, T90)
Benzene Content (wt%)
...
Process NMR Associates

Biodiesels

Diesel Fuels

Ethyl-benzene
Diethyl-benzene
Vinegar an Alcohol Fermentation
Process NMR Associates

Advantages and Disadvantages of NMR Applied to Process Control
Advantages:
Non-Optical Spectroscop...
Process NMR Associates

Application: Closed Loop Reformer Control - Installed 1998
Reformer Capacity: 34,000 Barrels per D...
Process NMR Associates

Application: Steam Cracking Optimization Installed 2000
Cracker Facility Capacity: 600,000 Tonnes ...
Process NMR Associates
Process NMR Associates

Toluene

5.5
17
45

10
31
8 15
2134
3
2
125
450
448
23
449
25 126159
161
37 160
157
156
158
434
43...
Process NMR Associates

Cyclohexane
203
204
205

10 10
267
268
266
2.5

Beta Coefficient ( F9 C1 )

Predicted Cyclohexane ...
Process NMR Associates
Process NMR Associates
Process NMR Associates

Cyclopentane

Wt%

GC
NMR

Date
Process NMR Associates
Process NMR Associates

96 Hours of NMR Process Output – iso-Paraffin Components
16
14
12
iso-C5
iso-C6
iso-C7
iso-C8
iso-...
Process NMR Associates

96 Hours of NMR Process Output – Aromatic Components
4
3.5
3
2.5

Benzene
Toluene
Ethyl-Benzene
Xy...
Process NMR Associates

Online NMR Applications Timeline
1993 -

Development of Laboratory Based process NMR Methodologies...
Process NMR Associates

3.0
2.5
2.0
1.5
F
A
C
T
O
R
3

VI 103

1.0

VI 100VI 103

IL

0.5

VI 115

AL

0.0
-0.5
-1.0

Dewa...
Process NMR Associates
7.00
6.00
5.00
4.00

Acid CH3 Intensity

3.00

Anhydride CH3 Intensity

2.00
1.00
0.00
0:00:00

0:1...
Process NMR Associates
9.00
8.00

Process NMR Associates
7.00
6.00
Methyl Ester CH3

5.00

Acetic Anhydride CH3

4.00

Acetic Acid/Ester CH3

3.0...
Process NMR Associates

12.00
10.00

Methyl Ester
CH3

8.00

Acetic
Anhydride CH3

6.00
4.00

Acetic
Acid/Ester CH3

2.00
...
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates
Process NMR Associates

Acknowledgements
Paul Giammatteo – PNA
Qualion NMR – Israel
Tal Cohen – ASPECT Italia and Modcon
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
Edwards   cpac - 5-7-12
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Edwards cpac - 5-7-12

  1. 1. Process NMR Associates Process NMR - Latest Technology Developments, Reaction Monitoring, Process Control Applications and At-Line Analysis Presented By John Edwards, Ph.D. Process NMR Associates, LLC Danbury, Connecticut May 7, 2012 CPAC Spring Meeting, Seattle, WA
  2. 2. Process NMR Associates 250+ Analytical NMR Customers TTC Labs, Inc. Process Engineering Excellence TopNIR Systems
  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. Third Generation NMR – Aspect Italia NMR System 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 - improve 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 Lab version On-Line version
  5. 5. Process NMR Associates 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
  6. 6. Process NMR Associates NMR Sample System and Placement
  7. 7. Process NMR Associates NMR Lock - External 7Li Lock @ 22.5 MHz Matrix Shimming Performed by Optimizing FID RMS Shim DACs Built into the Magnet Enclosure
  8. 8. Process NMR Associates
  9. 9. Process NMR Associates PEG D F E CH3 C G A 300 MHz H B H3C OH CH 3 O P OH EG FT-13C FT-1H D A F E C G B H D C I F E CH3 6 5 4 3 H B CH3 1 OH O 58 MHz A D 2 G A H3 C 7 PE G J E PEG H J CDCl3 I B F G PE OH G C A D F C E G H 1 60 1 40 120 10 0 80 60 40 ppm B pp m
  10. 10. Process NMR Associates Gasoline 1H NMR CH3 60 MHz a-CH3 300 MHz 8 Aromatics Ethanol Alkenes 7 6 5 4 CH a-CH2 3 CH2 2 1 ppm
  11. 11. 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
  12. 12. Process NMR Associates Biodiesels Diesel Fuels Ethyl-benzene Diethyl-benzene Vinegar an Alcohol Fermentation
  13. 13. Process NMR Associates Advantages and Disadvantages of NMR Applied to Process Control Advantages: Non-Optical Spectroscopy No Spectral Temperature Dependence Minimal Sampling Requirements Spectral Response to Sample Chemistry is Linear Chemical Regions of NMR Spectra are Orthogonal Entire Volume is Sampled by the RF Experiment Water is in Distinct Region and can be digitally removed Detailed Hydrocarbon information is readily observed. Fundamental Chemical Information Can be Derived Directly from Spectrum. Colored/Black Samples Readily Observed Without Impact Disadvantages: Solids Cannot be Observed in a Liquid Stream Individual Molecular Component Sensitivity Not Observed Directly in the Spectrum. Low Sensitivity to Impurities – Quantitative > 500 ppm. Sensitive to Ferromagnetics. Sample Viscosity Causes Decrease in Resolution Non-Hydrogen Containing Species are Not Observed (Exceptions Na, P, F, Al)
  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 108 107 106 105 NMR CFR 104 103 102 101 100 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39
  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 5.5 17 45 10 31 8 15 2134 3 2 125 450 448 23 449 25 126159 161 37 160 157 156 158 434 433 435 431 432 430 405 429 404 428 403 427 42 26 22 68 41 9 43 294 407 292 406 293 408 362 363 361 365 340368 364 345453 34136770 344452 366 392 343451 393 342369 445409 456 455 410 411 454 391 193 102246 76446238 447241 192 244 251 243 390 240 245 242 389 239 194 388 237 253 250 252 197249 254 195247 201196248 202 168165 203 169167 54 170166 56 199 198 200 135 350 349 137 176 175 174 351 136 188263 187261 131 186133 205 347260 346258 348262 296130 295129 206 204 438134 436132 414 412 413 185172 183256 299259 257 184255 300 298 297 437 173 112 86 171 46662 180 302 467 181 182 465 301 303 189 63 191 190 178 280 90 121 95 281 279 116 282 179 461108 177 46082 462 312 58 99 494 489 310 311 484 493 496 495 306 490 485 304 305 483 91 314 73 315 313 66 7117 83 109 11 53 471 146 145 144 46 441 439 473 373 375 472 28 14 374 39 38 353440 354 482 324 481 27 13 36 327 111 325 85 322 352 323 326 93 18 33940 338 464 337 463 118 92 13932 75 6950 140 360 138 477376 120 94 478377 359 101 358 142 387 149 143 49119 386 378 141 385 236 234 147 355 148 235 357 356 61 371 370 372 384 383 382 398 51 379 399 400 401 381 402 394 380 307397 228 396 395 229 309 459 308 268 267 457 269 33 152 230 29 226 162 227 164 19 458 163 336 151 225 335 334 272 271 33144 150 88319 320 30 321 333 114270 332 289 219212 20 291 233 224 285 222 284 79232 16 223 105290 216 220210 208 221211 283 266 209 273 207 123 26497 217 275 265 231 274 218 122 96 328 113 329 8777 115 288 103 286 287 213 330 214 215 80 106 59 98 124 4 2.5 1 1 1.5 0 -1.5 10 71 78 104 128 110 84 127 40 70 Spectral Units ( ) -.5 0 Beta Coefficient ( F9 C1 ) Predicted Toluene (Wt%) ( F9 C1 ) 35 12 4 5 1.5 3 Actual Toluene (Wt%) 4.5 100 130
  18. 18. Process NMR Associates Cyclohexane 203 204 205 10 10 267 268 266 2.5 Beta Coefficient ( F9 C1 ) Predicted Cyclohexane ( F9 C1 ) 209 210 211 223 221 222 77 278 92 68140 276 277 265 141 142 263 264 100 217 76215 216 44 11 212 213 101 274 214 275 42 273 138 96 279 19677 72 110 139 86 137 194 280 281 111 299 193 87195 298 297 219 52 97 192 218 220 191 73 324 224 225 105 226 326 325 180 179 81 181 311 166 310 187 485 185 449 447 186 174 484 164 448 309 183 165 178 176 182 177 482 162 184 199 320445 161 197 488173163 254483 116402 489175 35403 255260 404 256487 319444 153 318446 198 486 154 51 172 127 146 145 126 150 18262 115 152 227125 171 169 261 16747 148 151 144 207 143 170 149 208 9 168 147 30 55206 282 122 228 124 10 283 333 229 334 123 400 335 401 98 331 284 420383 332 74 457429 439 201 16399 50431 13 425381 456382 42227 37430 200 232 440 202 514 398 424 423 421 231 433 330 397 396 230 394 4 389 438 432 354 442 379 378 60 434 393 252 380 443 395 91388 120 119 323 355 359 357 59 53 121 322 356 134 67387 321 465 249441 37548 391 358 392 390 466 135 136 368828 353 258 23 253 367415 248 259 251 33736 366416 376 257 352 374464 305 419 3 250 34019 373414 234 287 377 33633 372 351 338 11 455106 34182 304 235 2462 290 233 453 417 339 418 247 7 285 289 286 25288 303 295 454 112 294 118 117 296 460 458 245 103 292 88 49 459 9956 293 34824 371241 386 272 270 350239 291 238 385 132 13139 349240 384 129 128 406 370 79 407 133 130 237 236 409 34269 75 36226 369 102 361 36046 408 104 41271 40 405 54 410 78 34538 94 34629 22 80 34743 70 244 243 1 113 6 89 301 1795 302 2071 300 313 3258 85 342 314 328312 343108 329 327 36531 36421 36312 109 31715 31669 31593 84 Beta Coefficients 1 -.5 -2 10 40 70 100 Spectral Units ( ) 1 4 7 Actual Cyclohexane (Wt%) 10 130
  19. 19. Process NMR Associates
  20. 20. Process NMR Associates
  21. 21. Process NMR Associates Cyclopentane Wt% GC NMR Date
  22. 22. Process NMR Associates
  23. 23. Process NMR Associates 96 Hours of NMR Process Output – iso-Paraffin Components 16 14 12 iso-C5 iso-C6 iso-C7 iso-C8 iso-C9 10 8 6 4 2 0 1 147 293 439 585 731 877 1023 1169 1315 1461 1607 1753
  24. 24. Process NMR Associates 96 Hours of NMR Process Output – Aromatic Components 4 3.5 3 2.5 Benzene Toluene Ethyl-Benzene Xylenes 2 1.5 1 0.5 0 1 167 333 499 665 831 997 1163 1329 1495 1661
  25. 25. Process NMR Associates Online NMR Applications Timeline 1993 - Development of Laboratory Based process NMR Methodologies 1995 - BTU Analysis of Refinery Fuel Gas 1995 - Sulfuric Acid Strength in Emulsion Zone of Stratco Acid Alkylation Unit 1999 - Diesel Blending System 1999 - Reformer Control System 2000 - Naphtha Cracker Feed Analyzer – Full GC PIONA 2000 - Crude Unit Analyzer 2000 - Crude Blending System 2001 - Gasoline Blending System, 2001 - Base Oil Manufacturing Analyzer 2002 - FCC Unit Analyzer
  26. 26. Process NMR Associates 3.0 2.5 2.0 1.5 F A C T O R 3 VI 103 1.0 VI 100VI 103 IL 0.5 VI 115 AL 0.0 -0.5 -1.0 Dewaxing Dearomatization -1.5 -2.0 -2.5 -3.0 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 FACTOR1 Base Oil Manufacturing – NMR Control 20 40 60 80 100 120 140
  27. 27. Process NMR Associates 7.00 6.00 5.00 4.00 Acid CH3 Intensity 3.00 Anhydride CH3 Intensity 2.00 1.00 0.00 0:00:00 0:14:24 0:28:48 0:43:12 Process NMR - Latest Technology Developments, Reaction Monitoring, Process Control Applications and At-Line Analysis
  28. 28. Process NMR Associates
  29. 29. 9.00 8.00 Process NMR Associates 7.00 6.00 Methyl Ester CH3 5.00 Acetic Anhydride CH3 4.00 Acetic Acid/Ester CH3 3.00 2.00 1.00 0.00 0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17 0:20:10
  30. 30. Process NMR Associates 12.00 10.00 Methyl Ester CH3 8.00 Acetic Anhydride CH3 6.00 4.00 Acetic Acid/Ester CH3 2.00 0.00 0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17 6 5 4 3 2 ppm
  31. 31. Process NMR Associates
  32. 32. Process NMR Associates
  33. 33. Process NMR Associates
  34. 34. Process NMR Associates
  35. 35. Process NMR Associates
  36. 36. Process NMR Associates
  37. 37. Process NMR Associates Acknowledgements Paul Giammatteo – PNA Qualion NMR – Israel Tal Cohen – ASPECT Italia and Modcon

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