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
TTC Labs, Inc.
Process Engineering Excellence
Process NMR Associates
TopNIR Systems
250+ Analytical NMR Customers
Analytical Services And Consulting
Process NMR Associates
High Resolution FT-NMR – Online / in Process
First Generation NMR – 1998 Elbit-ATI/Foxboro NMR Second Generation NMR – 2003
Qualion
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
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
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
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
IJ
DE
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
Process NMR Associates
ppm 1 2 3 4 5 6 7 8
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%)
Total Aromatics (Wt%)
Total Olefins (Wt%)
Total Saturates (Wt%)
Oxygenates (Wt%)
Reid Vapor Pressure
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
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
Process NMR Associates
Toluene
Actual Toluene (Wt%)
Pre
dic
ted T
olu
ene (
Wt%
) (
F9 C
1 )
1
1
2 3
4 5
6
7
8
9
10
11
12
13 14
15
16
17
18
19 20
21
22
23 25
26
27 28
29 30
31
32
33
34
35
36
37
38 39 40
41 42
43
44
45
46
49 50
51
53
54 56
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
92 93 94
95
96 97
98
99
101
102
103
104
105
106
108
109
110
111
112
113
114
115
116
117
118 119 120
121
122 123
124
125 126
127 128
129 130 131 132 133 134 135 136 137
138 139 140 141 142 143
144 145 146
147 148 149
150 151 152
156 157 158 159 160 161
162 163 164
165 166 167 168 169 170
171 172 173
174 175 176
177 178 179
180 181 182
183 184 185 186 187 188
189 190 191
192 193 194 195 196 197
198 199 200
201 202 203
204 205 206
207 208 209 210 211 212
213 214 215
216 217 218 219 220 221 222 223 224
225 226 227 228 229 230
231 232 233
234 235 236
237 238 239 240 241 242 243 244 245 246 247 248 249 250 251
252 253 254
255 256 257 258 259 260 261 262 263
264 265 266
267 268 269 270 271 272
273 274 275
279 280 281 282
283 284 285
286 287 288
289 290 291
292 293 294
295 296 297 298 299 300
301 302 303
304 305 306
307 308 309
310 311 312
313 314 315
319 320 321
322 323 324 325 326 327
328 329 330
331 332 333 334 335 336
337 338 339
340 341 342 343 344 345
346 347 348 349 350 351
352 353 354
355 356 357 358 359 360
361 362 363 364 365 366 367 368 369
370 371 372
373 374 375
376 377 378
379 380 381 382 383 384 385 386 387
388 389 390 391 392 393
394 395 396 397 398 399 400 401 402
403 404 405
406 407 408
409 410 411
412 413 414
427 428 429 430 431 432 433 434 435
436 437 438
439 440 441
445 446 447
448 449 450
451 452 453 454 455 456
457 458 459
460 461 462
463 464
465 466 467
471 472 473
477 478
481 482
483 484 485 489 490 493 494 495 496
-.5
1
2.5
4
5.5
0 1.5 3 4.5
Spectral Units ( )
Be
ta C
oe
ffic
ient (
F9 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
Coeff
icie
nt (
F9 C
1 )
-2
-.5
1
2.5
10 40 70 100 130
-2
-.5
1
2.5
10 40 70 100 130
Pre
dic
ted
Cyclo
he
xa
ne
( F
9 C
1 )
1
4
7
10
1 4 7 10 1 4 7 10
1
2 3
4 5
6
7 8
9 10
11
12
13 14
15
16
17
18
19
20 21
22
23
24 25
26
27
28
29
30
31 32
33
34
35
36
37
38
39
40 41
42
43 46
47
48
49
50
51
52
53
54
55
56
58
59 60 67
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
108 109
110 111
112
113
115 116
117 118
119 120 121
122 123 124
125 126 127
128 129 130 131 132 133
134 135 136
137 138 139
140 141 142
143 144 145 146
147 148 149 150 151 152 153 154
161 162 163 164 165 166
167 168 169 170 171 172 173
174 175 176 177 178
179 180 181
182 183 184
185 186 187
191 192 193 194 195 196
197 198 199
200 201 202
203 204 205
206 207 208
209 210 211
212 213 214
215 216 217
218 219 220
221
222
223
224 225 226
227 228 229
230 231 232
233 234 235
236 237 238 239 240 241
243 244
245 246 247 248 249 250 251
252 253
254 255 256
257 258 259
260 261 262
263 264 265
266 267 268
269 270 271 272
273 274 275
276 277 278
279 280 281
282 283 284
285 286 287
288 289 290
291 292 293 294 295 296
297 298 299
300 301 302
303 304 305
309 310 311
312 313 314
315 316 317
318 319 320
321 322 323
324 325 326
327 328 329
330 331 332 333 334 335
336 337 338 339 340 341
342 343
345 346 347
348 349 350
351 352 353 354 355 356 357 358 359
360 361 362
363 364 365
366 367 368
369 370 371
372 373 374 375 376 377
378 379 380 381 382 383
384 385 386
387 388 389 390 391 392
393 394 395 396 397 398
399 400 401
402 403 404
405 406 407 408 409 410
414 415 416 417 418 419
420 421 422 423 424 425 429 430 431
432 433 434 438 439 440 441 442 443
444 445 446
447 448 449
453 454 455
456 457
458 459 460
464 465 466
482 483 484 485
486 487 488 489
1
4
7
10
1 4 7 10
Actual Cyclohexane (Wt%)
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
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
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
CH3
CH3
CH3
O
O
CH3
CH3
CH3
CH3
OH
OH
O
CH3CH3
O
O
O
CH3
CH3
CH3
CH3
O
O
CH3
CH3
CH3
CH3
OH
OH
O
CH3CH3
O
O
O
CH3
CH3
CH3
CH3
O
O
CH3
CH3
CH3
CH3
OH
OH
O
CH3
CH3
O
O
O
CH3
CH3
O
O
O
CH3
A
B
C
D
E
E
B
D
A
C
2.5 2.0 1.5 1.0 ppm
Esterification of t-BuOH Integral Graph And Integration Plot
AcAn
Acetic Acid
Ac-Ester
OH
O
CH3
CH3
O
O
O
CH3
O
O
CH3
CH3
CH3
OH
1H NMR Zreaction Monitoring –propanol esterified with acetic anhydride
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
Aromatic Region
40 50 60 70 80 90
140 150 160 170 180 190
Aliphatic Region
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
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