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. TTC Labs, Inc.
Process Engineering Excellence
Process NMR Associates
TopNIR Systems
250+ Analytical NMR Customers
Analytical
Services
And
Consulting

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. 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. 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. NMR Sample System and Placement
Process NMR Associates

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. Process NMR Associates

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. 60 MHz NMR of Essential Oils

11. Adhesive Prepolymers

14. Process NMR Associates
ppm12345678
300 MHz
CH3
CH2
CH
a-CH3
a-CH2
Aromatics
Ethanol
Alkenes
60 MHz
Gasoline 1H NMR

15. 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

16. 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

17. 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

18. Process NMR Associates

19. 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

20. 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%)

21. Process NMR Associates

22. Process NMR Associates

23. Process NMR Associates
Cyclopentane
Date
Wt%
GC
NMR

24. Process NMR Associates

25. 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

26. 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

27. 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

28. 1H NMR Reaction Monitoring – Esterification of t-butanol with acetic anhydride

29. 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

30. 2.0 1.5 1.0 ppm
Esterification of t-BuOH
Integral Graph
And Integration Plot
AcAn
Acetic Acid
Ac-Ester

31. 1H NMR Zreaction Monitoring –propanol esterified with acetic anhydride

34. Sucrose
a-glucose
1H NMR – Sucrose Hydrolysis

35. Microreactor Process Monitoring – 1H NMR – Reaction: Cyclohexene -- Cyclohexane

36. Process NMR Associates

37. Process NMR Associates

38. Process NMR Associates

39. 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

40. Process NMR Associates
Acknowledgements
Paul Giammatteo – PNA
Tal Cohen – ASPECT AI and Modcon