Edwards cpac - 5-7-12

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

TTC Labs, Inc.

Process Engineering Excellence


TopNIR Systems

250+ Analytical NMR Customers


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 - 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

Third Generation NMR – Aspect Italia 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


NMR Sample System and Placement



NMR Lock - External 7Li Lock @ 22.5 MHz Shim DACs Built into the Magnet Enclosure

Matrix Shimming Performed

by Optimizing FID RMS


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


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


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


Diesel Fuels

Biodiesels

Ethyl-benzene

Diethyl-benzene

Vinegar an Alcohol Fermentation


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)


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


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


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


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%)


Cyclopentane

Date

Wt%

GC

NMR


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


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


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


20 40 60 80 100 120 140

VI 103

FACTOR1

F A C T O R 3

IL VI 115

VI 103

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

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

Dewaxing Dearomatization

VI 100

AL

Base Oil Manufacturing – NMR Control


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

0:00:00 0:14:24 0:28:48 0:43:12

Acid CH3 Intensity

Anhydride CH3 Intensity

Process NMR - Latest Technology Developments, Reaction Monitoring, Process Control Applications and At-Line Analysis


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17 0:20:10

Methyl Ester CH3

Acetic Anhydride CH3

Acetic Acid/Ester CH3


0.00

2.00

4.00

6.00

8.00

10.00

12.00

0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17

Methyl Ester CH3

Acetic Anhydride CH3

Acetic Acid/Ester CH3

2 ppm 3 4 5 6


Acknowledgements

Paul Giammatteo – PNA

Qualion NMR – Israel

Tal Cohen – ASPECT Italia and Modcon

Edwards cpac - 5-7-12

Technology

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