Practical Applications of Compact High Resolution60 MHz Permanent Magnet NMR Systems forReaction...

Process NMR Associates

Practical Applications of Compact High-Resolution60 MHz Permanent Magnet NMR Systems for

Reaction Monitoring and On-line Process Control

Presented By

John Edwards, Ph.D.

Process NMR Associates, LLC

Danbury, Connecticut

September 28, 2010

Small Molecule NMR Conference, Portland Oregon

TTC Labs, Inc.

Process Engineering Excellence


TopNIR Systems

250+ Analytical NMR Customers


High Resolution FT-NMR – Online / in Process

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

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



CH3

CH3

CH3

O

OH

A

B

C

D E F

G

H

A

F

B

CG

H

D E

PEG OH

PEG

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


ppm12345678

300 MHz 1H NMR of Gasoline

CH3

CH2

CH

a-CH3

a-CH2

AromaticsEthanol

Alkenes

60 MHz 1H NMR of Gasoline


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 1998Reformer 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 2000Cracker 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

23

45

6

7

8

9

10

11

12

1314

15

16

17

18

1920

21

22

2325

26

2728

2930

31

32

33

34

35

36

37

383940

4142

43

44

45

46

4950

51

53

5456

58

59

6263

66

68

69

70

71

73

75

76

77

78

79

80

82

83

84

85

86

87

88

90

91

929394

95

9697

98

99

101

102

103

104

105

106

108

109

110

111

112

113

114

115

116

117

118119120

121

122123

124

125126

127128

129130131132133134135136137

138139140141142143

144145146

147148149

150151152

156157158159160161

162163164

165166167168169170

171172173

174175176

177178179

180181182

183184185186187188

189190191

192193194195196197

198199200

201202203

204205206

207208209210211212

213214215

216217218219220221222223224

225226227228229230

231232233

234235236

237238239240241242243244245246247248249250251

252253254

255256257258259260261262263

264265266

267268269270271272

273274275

279280281282

283284285

286287288

289290291

292293294

295296297298299300

301302303

304305306

307308309

310311312

313314315

319320321

322323324325326327

328329330

331332333334335336

337338339

340341342343344345

346347348349350351

352353354

355356357358359360

361362363364365366367368369

370371372

373374375

376377378

379380381382383384385386387

388389390391392393

394395396397398399400401402

403404405

406407408

409410411

412413414

427428429 430431432433434435

436437438

439440441

445446447

448449450

451452453454455456

457458459

460461462

463464

465466467

471472473

477478

481482

483484485489490493494495496

-.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

23

45

6

78

910

11

12

1314

15

16

17

18

19

2021

22

23

2425

26

27

28

29

30

3132

33

34

35

36

37

38

39

4041

42

4346

47

48

49

50

51

52

53

54

55

56

58

596067

68

69

70

71

72

73

74

75

76

77

7879

80

81

82

84

85

8687

88

89

91

92

93

9495

96

97

98

99

100

101

102103

104

105

106

108109

110111

112

113

115116

117118

119120121

122123124

125126127

128129130131132133

134135136

137138139

140141142

143144145146

147148149150151152153154

161162163164165166

167168169170171172173

174175176177178

179180181

182183184

185186187

191192193194195196

197198199

200201202

203204205

206207208

209210211

212213214

215216217

218219220

221

222

223

224225226

227228229

230231232

233234235

236237238239240241

243244

245246247248249250251

252253

254255256

257258259

260261262

263264265

266267268

269270271272

273274275

276277278

279280281

282283284

285286287

288289290

291292293294295296

297298299

300301302

303304305

309310311

312313314

315316317

318319320

321322323

324325326

327328329

330331332333334335

336337338339340341

342343

345346347

348349350

351352353354355356357358359

360361362

363364365

366367368

369370371

372373374375376377

378379380381382383

384385386

387388389390391392

393394395396397398

399400401

402403404

405406407408409410

414415416417418419

420421422423424425429430431

432433434438439440441442443

444445446

447448449

453454455

456457

458459460

464465466

482483484485

486487488489

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

FACTOR3

ILVI 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

DewaxingDearomatization

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


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


Acknowledgements

Paul Giammatteo

– PNA

Qualion NMR – Israel

Tal Cohen – ASPECT Italia

Practical Applications of Compact High Resolution60 MHz Permanent Magnet NMR Systems forReaction...

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