Advances in Field-Deployable NMR Instrument for …process-nmr.com/pdfs/Edwards - NMR - ACS -...

Process NMR Associates

Advances in Field-Deployable NMR Instrument for Laboratory and Process Applications in the Petroleum and Petrochemical Industries:

Chemometrics, Direct Measurements, and Data Fusion

John Edwards1, Paul Giammatteo1, Tal Cohen2

1. Process NMR Associates, LLC, Danbury, Connecticut2. Modcon Systems and Aspect Imaging, Israel

September 12, 2013246th ACS National Meeting, Indianapolis, IN

TTC Labs, Inc.

Process Engineering Excellence


TopNIR Systems

250+ Analytical NMR Customers

Analytical ServicesAndConsulting


High Resolution FT-NMR – Online / in Process

First Generation NMR – 1998Elbit-ATI/Foxboro NMR Second Generation NMR – 2003

Qualion

Lab versionOn-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 capabilitiesProbe - Improved Probe Q for Higher Sensitivity.Software – Windows 7 – Improved Chemometric Capabilities

Third Generation NMR - 2013– Aspect AI NMR System


NMR Sample System and Placement



NMR Lock - External 7Li Lock @ 22.5 MHzSpectrum 1H Frequency Lock

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

60 MHz NMR of Essential Oils

EPA PLS1 Model 5 Factors R2=0.984

Eicosapentanoic acid (EPA)Docosahexanoic acid (DHA)

Omega-3 Fatty Acid Concentration

Fish Oil Nutritional Supplement - Manufacturing Process

Adhesive Pre-polymers


ppm12345678

300 MHz

CH3

CH2

CH

a-CH3

a-CH2

AromaticsEthanol

Alkenes

60 MHz

Gasoline 1H NMR


NMR Data Processing for Input into Chemometrics


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


0

2

4

6

8

10

20 40 60 80 100 120 140

Density

0.691 g/ml

0.753 g/ml

0.791 g/ml

0.827 g/ml

Superimposed 1H NMR spectra for samples spanningthe entire density range


0

2

4

6

8

20 40 60 80 100 120 140

MON78.3

82.7

85.0

88.9

Superimposed 1H NMR spectra for samples spanning

the entire MON range


Actual MON

Pre

dic

ted M

ON

1

2

3

4

5

6

7

8

9

10

11

12

1314

15

16

17

18

19

202122

23

24

25

26

29

30

31

32

33

34

3536

37

3839

40

4142

43

45

46

47 49

50515253

54555657

58596061

62

64

6667

6869

7071

74

7576

77

78

80

81

82

83 84

85

86

87

88

90

91

92

93

97

98

99

100

103104105

106

107

108

109

110

111

114

115

116

117

118

119

120121

122

123124

125

126

127128

129

130

131

132

133

134135136

137

138

139

140

141

142

143

144

146

149150

151

152

153

155156

157

158

160

161

162

164

165

166

167

168

169170171

173174

175176

177

179

180182

183184

185186187

189190191192193194

196197198199

200203204205

206207208209210

211212

213214215

216217218219220221

222223224225226227

228

229230

231

232233

234235236237238239240244

245246

247

248249

250255256257258

259260

261262263264268

269270

271

272274275

276277

278279280281284285

287288289

290291

292293

294295

296

302

303304305306307

308310311

312314

315316317

318319320321322323

324325

326

327

328

329

330331333334335336337338

339

340341342343

344

345346

347

348349350351352

353

354355

356

357

358359

360

361362

363

364365366

367

368

369370371372

373374

375

379

380

382383

384

385

386

387

389

391

392

393

394

395397

398

399

400

401

402

403

404

405

74

80

86

92

74 77 80 83 86 89 92

MON

R2=0.976

secv=0.60 Octane

9 Factors

346 Samples


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

C1

)

-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

Application: Crude Distillation Unit Optimization and Control Installed 2001Crude Unit Capacity: 180,000 Barrels per Day

Control Strategy: Control on Kero Freeze Point and Crude Tower Optimization

NMR Analysis: 15 Minute Cycle - NMR Results into ROMEO CDU Optimization NMR PLS

Outputs: Naphtha – T10, T50, T90, EP - D86 Distillation

Kero – Freeze, Flash

Crude –API, Sulfur, TBP (38, 105, 165, 365, 565C)


Kero Freeze Lab Vs NMR

-65

-60

-55

-50

-45

-40

2002

/05/

01

2002

/05/

03

2002

/05/

05

2002

/05/

07

2002

/05/

09

2002

/05/

11

2002

/05/

13

2002

/05/

15

2002

/05/

17

2002

/05/

19

Lab Freeze (DegC)

NMR Freeze (DegC)


Crude Adjustment

0

10

20

30

40

50

60

70

80

90

100

-150 50 250 450 650 850 1050

CutPoint Deg C

WT

% Y

ield

Before

After

NMR

Crude Reconciliation


60 MHz NMR3-10 mm SamplesLab or On-Line

aspectimaging60 MHz NMR3-10 mm SamplesLab or On-Line

60 MHz NMR3-5 mm SamplesLab Only




45 MHz and 82 MHz NMR300 micron capillary injectionLab Only

85+ MHz NMR3-5 mm SamplesLab Only

Picospin 45 and 80NMReady 60

PulsarFourier 60 MobiLab™ SPECTRA 2T

September 12, 2013


Why the Entrance of so many players into low field NMR analyzers ?

Vindication of potential value and markets ?

Petroleum, Petrochemical, Food, Pharmaceutical, DiagnosticMaterials, Agriculture, Mining, Consumer Goods, Cosmetics


Direct Measurements

Integration of Particular Peaks in Spectrum to Obtain:

Quantitative Analysis

Monomer Ratios

Reaction Monitoring – Kinetic Modeling from Reactant Peak Intensity

Molecular Ratios and Mixture Analysis

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

CH3

O

O

O

CH3

B

B

D

A

A

CH3CH3

CH3OH

CH3

CH3

CH3

O

O

CH3

+ +

CH3

O

OH

C

C

D

E

EH+

Acid Catalyzed Esterification of Iso-Butanol with Acetic Anhydride

2.5 2.0 1.5 1.0 ppm

Esterification of t-BuOH

Integral GraphAnd Integration Plot

AcAn

Acetic Acid

T-BuOHT-Bu-Ester

Ac-Ester

Sucrosea-glucose

1H NMR – Sucrose Hydrolysis by Invertase Enzyme

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

At-Line Analyzer - 1H NMR Observation of Alkene Saturation


Data Fusion ….. ?

200 400 600 800 1000 1200 1400 1600 1800 2000 2200-2

0

2

4

6

8

10

12

14

16

Variables

Data

NMR

FTIR-ATR

FCC Feeds

No Benefit Observed in Analyses Performed so Far ….


Acknowledgements

Paul Giammatteo – PNA

Tal Cohen –ASPECT AI and Modcon

Adam Dicaprio, Daniel Edwards - PNA

For more information and applications visit www.process-nmr.com

Advances in Field-Deployable NMR Instrument for …process-nmr.com/pdfs/Edwards - NMR - ACS -...

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