Practical Applications of Compact, Cryogen-Free High-Resolution 60 MHz Permanent Magnet NMR Systems for
Reaction Monitorin...
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60 MHz NMR Applications SMASH 2012

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60 MHz NMR Applications SMASH 2012

  1. 1. Practical Applications of Compact, Cryogen-Free High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online/At-Line Process Control Observing 1H, 19F, and 31P John C. Edwards*, Tal Cohenⱡ, Paul J. Giammatteo* *Process NMR Associates, LLC, 87A Sand Pit Rd, Danbury, CT 06810 USA, ⱡ Aspect AI, Shoham, Israel For the past two decades high resolution 1H NMR at 60 MHz has been utilized to monitor the chemical physical properties of refinery and petrochemical feedstreams and products1. These approaches involve the use of partial least squares regression modelling to correlate NMR spectral variability with ASTM and other official test methods, allowing the NMR to predict results of physical property tests or GC analysis. The analysis is performed in a stop flow environment where solenoid valves are closed at the beginning of the NMR experiment. This approach allows up to 5 or 6 different sample streams to be sent to the sample in order to maximize the impact of the instrument. The current work with these permanent magnet NMR systems is to utilize them as chemistry detectors for bench-top reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring. In the past use of NMR for these applications has been limited by the need to bring the “reaction” to the typical "superconducting” NMR lab. A compact high resolution NMR system will be described that can be situated on the bench-top or in the fume hood to be used as a continuous or stop-flow detector and/or an “in-situ” reaction monitoring system. The system uses a unique 1.4 Tesla permanent magnet that can accommodate sample diameters of 3-10 mm with half-height resolution approaching 1-3 Hz (depending on the sample size) and excellent single pulse sensitivity. Reaction monitoring can be performed using a simple flow cell analyzing total system volumes of 2 to 5 mL depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 1 to 20+ ml/minute. Reaction monitoring directly in standard 5-10 mm NMR tubes using conventional (non-deuterated) reactants, solvents and analytes will also be described. Examples of 1H, 19F and 31P analyses will be described. 1. “Process NMR Spectroscopy: Technology and On-line Applications” John C. Edwards, and Paul J. Giammatteo, in Process Analytical Technology: Spectroscopic Tools and Implementation Strategies for the Chemical and Pharmaceutical Industries, 2nd Ed., Editor Katherine Bakeev, Blackwell-Wiley, 2010 Abstract Example Application: Steam Cracking Optimization Installed at BASF, Ludwigshaven 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 Hydrocarbon PONA Analysis, Density C4-C10 normal-paraffin, iso-paraffin, aromatics, naphthenes 1st Generation NMR Analyzer Invensys –Foxboro - 1998-2003 2nd Generation NMR Analyzer Qualion Ltd. 2003-2011 Typical NMR Analyzer Environment Shelter House at Base of Vaccuum Tower Sample system providing 2 conditioned streams to NMR Analyzer 3rd Generation NMR Analyzer Modcon-Xentaur-Aspect AI Actual Toluene (Wt%) PredictedToluene(Wt%)(F9C1) PLS Model for Toluene Wt% by PIONA GC 1 2 3 45 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 2325 26 27 28 29 30 31 32 33 34 35 36 37 3839 40 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 124 125 126 127 128 129130131132133134135136137 138 139140 141142143 144145146 147148 149 150151152 156157158 159160161 162163164 165166167 168169170 171172173 174175176 177 178179 180181182 183184185 186187188 189190191 192193194 195196197 198199200 201202203 204205206 207208209210211212 213214215 216217218 219 220221 222223224 225226227 228229230 231232233 234235236 237238 239240241242243244245246247248249250251 252 253 254 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 430431432 433434435 436 437 438 439440441 445446447 448449450 451452453454455456 457458 459 460461 462 463464 465 466 467 471472473 477478 481482 483484485 489490493494495496 -.5 1 2.5 4 5.5 0 1.5 3 4.5 Spectral Units ( ) BetaCoefficient(F9C1) 0 10 40 70 100 130 -1.5 1.5 10 40 70 100 130 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 4 Month Comparison of Online NMR Prediction and Laboratory GC Analysis Predictive Vector for Toluene PLS Model 96 Hours of Online Variability Observed by NMR Analyzer for 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 Online Variability Observed by NMR Analyzer for aromatic components Examples of the expected resolution obtained on various essential oils at 60 MHz 2.5 2.0 1.5 1.0 ppm CH3 CH3 CH3 O O CH3 CH3 CH3 CH3 OH OH O CH3 A B C D CH3 O O O CH3 E E B D A C 2.5 2.0 1.5 1.0 ppm 60 MHz NMR Reaction 5mm NMR Tube T-Butyl Alcohol Reacting with Acetic Anhydride In the presence of dilute acid. Aspect 60 MHz NMR System Sucrose Hydrolysis Sucrose a-glucose b-glucose Esterification of t-BuOH Integral Graph And Integration Plot Esterification of t-BuOH Superimposed Spectrum Plot 1-Propanol Esterification with Acetic Anhydride Pure Solution – No Solvent – No Acid Catalyst 8 Hour Reaction Profile AcAn (7) AcAn Acetic Acid T-BuOH T-Bu-Ester Ac-Ester OH O CH3 CH3 O O O CH3 O O CH3 CH3 CH3 OH 1,2 1 2 3 3 4 4 5 56 6 7 7 8 8,9 9 Esterification of 1-Propanol by Acetic Anhydride Integral Plots for Reaction Profile Ac-Ester Acetic Acid 1-Pr-Ester 1-PrOH

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