Practical Applications of Compact High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online Process Control Presented By John Edwards, Ph.D., LLC Danbury, Connecticut March 22, 2011 RSC Reaction Monitoring Symposium, Sandwich, Kent, UK
300+ Analytical NMR Customers TTC Labs, Inc. Process Engineering Excellence TopNIR Systems
High Resolution FT-NMR Online / in Process
NMR Sample System and Placement
NMR Lock - External 7 Li 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 Magnet System 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
PEG D E F CH3 A H 3 C C B CH 3 G O H OH 300 MHz PEG OH A FT- 13 C D FT- 1 H E H G C B F D E F CH 3 A H 3 C C B I J G H OH PEG D E CH 3 O PEG A 58 MHz H I J CDCl3 G B F C PEG OH A D E H G C B F
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: 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%) Predicted Toluene (Wt%) ( F9 C1 ) 1 1 2 3 45 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 342343 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 ( ) Beta Coefficient ( F9 C1 ) -1.5 0 1.5 10 40 70 100 130-1.5 0 1.5 10 40 70 100 130
Predicted Cyclohexane ( F9 C1 ) Beta Coefficient ( F9 C1 ) Cyclohexane 203 204 205 10 10 209 210 211 267 266 268 2.5 221 223 222 Beta Coefficients 7 7 278 68 92140 141 142 263 265276 277 264 1 100 76215 217 216 4 4 1 1 212 101213 214 274 77 42 273 275 72 96 111 86 110 194 196137 138 139 279 280 87 195 193 281 218 219 220 191 192 52 73 297 298 299 224 105 161 162 163 164 165 166 179 180 225 324 226 181 325 326 185 174 186 187 309 310 311 182 183 447 184 448 449 35 18 146 116 153 47 51 5510 30 115 125 126 127 122 9 16 37 50 13 14 27 23 67 2 3 8 11 60 74 98 123 124 143 144 145 147 148 149 150 151 152 154 167 168 169170 171 172 173 175 176 177 178 254 255 256 318 319 320197 199 482 483 198 444 445 484 485 488 489 227 260 261 262 486 487 446 402 403 404 282 228 206 207 208 331 283 229 230 231 232 200 201 202 91 119 120 121 134 28 48 53 248 249 36 33 82 106 135 136 7 25 99 38 22 6 1 29 43 54 46 56 75 78 79 88 102 103 112233 234 235 117 118 131 132 104 133 128 129 130 236 237 238 239 246 250 257 258 259 240 241 245 247 251 252 284 330 332 333 334 335 321 322 323 253 285 287 288 289 290 286 272 291 292 293 269 270 294 336 337 338 295 296303 304 305 339 340 341 351 352 353 354 381 382 383 357 358 359 355 356 366 367 368 372 373 374 375 378 379 380 387 388 389 376 390 391 392 393 394 395 396 397 398 399 400 401 423 424 425 420 421 422 456 457 429 430 431 438 439 440 432 433 377 414 415 416 434 441 442 443 417 418 419 464 465 466 453 454 455 458 348 349 350 360 361 362 369 370 371 384 385 386 405 406 459 460 407 408 409 271 345 410 346 347 113 94 70 243 244 80 89 17 95 20 12 21 31 15 32 71 85 312 313 314 300 301 302 342 58 343 327 328 329 93 109 108 315 316 317 363 364 365 69 84 -.5-2 10 40 70 100 130 1 4 7 10 Spectral Units ( ) Actual Cyclohexane (Wt%)
Wt% Cyclopentane GC NMR Date
96 Hours of NMR Process Output iso-paraffin Components 16 14 12 10 8 6 4 iso-c5 iso-c6 iso-c7 iso-c8 iso-c9 2 0 1 147 293 439 585 731 877 1023 1169 1315 1461 1607 1753
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
7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 0:00:00 0:14:24 0:28:48 0:43:12 Acid CH3 Intensity Anhydride CH3 Intensity
9.00 8.00 7.00 6.00 5.00 4.00 3.00 Methyl Ester CH3 Acetic Anhydride CH3 Acetic Acid/Ester CH3 2.00 1.00 0.00 0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17 0:20:10
12.00 10.00 8.00 6.00 4.00 2.00 Methyl Ester CH3 Acetic Anhydride CH3 Acetic Acid/Ester CH3 0.00 0:00:00 0:02:53 0:05:46 0:08:38 0:11:31 0:14:24 0:17:17 6 5 4 3 2 ppm
Acknowledgements Paul Giammatteo PNA Qualion NMR Israel Tal Cohen ASPECT Italia Leonid Grunin Resonance Systems, Russia Mark Zell Pfizer Groton CT