SPECTSCPY BASED CUDE ASSAYS F LABATY, AT-LINE, AND N-LINE APPLICATINS Paul J. Giammatteo and John C. Edwards Process NM Associates, LLC Danbury, Connecticut
Traditional True Boiling Point which accurately measures product yields Water Content API Gravity Metals and Inorganic Content (nickel, vanadium, sulfur, sodium, chlorine) Corrosivity Spectroscopic Full distillation yields (True boiling point vol% and wt%) by NM Water content (Microwave water cut and NM) API Gravity (NM) Carbon distribution (aromatics, olefins, naphthenics, paraffins) (NM) Metals (nickel, vanadium) (ES) Acidity/Corrosivity (ES / Microwave)
NM Nuclear Magnetic esonance» Time-Domain/Low esolution» High esolution ES Electron Spin esonance FTI Fourier Transform Infra ed with Diamond AT» Mid-infra-red region ( 6) LIBS - Laser Induced Breakdown Spectroscopy 1. Can be applied in a variety of laboratory, at-line, and/or online configurations. 2. ffer rapid, cost effective and simultaneous multi-parameter analyses. 3. Measurement of both bulk and trace properties. 4. Ideal for use in combination with software planning tools.
Crude il Chemistry: Alkanes, cycloalkanes (naphthenes), aromatics, polycyclic aromatics, S-containing compounds, etc. Gasoline: branched alkanes Diesel: linear alkanes
Polycyclic Aromatics and Asphaltene Precursors
il efining, one of the most complicated manufacturing operations in all industry, taking extremely diverse feed stocks to make products of consistent quality worldwide.
2 NM Spectra Showing Spectral Variability of 6 Crudes CH 2 Gasolines CH 3 CH All Diesels: (Data date range 1999 to present) Atmospheric Crude Straight un Vacuum Crude Straight un CH 2 CH 3 Coker Diesel CH 3 CH 3 Diesel Hydro Cracker Feed Diesel Hydro Cracker Product Mild, Moderate and Severely Hydro Treated Diesel Blend Header Diesel CH 3 FCC Diesel H H H H H 8 6 4 2 ppm 8 67 4 2
2 NM Spectra Showing Spectral Variability of 6 Crudes CH 2 CH 3 CH CH 3 CH 3 8 6 4 2 ppm
Table 1: Initial Study Crude ils - 23 to 28 Alaskan North Slope Forties Nile Blend Amna Fosterton dudu Arab Heavy Gos Mix ily ock Arab Medium Grand Isle Qatar Marine Arab X-light High Island Qua Iboe Bach Ho Kerapu ang Dong Badak Khafji as Garib Basra Kiame atawi (Neutral Zone) Basra Light Kirkuk oss Bay Marchand Kuwait uby Bay Marchand Lago Medio Schiehallion BCF-17 Lavan Blend Shell Delta Belayim (Egypt) Light Louisiana Sweet South Arne Brent Liverpool BlendStag Cheleken Loyal Syrian Light Cuisiana Lu Feng Tantawan Cupiago Mandji Tapis Blend Cupiagua Marib light Tengiz Curlew Mars Torcados (Nigeria) Didon Masa Upper Zakum Dubai Masila Wafra (Neutral Zone) Dulang Maui Condensate Walio Dulang Maya West Texas Intermediate Duri Minas Xi Xiang Es Sahara Mudi YME Flotta Nemba Zafiro Blend
TBP Weight Percent Cut Point (Actual versus NM Predicted) Partial Least Squares results for Table 1 Crude oils. Graphs are for (clockwise) deg C, 2 deg C, 7 deg C, and, deg C. Correlation Coefficients ( 2 ) for each plot are greater than.96 8 Actual Crude TBP Curves 7 19 NM Predicted 11 8 2-1 16 1 18 7 42 3 31 32 2328 37 17 3 8 14 4 12 8 21 2 41 39 26 43 36 47 44 2 13 9 29 2 4 6 3 11 9 6 46 34 22 1 2 4 48 24 3 6 38 33 TBP at C (Wt%) -1 2 8 11 14 Actual NM Predicted 2 - - 27 7 16 33 37 1 41 42 43 47 8 32 44 29 18 7 11 21 12 39 2 34 14 28 31 2 336 23 228 36 17 2 926 3 46 2 4 4 13 1 9 6 6 49 48 34 24 38 TBP at 2C (Wt%) 2 7 Actual Cumulative Weight Loss (Wt%) 9 8 7 6 3 2 3 13 23 33 Temperature (C) Kuwait Marib Light Nemba GS Mix Dulang Bacho NM Predicted 9 7 6 4 16 19 37 42 7 41 8 29 43 47 33 6 14 11 22 39 1 49 44 17 27 2 8 3 12 32 36 9 3 2 28 36 7 1 46 31 4 18 21 26 2 2324 3 38 4 48 9 6 4 13 TBP at C (Wt%) 34 6 8 9 Actual NM Predicted 98 92 86 8 74 34 16 19 14 37 29 427 8 6 33 11 43 41 49 47 44 17 27 1 22 32 8 27 12 23 3 6 28 36 39 93 31 18 4 1 2646 23 21 24 2 3 38 4 9 48 6 13 4 TBP at 7C (Wt%) 76 82 88 94 Actual Cumulative Weight Loss (Wt%) NM Predicted TBP Curves for Crudes 9 8 7 6 3 2 3 13 23 33 Temperature (C)
pna--9.tdf,9 (² =.89283773) pna--9.tdf, (² =.914837471) 4 86 8 14 44 Predicted Concentration ( F17 C1 ) 3 44 87 16 68 139 37 8 79 43 2 114 8 111 137 2 66 31 34 123 77 73 12 13 9 24 49 83 6 119 12 141 2 113 64 124 37 88 48 42 17 38 94 23 132 121 61 126 9 3 99 81 32 28 7 129 11 112 12 78 81 13 116 19 2 71 69414 4 1 1 29 39 142 7 1 7 36 82 9 96 72 84 4 13 138 67 122 33 128 76 133 62 3 4 47 98 74 91 7 118 2 27 6 127 134 63 136 6 46 117 Predicted Concentration ( F C1 ) 48 42 36 3 97 67 138 133 62 42 81 142 71 82 113 111 48 1 4 12 76 119 114 38 11 43 3 9 4 124 69 6 7 1 4 2 3 391126 83 12 116 13 86 8 132 129 61 64 27 127 88 17 74 98 8 6 24 3 4 14 13 33 6 1189 1647 84 77 93 9 117 1 22 34 19 46 3 32 31 66 87 7 13 29 137 141 2 8 7 7 36 72 78 92 96 1 18 9 21 2 89 8 79 2 18 89 1 22 93 Normal-Paraffins of -9C Cut 28 99 Iso-Paraffins of -9C Cut 24 18 24 3 36 42 48 24 3 36 42 48 4 6 Actual Concentration ( C1 ) Actual Concentration ( C1 ) pna--9.tdf,14 (² =.847799) 14 pna--9.tdf,19 (² =.91778164) 89 18 92 21 22 93 11 6 131 43 114 Predicted Concentration ( F14 C1 ) 2 121 127 14 8 86 91 2 7 4 98 27 99 28 137 66 68 88 77 64 2 31 139 17 7 13 138 141 2 67 9 12 13 96 24 9 3 83 34 38 119 78 1 72 48 116 112 36 41 134 1 1 117 124 7 7 4 29 122 46 113 42 3 33 73 3 9 4 84 13 2 32 6 3 9 126 63 136 129 8 19 69 6 39 62 76 133 1 114 43 44 47 79 8 74 3 49 812 11 4 118 12 132 61 142 82 94 23 71 111 Naphthenes of -9C Cut Predicted Concentration ( F17 C1 ) 8 2-1 48 3 3 32 119 73 111 9 97 2 1 136 13 6 113 26 28 84 29 76 3 74 99 46 9 77 88 7 3 12 17 22 31 66 3 37 124 42 93 117 6 87 79 137 2 167 4 122 13 1 78 38 81 11 6 69 8 6 8 83 9 126 13 134 127 63 64 8 27 94 86 1 98 23 1 12 82 116 4 4 33 71 14 4 142 44 8 121 1 139 123 2 34 68 9 141 19 7 72 47 36 92 7 61 21 132 96 2 9 24 Aromatics of -9C Cut 8 14 2 26 32 38 6 12 18 24 3 36 42-1 2 8 11 14 Actual Concentration ( C1 ) Actual Concentration ( C1 ) density-api-s.tdf,12 (² =.9719611) con res-asphaltenes.tdf,2 (² =.97418733) Predicted Concentration ( F16 C1 ) 4 3 9 2 36 66 139 29 144 7 13 99 26 2 98 4 87 88 14 129 6 82 9 81 8 7 4 118 3 118 72 43 41 8 74 14116 119 46 121 48 91 114 12 47 37 13 61 6 89 4 31 16 27 3111 134 138 38 2 39 7 86 862 93 97 1 3 112 78 6 19 8 7 2 124 133 7 921 13 142 23 1 69 6 1433 141 28 6 79 96 4 68 32 113 128 42 123 22 3 9 136 76 77 17 63 9 API Gravity 84 83 11 67 132 9 1 21 94 Predicted Concentration ( F16 C1 ) 11 8 2-1 26 99 127 4 42 28 2 17 91 1 133 113 7 276 12 6 33 19 92 981 124 138 1 69 383 32 6822 6 13 37 2 6 29 61 78 79 142 134 111 141 3 12 7 16 86 126 114 128 47 41 89 83 8 44 2 84 81 39 43 11212 74 67116 24 1 73 11 117 119 97 48 34 62 8 94 9 446 121 21 13 1 137 3 7 146 64 72 18 7 91 8118 14 143 132 31 4 144 139 13 7 71 66 88 14 131 8 129 6 82 9 77 4 76 3 23 96 2 98 2 93 Carbon esidue 36 9 3 4-1 2 8 11 Actual Concentration ( C1 ) Actual Concentration ( C1 )
Water in Crude By Process 1 H NM 9 ² =.9982 rmsd=.11 Wt% 24 22 Wt% Predicted Water Content (Wt%) 6 3 21 16 26 7 2 17 12 3 19 8 69 4 12 28 29 27 3 3 31 32 34 2 11 1.7 3. 7.1 9.4 19.8 3 6 9 Actual Water Content (Wt%) 3 6 7 8 9 1 12
Crude Analysis
Lagomar/Basrah 71/29 GP(Lagotreco/DZ/Boscan) 9/4/1 GP(Lagotreco/DZ/Boscan/Slops) 9/4/1/ GP(Lagotreco/DZ) 9/ GP(Lagotreco/riente/DZ/Slops) 68/23/4/ GP(Lagotreco/riente/DZ) 92/3/ GP(Lagotreco/riente/mesa/DZ) 74/14/7/ GP(Lagotreco/riente/mesa/DZ/slops) 1/11/28// GP(Lagotreco/LagotrcoMediano/riente/mesa/DZ/Slops) 37/2/24/28/4/ GP(DZ/MESA/Lagotreco/LagotrcoMediano/rientae/Slops) /27/42/6/12/3 GP = General Purpose Crude. Slops = refinery slop re-blends of unknown composition and quality.
Crude Adjustment 9 8 7 Blue line represents the predicted curve using only an off-line LP program based on historical crude properties of the blend. W T % Y i e l d 6 LP econ NM 3 Magenta line is the actual yield curve for the same crude 2 blend obtained using the reconciliation function of the optimizer. The triangles are the feed forward NM predicted yield curve demonstrating the NM accuracy compared to the LP. - 2 4 6 8 Cut Point Deg C
3 34 33 32 31 3 29 28 27 26 2 Crude API 8/2-9/6/1 :3:38 :16:27 6:29:22 21:42:2 12::32 4:8:17 19:21:2 :33:2 1:46:49 18:49:43 ::13 1:3:48 16:1:3 8:12:22 :48:7 21:7:14 12:2:33 23:32:13 14:3:9 6:14:16 Crude Switch Tank Switch Feed change causing CDU upset.
6 MHz NM of on-line and laboratory analyzed crude samples. ed Spectrum is ASTM 93 (Cushing) run in PNA lab. 2 6 8 12 1
.7.6 lefins in crude are typically from the blending of cracked stocks found in refinery slops, condensate, etc, or from thermal cracking in enhanced recovery processes...4.3 2 distinct water peaks are observed, some centered at 74 and most centered at 78. Water peak position is indicator of polarity of crude matrix. lefins from coker diesel for reference.2.1 3 6 7 8
.8 Aromatic and Water egion Expansion ed Spectrum is ASTM 93.6.4.2.8.6 n-line spectra showing two distinct water peaks. Crude spectra are after pre-heaters and desalters. Water position is indicator of crude polarity..4.2 3 6 7 8
Predicted Concentration ( F8 C1 ) Predicted Concentration ( F8 C1 ) 3 28 22 16 8 6 SimDis T 242 241 243 239 173 2 18 4236 181 182 238 46 192 193 9 21 23 23 231229 237 232227 228 247 248 196 213 19 197 211 3 8 198 191 7 212 137 218 222 2236 138 139 22 3 132 32 2 221 26 14 13 16 33 22 226 216 128 129 2246 822 2 12 23 7 81 8 13 41 27 43 37 39 42 8782 24 116 117 4 6 113 86 88 118 8 91 47 48 491 2 9 6 616 74 9 7 1 111 112 114 1 17 174 176 66 7 8 98 6984 89 76 67 99 1 2 3 68 7 83 9 124 127119 12 121 9 96 12 77 78 122 126 97 79 92 93 94 123 combined crude simdis t(f) 629.tdf,6 (² =.9281493) 149 1 161 163 16 22 28 3 SimDis T 146 7 6 183 143 combined crude simdis t (f) 629.tdf, (² =.933427) Actual Concentration ( C1 ) 24 26 261 2244 27 21 23 2 26 28 29 262 263 242 243 226 248 249 24 246 247 148 227 22 146 14 228 18 147 237 144 238 233 23 143 9 19 17241 236 72 16 239 2 6 4 8 41 2 3 3 32 31 3638 2 39 42 1213 28 27 26 7 29 44 47 71 79 2 78 43 34 4 46 266 73 77 2 6 124 267 3 48 137 4976 33 1 22 6466 67 74 7 68 69 9 96 121 119 12 122126 127 128 13 1 89 6 113 1 12312 129 131 7 9 97 132 1 116 118 23 62 63 11117 114 139 142 1 133 91 137 141 112 134 13 136 4 82 7 8 9 138 99 92 93 98 193 194 27 29 212 192 187 213 264217 2 211 216 218 188 28 177 4 3 61 176 178 7 16 167 168 169 171 17 164 182 186 183 184 18 Predicted Concentration ( F8 C1 ) Predicted Concentration ( F8 C1 ) 62 6 4 38 32 1 combined crude simdis t3(f) 629.tdf, (² =.93916) 146 7 2 147 9 161 2 8 118 1 1486 162 9 8996 97 98 113 143 144 143 4 16117 119 164 3 163 111114 112 7 134 136 127 138 139 129 128 9 137 9 91 92 16 172 141 142 3914 17 171 42 132 3 8174 178 181 169 167 17 48 173 1137 179 7 41 31 123 38 44 168 194 18 24 33 26 198 23 2 19 4727 32 6 28 193 199 2 21 224 217 218 4 19 187 196 1972 22 246 29 211 219 212 191 186 189232 244 24 248 249 21 22 26 222 23 3 184 18 188 221 24213 223 22 241 242 243 23 247 233 23 24 2 1927 214 2 236 237 238 239 26 27 28 228234 2 216192 261 22 29 226 262 264 263 227 26 32 38 4 6 62 9 8 SimDis T3 SimDis T7 3 4 1117 143 3 144 161 9133 142 11614 146 147 148 149 1 2 8 9 161 162 7 11 14 9 12 132 287 331326 2 14 9 21 17 22 38 131 4 12 126 124 24 2 137 139 138 182 23 26 13 33 127 12 122 3 3 39 136 134 13 141 34 27 188 189 212 128 37 36 121 17 229 231234 213 129 186 29 187 6 211 178 184 18 177 174 179 18 2 26 223 22 23 232 23323 236 237 238 2 226 228 241 239 224 18 227 176 22 221 242 199 2492 22 2 2 172 173 247 21 243 222 218 29248244 24 246 217 219 19 192 28 74 76 16 7 77 79 combined crude simdis t7 (f) 629.tdf,6 (² =.9648) Actual Concentration ( C1 ) 76 98 1 8 77 6381 83 2 9 99 84 86 82 8 6 7 66 43 41 46 6 674 97 42 78 71 772 73 74 44 4 3 87 83 84 8 86 9 61 6 6 62 68 7 8 Actual Concentration ( C1 ) 6 7 8 Actual Concentration ( C1 )
combined crude simdis t9 (f) 629.tdf,7 (² =.938811) 12 Predicted Concentration ( F7 C1 ) 1 9 SimDis T9 24 19 26 173 9 1 22 2 23 8 7 139 3 177 174 17 4 14 178 1637182 179 6181 183 1 18 21 229 193 12 36 227 228 22 23 218 29 219 216 27 28 221 222 223 41 69 891992 212 6 32 71 87 211 4 61 84 86 88 92 7 9 31 8 6291 78 7 4 293 94 81 83 79 4 8 6 26 22 217 23 21 2 82 76 7 198 231 99 1224 7747 6 232 3 64 63 13 131 129 126 147 1 149 137 136 134 38 36 34 32 3 28 26 24 22 2 Fraction 1 (Vol%) 9 6 112 118 12 13 Actual Concentration ( C1 ) 3 34 33 32 31 3 29 28 27 26 2 3 day API Gravity Same model - two crude feeds 44 42 38 36 34 32 3 Fraction 2 (Vol%)
Comparison of Bitumen And Precipitated Asphaltenes Bitumen 8 Asphaltenes 6 4 2 4 ring+ 2 6 8 12 1
An electron spin resonance (ES) spectrometer detects the concentration and composition of chemical species with unpaired electrons that are present in a sample. Typical chemical species are free radicals and many transition metal ions, depending on their valence state. The sample is loaded into a high frequency resonant cavity in a magnetic field. Free radicals irradiated with microwave radiation will undergo transitions at a characteristic frequency Sample Number Location 1 Vasconia, Magdalena Basin, Columbia 39 2 Merey, Eastern Venezuela Basin, Venezuela 33 3 riente, riente Basin, Ecuador 6 4 Qua Iboe, Agbada Formation, Niger Delta 2 Basrah Light, Zubair Zone, Iraq 29 Vanadium Content (ppm) riginal Assay
Kero Blnk BasLt Merey riente QuaIboe Vasconia.6..4.3.2.1 -.1 6 7 8 1. 9 9 22 2 1 2 3 4. 2 6
.2..1. -. -.1 Kero Blnk BasLt Merey riente QuaIboe Vasconia 2. 1 2. 1 2. 1 1 2. 1 1 2. 1 1 2. 1 1 2. 1 2 2. 1 2 2. 1 2 2. 1 3 2. 1 3 2. 1 3 2. 1 3 2. 1 4 2. 1 4 2. 1 4 2. 1 2. 1 2. 1 2. 1 6 2. 1 6 2. 1 6 2. 1 6 2. 1 7 2. 1 7 2. 1 7 2. 1 8 2. 1 8
SAMPLING and TESTING All Diesels: (Data date range 1999 to present) CH 2 Atmospheric Crude Straight un Vacuum Crude Straight un CH 3 Coker Diesel FCC Diesel Diesel Hydro Cracker Feed Diesel Hydro Cracker Product Mild, Moderate and Severely Hydro Treated Diesel Blend Header Diesel CH 3 H H H H H 8 67 4 2
Crude Diesel 124733 7 72 7 67 6 62 6 7 2 47 4 42 37 3 32 3 27 2 22 2 SimDis D86 Numerous factors (especially aromatics) are responsible for deviations between distillation methods. SimDis (actual) Corr D86 Actual D86 9 8 7 6 3 2 8% 9% 9 % 96% 97% 9 8% 99% FB D S T T T 9 9 L C G T T T 9 HCU CH T T T 9 D S T T T 9 L A D T T T 9 B/MA T T T 9 CAB DS T T T 9 7% 8 % 6% 6 % 7% 4% % % 3% 3 % % 2% IB 1 % 2 % 3% 4 % % % % 2 %
Numerous factors (especially aromatics) are responsible for deviations between distillation methods. SimDis (actual) Corr D86 Actual D86 9 8 7 6 3 2 DSL T T T9 9 LCG T T T9 HCU CHG T T T9 DSL T T T9 LAD T T T9 B/MAD T T T9 CAB DSL T T T9
ISSUES Traditional and Spectroscopic Sampling, Sampling, Sampling epresentative Sample Time and Money Accuracy Value of the Information Questions?