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Highly Complex Analysis from Petroleum to Polymers

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Highly Complex Analysis from Petroleum to Polymers Highly complex analysis from petroleum to polymers Carlos Afonso Infrastructure de recherche nationale CNRS Spectrométrie de masse FTICR à très haut champs Responsable Guillaume Van der Rest Paris - UPMC Lille – ULille 1 FR 3624 SolariX 7T Rouen APEX Q 9.4T Univ. Rouen SolariX XR 12 T Metz Uni. de Lorraine Paris Ion Spec 9.4T ESPCI ParisTech LTQ FT 7T Palaiseau Ecole Polytechnique Orsay SolariX XR 9.4 T Uni. Paris Sud APEX Q 7T Hélène Lavanant : Responsable scientifique www.fticr.org Isabelle Schmitz : Responsable d’acceuil Installation C2MC joint lab • Complementary expertise Pierre TOTAL Giusti – Industrial applications RC – MS – ICP-MS Univ. Univ. Pau Rouen Brice Bouyssière 23 octobre 2015 Complex mixtures 6 LC/MS a 2D separation 7 Analysis of heavy petroleum product Post ionization separation 1D separation 2D separation Ion mobility – mass spectrometry Ultra high resolution FT-MS Drift Drift time (ms) m/z 8 Isotopic Fine Structure 34S R: 1.3 106 • Lincomycin (C18H34N2OS) 13C 18O 2 13C 13C 15N 33S [M+H]+ 9 Petroleum complexity ? C H S+• • C vs SH 330.2353 22 34 3 4 330.237541 +• – 3.4 mDa C25H30 330.234170 R=40000 R=900000 m1/2 330.1996 330.20 330.25 m/z R=m/m1/2 Petroleum refining processes Context Conventional crude composition Market (Arabian Light) demand 0 0 Increase of light and middle fractions cuts (diesel) Light demand: conversion units 10 fractions 10 Light 20 fractions 20 Need for hydrodemetallation, hydrodesulfuration, hydrodenitrogenation and hydrocracking 30 30 process understanding at the molecular level : Middle 40 fractions 40 50 50 60 Middle 60 fractions Rationalization and 70 70 Heavy prediction of processes at 80 80 fractions the molecular level 90 Heavy 90 fractions 100 100 wt % wt % 12 Why molecular characterization • Petroluem valued based on macroscopic descriptors – American petroleum institute (API) Gravity – Sulfur content – Total acidity number (TAN) – Metal content (V, Ni)… • Understand macroscopic properties at the molecular level – Corrosion – Fouling – Emulsion… • Petroleums with similar macroscopic descriptors may have different properties Properties Crude Oil Country of Origin Crude Oil Class Price USD Gravity °API Sulfur (wt.%) (2018/03) Brent UK 40.0 0.5 69.0 Light Sweet West Texas Intermediate USA 39.8 0.3 64.8 Arabian Extra Lt. Export Saudi Arabia Light Sour 38.1 1.1 68.9 Daqing China Medium Medium Sour 33.0 0.1 63.1 Arabian Light Expor Saudi Arabia 34.0 1.9 64.0 Medium Sour Kuwait Export Blend Kuwait 30.9 2.5 62.1 Oriente Export Ecuador 25.0 1.4 60.3 Heavy Sour Maya Heavy Export Mexico 21.3 3.4 57.0 Thèse de Johann Le Maitre Vacuum Gasoil ESI(−) VGO 0.5 mg/mL toluene/MeOH 3% NH4OH Intens. 529.46261 170406_VGOHC204_neg_000007.d: -isCID MS x108 390.31646 1.25 342.22270 286.16000 1.00 0.75 655.10611 0.50 0.25 811.12772 0.00 200 300 400 500 600 700 800 m/z 170406_VGOHC204_neg_000007.d: -isCID MS 15 13 Intens. C H N 170406_VGOHC204_neg_000007.d:C -isCID MS x107 26 38 m/z 377 377.30418 3 Accuracy better than 100 ppb 2 C28H25O C25H29OS C27H37O 13 377.28500 C27H26N C 377.21029 1 C25H45O2 C H O 377.34252 27 21 2 C26H33O2 377.19106 377.24861 377.15461 0 377.15 377.20 377.25 377.30 377.35 m/z 170406_VGOHC204_neg_000007.d: -isCID MS Meas. m/z # Ion Formula m/z err [ppm] 377.191059 1 C28H25O 377.191089 0.1 377.194431 1 C25H29OS 377.194460 0.1 377.248612 1 C26H33O2 377.248604 0 377.251936 1 C23H37O2S 377.251975 0.1 377.284998 1 C27H37O 377.284989 0 377.342524 1 C25H45O2 377.342504 -0.1 16 What is important for complex mixtures • Properties – Resolving Power – Mass accuracy – Dynamic range – Number of ions • High field FTICR – All properties increase – Linear – Quadratic Marshall, Rapid Commun. Mass Spectrom., 1996, 10, 1819 Molecular map Kendrick Diagram Van Krevelen Diagram DBE vs C# S. Gutierrez Sama, M. Farenc, C. Barrère-Mangote, R. Lobinski, C. Afonso, B. Bouyssiere, P. Giusti. Molecular Fingerprints and Speciation of Crude Oils and Heavy Fractions Revealed by Molecular and Elemental Mass Spectrometry: Keystone between Petroleomics, Metallopetroleomics, and Petrointeractomics. Energy Fuels18 2018. Data treatment • PetroOrg – http://petroorg.com • Composer (Sierra Analytics) – http://massspec.com/composer/ 19 Ion source comparison • ESI • APCI • APPI Electrospray ionization Atmospheric Pressure Chemical Ionization Atmospheric Pressure Photo Ionization Gaseous phase ionization Gaseous phase ionization Liquid phase ionization Using a corona discharge Using a UV lamp hυ = 10.6 eV 20 Equipment APCI • API sources o ESI o APCI o APPI o Direct insertion probe APCI • MALDI DIP-APCI APGC 21 Exemple: Complex petroleum mixtures - Basic vs Non Basic N - Z types (Z is the “hydrogen deficiency” relative to alkanes, CcH2c+zX, in which X denotes heteroatoms acridine (B) - classes (i.e., different combinations of N, O, and S atoms 2-hydroxyquinoline (B) 1,10-phenanthroline (B) oxindole (NB) carbazole (NB) 1-aminoanthracene (B) 22 Marshall, Energy & Fuels 2001, 15, 1186-1193 Ionization discrimination + C21H28N 294.2205 294.2205 100 100 ESI(+) % % 293.2083 294.1867 294.1304 294.1867 294.1304 0 m/z 0 m/z 294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260 294 +• 294.2343 294.2343 100 C H 100 23 18 294.1442 +• 294.1442 C22H30 293.2257 % % ASAP(+) +• C21H26O 293.1359 294.2005 294.1105 293.3194 294.1105 293.2857 294.2906 0 m/z 0 m/z 294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260 294 294.2358 293.2273 100 100 294.2358 +• + +• C23H18 C21H28N C22H30 294.1420 294.1420 % % APPI(+) C H O+• 293.1374 21 26294.1983 294.1082 293.3209 294.1082 0 m/z 0 m/z + 294 294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260 C H 1: TOF MS AP+ 293.229522 29 + 294.2230294.2305 100 2.26e4 100 C H N 21 28 12C 13C H +• APCI(+) C H +• 21 1 29 % 23 18 % 294.2230 294.1405 293.1359 294.1405 294.1967 0 m/z 0 m/z 294 294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260 23 ESI(-) NB nitrogen Charge C 1mg/ml MeOH/Toluene (50:50) + 1% NH4OH a 28% 1403543 204 (3.500) Cm (7:366) 1: TOF MS ES+ 308.2367 1.39e4 100 – C22H28N 306.2237 310.2524 304.2059 312.2709 298.2528 302.1909 % 314.2842 309.2399 300.2698 307.2275 311.2551 313.2729 299.2586 303.1956 305.2101 301.1802 0 m/z 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 N - Chemical Formula: C22H28N Exact Mass: 306.22272 24 DBE = c − h/2 + n/2 + 1 (for CcHhNnOoSs) DBE vs C# 20 20 N S 1 1 100 100 18 18 N1 80 80 16 16 60 60 14 14 DBE 12 40 DBE 40 12 10 20 10 20 8 0 8 0 6 6 15 20 25 30 35 40 45 10 15 20 25 30 35 40 45 50 55 C# C# 20 20 O 18 O1 100 OH 18 100 16 O2 80 16 14 80 14 12 60 12 60 10 DBE 10 40 DBE =5 8 DBE 8 40 6 20 6 4 20 O 4 2 0 OH 2 0 0 15 20 25 30 35 40 45 0 15 20 25 30 35 40 45 C# DBE =3 C# 25 Un peu de chimie structurale Intens. 490.44067 170415_VGOHC204_000002.d: +isCID MS [%] 50 40 Q ICR 30 m/z 490 20 10 0 300 400 500 600 700 800 m/z Intens. 170415_VGOHC204_000003 isol 490.d: +MS(isCID->CASI 489.60001) [%] 490.44073 80 60 40 20 0 26 300 400 500 600 700 800 m/z Isolation m/z 490.449 170415_VGOHC204_000003.d: +MS(isCID->CASI 489.60001) 490.44073 100 DBE 9 C35H56N 80 N H 60 + Chemical Formula: C36H44N Exact Mass: 490.34683 [%] DBE 16 40 C36H44N 490.34684 C33H48NS 20 C34H36NS 490.25632 490.31044 490.40434 0 490.250 490.275 490.300 490.325 490.350 490.375 490.400 490.425 490.450 m/z 27 Spectres CID Q ICR m/z 490 * * 30 V 40 V 50 V 60 V *harmonics 28 Selection m/z 490.449 Q ICR m/z 490 20 100 80 15 60 N1 Class DBE 10 40 20 5 0 0 10 20 30 40 C# N 20 100 H 80 + Chemical Formula: C36H44N 15 DBE 16 Exact Mass: 490.34683 N1 Class 60 Selection 490.4 DBE 10 DBE 9 40 20 5 0 0 10 20 30 40 29 C# 20 100 20 100 30 eV17 80 40 eV 80 15 15 60 60 DBE 10 10 40 DBE 10 40 20 20 5 5 0 0 0 0 10 20 30 40 10 20 30 40 C# C# 100 20 50 eV100 20 60 eV Losses of 80 80 15 15 DBE through 60 60 DBE ring opening DBE 10 40 10 40 20 20 5 5 N 0 + 0 Chemical Formula: C16H16N Exact Mass: 222.12773 0 0 10 20 30 40 10 20 30 40 30 C# C# DBE 10 N1 fragment series Ion core N + Chemical Formula: C16H16N Exact Mass: 222.12773 40 V 50 V 60 V 100 100 100 80 80 80 60 60 60 Intensity Intensity Intensity 40 40 40 20 20 20 0 0 0 15 20 25 30 15 20 25 30 15 20 25 30 C# C# C# 31 Asphaltenes • Reference asphaltene de in the framework of PetroPhase 2017 Le Havre.
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