Al darouich, Tammam (2005) Stabilité thermique de la fraction aromatique de l'huile brute Safaniya (Moyen Orient): étude expérimentale, schéma cinétique par classes moléculaires et implications géochimiques. PhD thesis Chimie Analytique, Chimie, ENSCP.

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Abstract

The thermal evolution of reservoired oils is controlled by the kinetics of cracking reactions. The present work is concerned with the study of the thermal stability of the light aromatic components (C6-C14) of crude oils under geological conditions. The aim is to predict this stability through a model derived from laboratory pyrolyses. The light cut <250 °C of Safaniya crude oil, corresponding to the C15- components, was obtained by fractionated distillation; pure aromatic fraction was then separated by liquid chromatography. Detailed molecular characterisation of the aromatic fraction was acquired using HPLC, GC and GC/MS. Then, quantified individual aromatic compounds were lumped into six molecular classes: BTXN, methylaromatics, alkylaromatics, naphthenoaromatics, indenes and sulphur-containing aromatics. Pyrolyses of the aromatic fraction were performed in gold tubes at 100 bars and different temperature/time conditions in a wide range (1 to 93%) of global conversion. Pyrolysis effluents were analysed and lumped into classes. The pyrolysis data were used to elaborate a semi-empirical kinetic scheme of 13 stoichiometric reactions for the primary and secondary cracking of the unstable classes. The scheme kinetic parameters were first estimated, and then numerically optimised, with the constraints of mass balance and hydrogen conservation.
A set of pyrolysis experiments was performed at 375 °C under high pressures: 400, 800 and 1200 bars. Increasing slowing down in conversion rate with increasing pressure was thus observed compared to experiments at 100 bars. A slight selective effect of pressure on the different aromatic classes of the charge and on the product distribution was evidenced. The extrapolation of the kinetic model to the conditions of Elgin Field (North Sea) showed that pressure effect should shift the thermal cracking of light aromatics to higher temperatures by almost 8 °C.

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Table of content

Avant propos - 7
Table de matières - 9
Abréviations - 15
Symboles - 16
Introduction générale - 17
Chapitre I
Cadre de l'étude
I.1. Formation du pétrole dans les bassins sédimentaires - 23
I.1.1. Formation du kérogène - 23
- Origine de la matière organique sédimentaire - 23
- Enfouissement de la matière organique - 23
- Maturation de la matière organique, la diagenèse - 24
- Préservation sélective - 24
- Sulfuration naturelle - 25
- L'encapsulation des protéines - 25
- La réticulation oxidative - 25
- Protection par des minerais argileux - 25
I.1.2. Caractérisation et classification des kérogènes - 25
I.1.3. Genèse du pétrole - 27
- La catagenèse - 27
- La métagenèse - 27
I.1.4. Migration du pétrole - 27
I.1.5. Evolution du pétrole dans le système pétrolier - 28
I.1.5.1. Craquage thermique secondaire - 28
I.1.5.2. Biodégradation et lessivage à l'eau - 28
I.1.6. Composition du pétrole - 30
I.1.7. Classification des huiles brutes - 30
I.1.7.1. Classification des huiles du point de vue géochimiste - 30
I.1.7.2. Classification des huiles du point des raffineurs - 32
I.2. Modélisation du craquage thermique - 32
I.2.1. principe - 32
I.2.3. Rappels cinétiques - 33
I.2.3. Schémas cinétiques - 35
- Approche théorique - 35
- Approche empirique - 35
- Discussion - 35
I.2.4. Travaux antérieurs - 36
I.2.4.1. Craquage thermique de composés modèles - 36
I.2.4.1.1. Craquage thermique de composés saturés - 36
I.2.4.1.2. Craquage thermique de composés aromatiques - 39
I.2.4.1.3. Craquage thermique de mélanges - 44
I.2.4.2 Modèles cinétiques - 45
I.2.4.2.1. Modèles théoriques - 45
I.2.4.2.2 Modèles empiriques compositionnels - 46
- Modèles de l'IFP (1988, 1991, 1992, 1999) - 46
- Modèles de Braun et Burnham (1990, 1992) - 50
- Modèle de Kuo et Michael (1994) - 51
I.2.5. Rôle de la pression dans les réactions de craquage - 52
I.2.5.1. Etude théorique - 52
I.2.5.2. Travaux antérieurs - 54
I.2.5.2.1. Effet de la pression sur le craquage du kérogène - 54
I.2.5.2.2. Effet de la pression sur le craquage des hydrocarbures saturés - 54
I.2.5.2.3. Effet de la pression sur le craquage des hydrocarbures
Aromatiques -
56I.2.5.2.4. Effet de la pression sur le craquage des mélanges - 57
I.2.5.2.5. Effet de la pression sur le craquage des huiles - 57
I.2.5.2.5. Discussion - 58
I.3. Objectifs de la thèse - 58
I.4. Stratégie générale - 60
- Choix de l'échantillon - 60
- Isolement et caractérisation de la fraction aromatique - 60
- Pyrolyse de la fraction aromatique - 61
- Elaboration du schéma cinétique compositionnel - 61
- Etude sur l'effet de la pression sur la stabilité thermique de la fraction aromatique -
61Références bibliographiques du chapitre I - 62
Chapitre II
Séparation et Caractérisation de la Fraction Aromatique C15de l'Huile Brute Safaniya
Résumé - 73
II.1. Introduction - 77
II.2. Echantillon - 81
II.3. Isolement de la fraction aromatique par chromatographie en phase liquide - 84
II.3.1. Séparation des fractions saturée et aromatique sur mini-colonne - 84
II.3.2. Isolement préparatif de la fraction aromatique - 87
II.4. Caractérisation de la fraction aromatique - 89
II.4.1. Fractionnement par PHPLC - 89
II.4.2. Identification moléculaire par GC/MS - 90
II.4.3. Analyse quantitative par GC-FID - 91
II.5. Conclusions - 95
Annexe: tableau des composées monoaromatiques et diaromatiques et de leurs pourcentage dans la fraction 250- °C -
96Références bibliographiques du chapitre II - 99
Chapitre III
Craquage Thermique de la Fraction Aromatique Légère de l'Huile Brute Safaniya - Etude Expérimental et Modélisation Compositionnelle par Classes Moléculaire
Résumé - 105
III.1. Introduction - 109
III.2. Matériels et méthodes - 111
III.2.1. Echantillon - 111
III.2.2. Préparation des tubes en or - 112
III.2.3. Pyrolyses - 112
III.2.4. Analyse des gaz - 113
III.2.5. Analyse de l'extrait - 115
III.2.6. Analyses par GC/MS - 116
III.2.7. Analyse par GC-FID - 117
III.2.8 Fractionnement par HPLC - 117
III.2.9. Conditions de pyrolyse et définition de la conversion globale - 118
III.3. Résultats et discussion - 119
III.3.1. Balayage en température - 119
III.3.2. Etude pyrolytique - 121
III.3.2.1. Résultats quantitatifs - 121
III.3.2.2. Evolution des différentes classes moléculaires de la charge en fonction de la conversion -
122III.3.2.3. Evolution des nouveaux types de composés produits lors des pyrolyses en fonction de la conversion -
125III.3.3. Cinétique - 131
III.3.3.1. Craquage des classes moléculaires de réactifs instables - 132
III.3.3.2. Craquage secondaire des classes de produits instables - 136
III.3.3.3. Modélisation compositionnelle - 139
III.3.3.4. Comparaison entre les valeurs expérimentales et les valeurs calculées à partir du modèle optimisé -
143III.3.3.5. Extrapolation aux conditions géologiques - 148
III.4. Conclusions - 153
Références bibliographiques du chapitre III - 155
Chapitre IV
Effet de la Pression sur le Craquage Thermique de la Fraction Aromatique Légère de l'Huile Brute Safaniya - Implications en prospects profonds
Résumé - 161
IV.1. Introduction - 165
IV.2. Matériels et méthodes - 170
IV.3. Résultats et discussion - 173
IV.3.1. Etude pyrolytique - 173
IV.3.2.1. Résultas quantitatifs - 173
IV.3.2.2. Effet de la pression sur les différentes classes moléculaires de la charge -
174IV.3.2.3. Effet de la pression sur les nouveaux types de composés produitslors des pyrolyses -
177IV.3.2. Intégration de l'effet de la pression dans le modèle cinétique - 179
IV.3.3. Implications en prospects profonds - 181
IV.4. Conclusions - 184
Références bibliographiques du chapitre IV - 185
Conclusions Générales - 189
Références bibliographiques - 199
Annexes - 213
Annexe 1: Mise au point du fractionnement Sat-Aro par chromatographie sur colonne préparative -
215Annexe 2: Photographies et schémas des dispositifs expérimentaux - 225

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