Le raffinage du p trole brut Refining : Presentation Outline

1
Le raffinage du pétrole brut
2
Refining Presentation Outline

• THE RAW MATERIAL
• THE INITIAL FRACTIONATION
• GOALS OF REFINING PURIFICATION, PRODUCTS
  IMPROVEMENT CONVERSION
• EVOLUTION OF THE REFINERIES AND MAIN REFINING
  PROCESSES
• FUTURE CHALLENGES
• THE WORLD REFINING INDUSTRY
• ECONOMICS

3
Raw Material

• RAW MATERIAL CRUDE OIL
• North Sea Ekofisk, Statfjord, Brent, Gullfaks-C
• Middle East Kuwait, Saudi Arabia, Iran, Iraq
• Ex-USSR Ural
• Africa Libya, Nigeria, Zaire, Angola
• North America Gulf of Mexico (on- off-shore),
  Alaska, Canada (Athabasca oil sands)
• Latin America Venezuela (SINCOR)

4
Raw Material (Continued)
North America
Middle-East
Latin America
Ex-USSR
Western Europe and Africa
Far-East and Oceania
Legend
Cumulative production from origin to end 1991
Proven Reserves by 1 Jan. 1992
7.5 mm 109 tons
5
Crude Oil Composition and Products

• Elementary analysis
• Primary components
• Carbon hydrogen
• Impurities
• Sulfur, nitrogen, metals (Ni, Va)
• Thousands of distinct compounds
• Classification of products ("cuts")

Residue
Wax
Name
Boiling Range
Application
Carbon Range
LPG, Fuelgas
LPG
lt 15C
C1 - C4
Gasoil
Motor Spirit
Naphtha
15 - 180C
C5 - C9
Kerosene
Petrochemistry
Jet Fuel
C10 - C14
Kerosene
180 - 250C
Naphtha
Diesel,
Gasoil
250 - 350C
LPG
C15 - C25
Heating Gasoil
(Lubricants)
Wax
350 - 550C
C25 - C60
Heavy Fuel
Residue
gt 550C
gt C60
Bitumen
6
Crude Oil Characterization

• Boiling point analysis TBP Curve (True Boiling
  Point)

Crude "Assay"

• Alternate methods ASTM D86 (atmospheric
  batch distillation, liquid volume
  basis) ASTM D1160 (vacuum batch
  distillation, liquid volume basis)
• ASTM D2887 (chromatography, liquid
  weight basis)

7
Crude Oil Characterization

• Two other important oil characteristics are
  specific gravity and sulfur content
• Specific gravity is normally presented in units
  of oAPI, which is defined as follows oAPI
  141.5/sp.gr. - 131.5
• A specific gravity curve, as a function of
  distilled, is sometimes established
• Crude oil naturally contains sulfur compounds.
  Crudes are classed as sweet or sour depending on
  their sulfur content. If a crude has less than
  0.5 sulfur in it, it is considered to be
  "sweet". If it has more than 2.5 sulfur, it is
  "sour". A crude with a sulfur content between
  these two endpoints is called "intermediate"

8
Crude Oil Characterization for Simulation

• Impossibility to identify all the chemical
  components present ? decomposition of cuts and
  crude into pseudo-components

• Taking into account the available "light-ends"
  analysis light components (C1 to butanes and
  pentanes have relatively few isomers and are
  easily separated from each other and from the
  crude)

9
Crude Oil Characterization for Simulation

• Determine average NBP, SPGR and MW for each
  pseudo-component
• NBP based on the TBP curve
• SPGR if no specific gravity curve is available,
  the SPGR of each cut is computed by assuming that
  the WATSON K factor (measure of the
  paraffinicity of a stock) of each cut is equal
  and equal to that of the crude
• MW based on correlation (NBP, SPGR) if no data
  available

?
10
Crude Oil Characterization for Simulation

• Determine average NBP, SPGR and MW for each
  pseudo-component
• Once the pseudo-components have been generated
  with all their physico-chemical properties, they
  are treated by the simulator in exactly the same
  way as "conventional" components

11
Goals of Refining

• CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS
• Separation of crude oil in intermediate products
• LPG, naphtha, kerosene, gasoil, wax, residue
• Improve the quality of the intermediate crude oil
  products in order to meet the final product
  specifications
• Decrease sulfur content in gasoil from 1 to 0.2
  for diesel
• Increase naphtha octane number from 60 to 98 for
  motor spirit (gasoline)
• Conversion of excess intermediate products into
  highly demanded products
• Conversion of wax into motor spirit (gasoline)
• Conversion of residue into gasoil

12
Refinery Overview

• Importance of the "tank-farm"

04-03-2.5
13
Hydroskimming Refinery (1st Generation)
FUEL GAS
C1 H2S
Sulfur Plant
Gasplant
SULFUR
LPG BUTANE PROPANE
C3 C4
Gas
LIGHT NAPHTHA TO PETROCHEMISTRY
Alkylation
C D U
Sulfur rich gas
Alkylate
MOTOR SPIRIT
Catalytic Reforming
Naphtha
Reformate
DHT
Kerosene
Hydrogen
JET FUEL
Gasoil
Merox
DIESEL
Desulfurization
Atmospheric Residue
HEATING GASOIL
BUNKER FUEL
HEAVY FUEL
14
Goals of Refining

• CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS
• Separation of crude oil in intermediate products
• LPG, naphtha, kerosene, gasoil, wax, residue

15
Initial Fractionation atmospheric distillation
Position ofthe desalter ??
16
Initial Fractionation atmospheric distillation

• Définition des "points de coupe"

17
Initial Fractionation atmospheric distillation

• Définition des "points de coupe"

18
Initial Fractionation atmospheric distillation

• La séparation des coupes n'est jamais parfaite

19
Initial Fractionation atmospheric distillation

• La séparation des coupes n'est jamais parfaite

20
Initial Fractionation atmospheric distillation

• Paramètres de réglage débits soutirés,
  pumparounds et strippers

21
Initial Fractionation atmospheric distillation

• Operation of the atmospheric distillation column

22
Initial Fractionation atmospheric distillation

• Pumparounds (reflux circulants)
• Réglage des points de coupe par la modification
  des débits L et V dans la colonne
• Récupération d'énergie à des niveaux thermiques
  plus intéressants pour le train de préchauffe que
  si tout était condensé en tête

23
Initial Fractionation atmospheric distillation

• Tray efficiency in the atmospheric distillation
  column

24
Goals of Refining

• CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS
• Separation of crude oil in intermediate products
• LPG, naphtha, kerosene, gasoil, wax, residue
• Improve the quality of the intermediate crude oil
  products in order to meet the final product
  specifications
• Decrease sulfur content in gasoil from 1 to 0.2
  for diesel

25
Hydrotreatment of Oil Products (HDS, HDN)
OVEN
Sour Gas (H2S-rich)
REACTOR
SEPARATION SECTION
Light Products
Hydrotreatment Catalyst Co-Mo
Ni-Mo
Hydrotreated Product
Feed
H2-rich Gas (ex-Reformer)
26
Goals of Refining

• CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS
• Separation of crude oil in intermediate products
• LPG, naphtha, kerosene, gasoil, wax, residue
• Improve the quality of the intermediate crude oil
  products in order to meet the final product
  specifications
• Decrease sulfur content in gasoil from 1 to 0.2
  for diesel
• Increase naphtha octane number from 60 to 98 for
  motor spirit (gasoline)

27
Motor gasoline (Mogas) octane
1st Stroke Admission of air gasoline
2nd Stroke Compression and Ignition
3rd Stroke Combustion and Expansion
4th Stroke Exhaust Exit of the burned gas
Pressure in bar
50
Maximum Pressure
40
30
Ignition
Opening Exhaust Valve
20
Average Effective Pressure
Closure Admission Valve
10
Closure Exhaust Valve
Opening Admission Valve
Atmospheric Pressure
28
RON/MON definition

• Research Octane Number (RON)
• ASTM D2699 lab simulation of engine performance
  at low speed (600 rpm)
• Motor Octane Number (MON)
• ASTM D2700 lab simulation of engine performance
  at high speed (900 rpm)
• Procedure
• Admit fuel in motor increase compression ratio
  up to knock
• At this C.R. find out what blend of n-C7/224
  trimethylpentane (iso-octane) causes the same
  knocking intensity. Percentage iso-octane ON

29
Typical octane numbers of gasoline components
Reforming
30
Process flow scheme of a SR catalytic reformer

• SR Semi-Regen

31
Downflow reactor (SR)
32
Radial flow reactor (SR)
33
Process flow of continuous regeneration reformer
Reactor section (CCR)
34
Process flow of continuous regeneration reformer
Regeneration section (CCR)
35
Crude Oil Composition
Source ATOFINA Research
36
Evolution of Demand in Western-Europe
Naphtha LPG
Gasoil Kerosene
Heavy Fuel Bitumen
Source IFP
37
Évolution de la consommation européennedepuis
1998

• Une croissance faible de la demande en Europe de
  0.3 par an 2000-2010
• Une tendance renforcée à la diésélisation, qui
  soutient lévolution contrasté des essences et du
  diesel
• La consommation de fioul lourd continue à diminuer

03-10-2.1
38
Goals of Refining

• CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS
• Separation of crude oil in intermediate products
• LPG, naphtha, kerosene, gasoil, wax, residue
• Improve the quality of the intermediate crude oil
  products in order to meet the final product
  specifications
• Decrease sulfur content in gasoil from 1 to 0.2
  for diesel
• Increase naphtha octane number from 60 to 98 for
  motor spirit (gasoline)
• Conversion of excess intermediate products into
  highly demanded products
• Conversion of wax into motor spirit (gasoline)
• Conversion of residue into gasoil

39
Conversion Refinery (2nd Generation)
FUEL GAS
C1 H2S
Sulfur Plant
Gasplant
SULFUR
LPG BUTANE PROPANE
C3 C4
Gas
LIGHT NAPHTHA TO PETROCHEMISTRY
MTBE
Alkylation
C D U
MTBE
Sulfur rich gas
Alkylate
MOTOR SPIRIT
Catalytic Reforming
Naphtha
Reformate
DHT
Kerosene
Cat Cracked Spirit
CRUDE
Hydrogen
JET FUEL
Gasoil
Merox
DIESEL
Desulfurization
Atmospheric Residue
HEATING GASOIL
Catalytic Cracking
Light Cycle Oil
Wax
Heavy Cycle Oil
BUNKER FUEL
V D U
Visbroken naphtha
Visbroken Gasoil
Visbreaking
HEAVY FUEL
Visbroken Residue
Vacuum Residue
Bitumen Plant
BITUMEN FOR ROAD CONSTRUCTION
40
Initial Fractionation vacuum distillation

• Use of vacuum enables separation of heavier cuts
  before cracking becomes significant e.g. wax is
  distilled below 400 C, whereas its TBP endpoint
  is around 550 C

41
Initial Fractionation vacuum distillation
42
Initial Fractionation vacuum distillation

• Operation of the vacuum distillation column

43
Initial Fractionation vacuum distillation

• Tray efficiency in the vacuum distillation column

44
Fluid Catalytic Cracker (FCC)
Cracked Gas Compressor
Water
Steam
Atm.
Expansion Turbine
Coke Combustion Flue Gas
Fuel Gas H2S
Heat Recovery
C3 Cut
Gas and Gasolines Separation
3rd stage Cyclone Catalyst Recovery
REACTOR
C4 Cut
Main Fractionator
S T R I P P E R
2nd stageCyclones
Gasolines Cut
Steam
Coke
REGENERATOR
Steam
Gasoil Cut (LCO)
Steam
Heavy Cycle Oil (HCO)
RISER
Air
Catalyst
Heavy Cuts (HCO Slurry)
Slurry
Air Compressor
Temperature (C)
Feed
Pressure (barg)
Flow (t/h)
45
Deep Conversion Refinery (3rd Generation)
FUEL GAS
C1 H2S
Sulfur Plant
Gasplant
SULFUR
LPG BUTANE PROPANE
C3 C4
Gas
LIGHT NAPHTHA TO PETROCHEMISTRY
MTBE
Alkylation
C D U
MTBE
Sulfur rich gas
Alkylate
MOTOR SPIRIT
Catalytic Reforming
Naphtha
Reformate
DHT
Cat Cracked Spirit
Kerosene
CRUDE
Hydrogen
JET FUEL
Gasoil
Merox
DIESEL
Desulfurization
Atmospheric Residue
HEATING GASOIL
Hydrogen
ARDS
Gasoil
Catalytic Cracking
Light Cycle Oil
Residue
Wax
Heavy Cycle Oil
BUNKER FUEL
V D U
Visbroken naphtha
Visbroken Gasoil
Visbreaking
HEAVY FUEL
Visbroken Residue
Vacuum Residue
Bitumen Plant
BITUMEN FOR ROAD CONSTRUCTION
46
Deep Conversion

• CHEVRON ARDS (Atmospheric Residue
  DeSulfurization) TECHNOLOGY
• Conversion of atmospheric residue into
• Wax gt catalytic cracker feedstock
• Gasoil gt diesel
• Naphtha gt catalytic reformer
• - Conversion 35 - 40
• - Overall Refinery Conversion 50
  - 55 gt 60 - 70
• Sulfur and metals removal
• Allows to use high sulfur crude-oil to make
  products with (future) severe specifications
  alleviates metal problems in FCC
• New sulfur plant
• Hydrogen purification system

47
Deep Conversion (Continued)

• Arabian Mix with ARDS compared to Brent without
  ARDS
• More volume expansion
• More diesel
• Less sulfur in products
• Better wax quality
• Less gasoline
• ? (Brent - Arabian Mix) 3/BBL (Normally)
• More conversion of residue compared to Arabian
  Mix without ARDS

48
Refinery Operations

• Separation of crude oil into intermediate
  products
• Atmospheric distillation of crude oil into
• LPG
• NAPHTHA
• KEROSENE
• GASOIL
• ATMOSPHERIC RESIDUE
• Vacuum distillation of atmospheric residue
• WAX
• VACUUM RESIDUE
• Purification of intermediate products
• Desulfurization and denitrification of naphtha

49
Refinery Operations (Continued)

• Conversion and/or quality improvement of
  intermediate products
• Desulfurization of gasoil (HDS) sulfur removal
• Catalytic reforming of naphtha (CCR) increase
  octane number, H2 production
• Catalytic cracking of wax (FCC) conversion into
  gasoil and high octane gasoline (CCS)
• Alkylation conversion of C4 gases into high
  octane gasoline (Alkylate)
• Catalytic Polymerization of light olefins
  (CATPOLY) conversion into high octane gasoline
• Visbreaking of vacuum residue (VB) conversion
  into gasoil and reduction of residue viscosity
• ARDS of atmospheric residue sulfur removal and
  conversion into naphtha, gasoil and wax

50
Refinery Operations (Continued)

• Special processes
• Production of Jet-fuel (MEROX)
• Production of Propylene (Fixed Bed Cracking)
• Production of MTBE (Methanol I-Butene)
• Production of Bitumen (Blowing)
• Production of Sulfur (Claus)

51
Refinery Operations (Continued)

• Blending of intermediate products into finished
  marketable products of the desired quality and in
  the desired quantity
• Motor spirit (gasoline)
• Reformate, cracked gasoline (CCS) , MTBE,
  alkylate, butane
• Diesel
• Gasoil, kerosene, light cycle oil (LCO)
• Fuel Oil
• Visbroken residue, gasoil, kerosene, light cycle
  oil (LCO), heavy cycle oil (HCO)

52
Future Challenges in Refining

• Evolution of the market for oil products
• Decreasing market for fuel oil
• Increasing market for diesel
• Stagnant and slightly decreasing market for
  gasoline
• Increasing market for petrochemical feedstock
• ethylene, propylene, benzene, xylenes
• Deeper conversion of residues into more valuable
  products
• Better integration between refining and
  petrochemistry

53
The Future of Refining

• The traditional view of an oil refinery as a
  manufacturing plant that takes in crude oil and
  produces a slate of products is becoming
  increasingly outmoded.
• In todays competitive climate, unless
  particularly advantaged by location or cost, the
  refiner needs to do much more. By viewing
  themselves as energy centers providing oil
  products and services, or molecule managers
  providing petrochemical feedstocks and
  intermediate and finished products, refiners can
  make the economics work.
• Oil Gas Journal, 20/04/98

54
Future Challenges in Refining (Continued)

• Evolution towards cleaner products
• Motor spirit (gasoline) unleaded, lower sulfur,
  benzene and aromatics content
• Diesel lower sulfur and aromatics content
• Fuel oil only low sulfur fuel oil
• Low sulfur crude oils will become more expensive
• More severe specifications on refinery emissions
• Flue gas (CO2)
• Waste water

55
Les spécifications européennes, les principaux
changements

• Nécessaire adaptation de loutil de raffinage et
  de la logistique
• pour garantir lintégrité des produits
• Des incitations fiscales accélèrent larrivée de
  produits aux nouvelles spécifications

03-10-2.1
56
Une évolution mondiale
²

• Convergence des spécificationsdes nouveaux
  entrants

• Amérique du Nord
• 2006 Essence soufre à 30 ppm max
• 2006 Diesel routier soufre à 15 ppm max

• Asie- Pacifique
• Horizon 2005 2010 soufre à 500 ppm, voire 10
  50 ppm dans le spays avançés
• Suppression de lessence plombée (Indonésie)

• Afrique Moyen-Orient
• Suppression de lessence plombée

• Amérique du Sud
• Mise au point des spécifications soufre
  50-500ppm à horizon 2005-2010
• Suppression de lessence plombée (Pérou,
  Vénézuela)

• Tirée par
• Lamélioration de la qualité de lair
• Les exigences des nouveaux moteurs

03-10-2.1
Source of Data VEBA OIL REFINING
PETROCHEMICAL presentation to WG V Original
Data PFC
57
Évolution de la demande mondiale de produits
pétroliers - Mbd

• 1 Mbd ? 30.106 t/yr

03-10-2.1
58
Raffinage mondial 2002 de pétrole brut (Mt/an)
Capacité
Consommation
Europe Orientale
363
Extrême-OrientOcéanie
Europe Occidentale
Amérique du Nord
- 22
18

• 54

Proche-Orient
108
Amérique Latine
-249
Afrique
42
Total Mondial
3523
4098
575
03-10-2.1
59
TOTAL Refineries
60
TOTAL leader européen du Raffinage-Marketing
Source publications sociétés, estimations STD
45.3 CEPSA inclus
03-10-2.3
61
Données économiques

• Quotations du brut (à la date du cours de 2004)

62
Données économiques

• Quotations du brut (cette semaine)

63
Données économiques

• Marges de raffinage (à la date du cours de 2004)

64
Données économiques

• Marges de raffinage (cette semaine)

65
Données économiques

• Marges de raffinage évolution au jour le jour

2004
66
Données économiques

• Marges de raffinage évolution historique et
  dépendance géographique

Première guerre du golfe
Source Goldman Sachs / PetroFina
67
Données économiques

• Marges de raffinage évolution historique

Seconde guerre du golfe
68
Données économiques

• Marges de raffinage évolution historique