Le raffinage du ptrole brut

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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

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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)

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Raw Material (Continued)

North
America

Middle-East

Latin
Western Europe
America
and Africa

Ex-USSR
Far-East and
Oceania

Legend
Cumulative production
from origin to end 1991
Proven Reserves
by 1 Jan. 1992

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7.5 mm = 109 tons

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"):
Name

Boiling Range Carbon Range Application

LPG, Fuelgas
LPG
< 15C
C 1 - C4
Motor Spirit
Naphtha
15 - 180C
C 5 - C9
Petrochemistry
C10 - C14
Jet Fuel
Kerosene
180 - 250C
Diesel,
Gasoil
250 - 350C
C15 - C25
Heating Gasoil
(Lubricants)
Wax
350 - 550C
C25 - C60
Heavy Fuel
Residue
> 550C
> C60
Bitumen

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Boiling range of petroleum

products
900
800
Boiling Temperature (C)

700

Residue

600
500

Wax

400
300

Gasoil

200

Kerosene

100

Naphtha
LPG

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)

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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"
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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 "lightends" analysis : light
components (C1 to
butanes and pentanes
have relatively few
isomers and are easily
separated from each
other and from the
crude)

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Crude Oil Characterization for Simulation

Determine average NBP, SPGR and MW for each pseudocomponent

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

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Crude Oil Characterization for Simulation

Determine average NBP,

SPGR and MW for each
pseudo-component

Once the pseudocomponents have been

generated with all their
physico-chemical
properties, they are treated
by the simulator in exactly
the same way as
"conventional" components

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10

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
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Importance of the "tank-farm"

04-03-2.5

Refinery Overview

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Hydroskimming Refinery (1st Generation)

Gasplant

C1 + H2S

Sulfur Plant

C3 + C4

FUEL GAS
SULFUR

LPG + BUTANE
+ PROPANE

Gas

Alkylation

Sulfur rich gas

Alkylate

C
Naphtha

LIGHT NAPHTHA TO
PETROCHEMISTRY

Kerosene

DHT

Catalytic
Reforming

MOTOR SPIRIT

Reformate

Hydrogen

Gasoil

Atmospheric
Residue

JET FUEL

Merox
Desulfurization

DIESEL

HEATING
GASOIL

BUNKER FUEL

HEAVY FUEL

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Goals of Refining

CONVERT CRUDE OIL INTO MARKET-READY PRODUCTS

Separation of crude oil in intermediate products

LPG, naphtha, kerosene, gasoil, wax, residue

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Initial Fractionation : atmospheric distillation

Fuel Gas
Temperature C
Pressure bar(a)

Propane Cut

Deethaniser

Depropaniser
Crude Tank

Debutaniser
Butane Cut

Gas +
Naphtha
Preheat
Train

Position of
the desalter ??

Atmospheric
Column

Light Naphtha
Naphtha
Splitter

Naphtha

Heavy Naphtha

Desalter

Kerosene + Naphtha

Water
Preheat
Train

Stripper

Light Gasoil (LGO)

Heavy Gasoil (HGO)

Atmospheric Oven

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Atmospheric
Residue
15

Initial Fractionation : atmospheric distillation

Dfinition des "points de coupe"

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Initial Fractionation : atmospheric distillation

Dfinition des "points de coupe"

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Initial Fractionation : atmospheric distillation

La sparation des coupes n'est jamais parfaite

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Initial Fractionation : atmospheric distillation

La sparation des coupes n'est jamais parfaite

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Initial Fractionation : atmospheric distillation

Paramtres de rglage : dbits soutirs, pumparounds et strippers

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Initial Fractionation : atmospheric distillation

Operation of the atmospheric distillation column

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Initial Fractionation : atmospheric distillation

Pumparounds (reflux circulants)

Rglage des points de coupe par la modification des dbits L et
V dans la colonne

Rcupration d'nergie des niveaux thermiques plus

intressants pour le train de prchauffe que si tout tait

condens en tte
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Initial Fractionation : atmospheric distillation

Tray efficiency in the atmospheric distillation column

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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

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Hydrotreatment of Oil Products (HDS, HDN)

OVEN

Sour Gas
(H2S-rich)

REACTOR

SEPARATION
SECTION
Hydrotreatment
Catalyst : Co-Mo
Ni-Mo

Feed

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Light Products

Hydrotreated
Product

H2-rich Gas
(ex-Reformer)

25

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)

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Motor gasoline (Mogas) octane

Pressure in bar

1st Stroke:
Admission of
air + gasoline

50
40

2nd Stroke: 3rd Stroke:

4th Stroke:
Compression and
Combustion and
Exhaust
Ignition
Expansion Exit of the burned gas

HDP :High Dead Point

LDP : Low Dead Point

Maximum Pressure

30

Ignition
Average Effective Pressure
10
Closure
Opening
Admission Valve
Admission Valve

Opening
Exhaust Valve

20

Closure
Exhaust Valve
Atmospheric Pressure

HDP

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LDP

HDP

LDP

HDP

27

RON/MON definition

Research Octane Number (RON)

ASTM D2699 = lab simulation of
engine performance at low speed
(600 rpm)

Knockmeter

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

Sparking-plug

Control of the
Compression Ratio

Micrometer

At this C.R. find out what blend of

n-C7/224 trimethylpentane
(iso-octane) causes the same
knocking intensity. Percentage
iso-octane = ON

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Typical octane numbers of gasoline components

Cracking
Products

Present in crude oil

PARAFFINS

NAPHTHENES

AROMATICS

OLEFINS

Linear
Paraffins

(branched chains)

Isoparaffins

Liquid density

Low

Low

Medium

High

Low

Research Octane
Number

Very low

High

Medium

Very high

High

Sensitivity
(RON-MON)

Very low

Very low

Low

High

Very high

Reforming

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Process flow scheme of a SR catalytic reformer

SR = Semi-Regen

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Downflow reactor (SR)

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Radial flow reactor (SR)

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Process flow of continuous regeneration reformer

Reactor section (CCR)

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Process flow of continuous regeneration reformer

Regeneration section (CCR)

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Crude Oil Composition

120
100

LPG
Naphtha
Kerosene
Gasoil
Wax
Residue

80
60
40
20

MAYA

ARABIAN
HEAVY

IRANIAN
HEAVY

ARABIAN
LIGHT

EKOFISK

STATFJORD

Time Trend
Source : ATOFINA Research

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Evolution of Demand in Western-Europe

120

100
18.6

21.1

24.4

29.2

31.3

32

32.0

43.4

43.8

45.8

27.8

25.3

24.2

22.2

1985

1990

1993

2000

80

60

35.5

36.4

37.8
43.0

40

20

45.9

42.5

Naphtha + LPG
Gasoil + Kerosene
Heavy Fuel + Bitumen

37.8

0
1973

Source : IFP

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1975

1980

Time Trend
36

volution de la consommation europenne

depuis 1998
220
200
GOM

180

MT/an

160
140
Essences
120

FOD

100
80

Jet/kero

Fuel Lourd

2010

2009

2008

2007

2006

2005

2004

2003

2002

2001

2000

croissance faible de la demande en Europe de + 0.3% par an 2000-2010

Une tendance renforce la dislisation, qui soutient lvolution contrast des essences et
du diesel
La consommation de fioul lourd continue diminuer

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03-10-2.1

Une

1999

40

1998

60

37

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
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Conversion Refinery (2nd Generation)

Gasplant

C1 + H2S

FUEL GAS

Sulfur Plant

C3 + C4

SULFUR

LPG + BUTANE
+ PROPANE

Gas

Naphtha

CRUDE

MTBE

Alkylate

C
D

MTBE

Alkylation

Sulfur rich gas

DHT

Kerosene

Catalytic
Reforming

LIGHT NAPHTHA TO
PETROCHEMISTRY
MOTOR SPIRIT

Reformate
Cat Cracked Spirit

Hydrogen

Gasoil

JET FUEL

Merox
Desulfurization

Atmospheric
Residue

DIESEL

HEATING
GASOIL

Catalytic
Cracking

Wax

V
D
U

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Visbroken naphtha

Visbreaking
Vacuum
Residue

Bitumen Plant

Light Cycle Oil

Heavy Cycle Oil

BUNKER FUEL

Visbroken Gasoil
HEAVY FUEL
Visbroken Residue
BITUMEN FOR
ROAD CONSTRUCTION

39

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
Vacuum System
Vacuum Gasoil (VGO)
Atmospheric
Residue

Vacuum Column

Wax

Heavy Wax

Vacuum Oven

Vacuum Residue (Pitch)

Bitumen
Deasphalting

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Initial Fractionation : vacuum distillation

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Initial Fractionation : vacuum distillation

Operation of the vacuum distillation column

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Initial Fractionation : vacuum distillation

Tray efficiency in the vacuum distillation column

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Fluid Catalytic Cracker (FCC)

Water

Cracked Gas
Compressor

Atm.
Coke Combustion
Flue Gas

Fuel Gas + H2S

Gas and Gasolines
Separation

Expansion
Turbine

Steam

Heat Recovery

3rd stage Cyclone

Catalyst Recovery

REACTOR

2nd stage
Cyclones
REGENERATOR

Coke

Main Fractionator

S
T
R
I
P
P
E
R

C3 Cut

C4 Cut
Gasolines Cut

Steam

Steam

Gasoil Cut (LCO)

Steam

RISER

Heavy Cycle Oil (HCO)

Air
Catalyst
Air Compressor
Feed

Slurry
Temperature (C)
Flow (t/h)

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Heavy Cuts
(HCO + Slurry)

Pressure (barg)

44

Deep Conversion Refinery (3rd Generation)

C1 + H2S

Gasplant

FUEL GAS

Sulfur Plant

C3 + C4

SULFUR

LPG + BUTANE
+ PROPANE

Gas

Naphtha

CRUDE

MTBE

Alkylate

C
D

MTBE

Alkylation

Sulfur rich gas

DHT

Kerosene

Catalytic
Reforming

LIGHT NAPHTHA TO
PETROCHEMISTRY
MOTOR SPIRIT

Reformate
Cat Cracked Spirit

Hydrogen

Gasoil

JET FUEL

Merox
Desulfurization

Atmospheric
Residue

HEATING
GASOIL

Hydrogen

ARDS

Gasoil

Residue

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Catalytic
Cracking

Wax

V
D
U

Visbroken naphtha

Visbreaking
Vacuum
Residue

DIESEL

Bitumen Plant

Light Cycle Oil

Heavy Cycle Oil

BUNKER FUEL

Visbroken Gasoil
HEAVY FUEL
Visbroken Residue
BITUMEN FOR
ROAD CONSTRUCTION

45

Deep Conversion

CHEVRON ARDS (Atmospheric Residue DeSulfurization)

TECHNOLOGY
Conversion of atmospheric residue into
Wax ==> catalytic cracker feedstock
Gasoil ===> diesel
Naphtha ===> catalytic reformer
- Conversion : 35 - 40 %
- Overall Refinery Conversion 50 - 55% ==> 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

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Deep Conversion (Continued)

Yield (vol %)
LPG

Arabian Mix
Brent
with ARDS without ARDS
2.3
4.1

Light
Distillates
Medium
Distillates
Wax

18.2

21.8

47.9

40.7

23.6

23.5

Fuel Oil (L.S)

10.0

10.3

Total

102.0

100.4

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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
47

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

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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

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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)

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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 :

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Visbroken residue, gasoil, kerosene, light cycle oil

(LCO), heavy cycle oil (HCO)
51

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

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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

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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

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 Ncessaire adaptation de loutil de raffinage et de la logistique

pour garantir lintgrit des produits
Des incitations fiscales acclrent larrive de produits aux nouvelles spcifications

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03-10-2.1

Les spcifications europennes,

les principaux changements

55

Une volution mondiale

Convergence

Amrique
Amriquedu
duNord
Nord
2006 : Essence soufre 30 ppm max
2006 : Essence soufre 30 ppm max
2006 : Diesel routier soufre 15 ppm max
2006 : Diesel routier soufre 15 ppm max

des spcifications
des nouveaux entrants

AsieAsie-Pacifique
Pacifique

Afrique & Moyen-Orient

Afrique & Moyen-Orient
Suppression de lessence
Suppression de lessence
plombe
plombe

Tire par :
Lamlioration de la qualit de lair
Les exigences des nouveaux moteurs

Source of Data : VEBA OIL REFINING & PETROCHEMICAL presentation to WG V

Original Data : PFC

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03-10-2.1

Amrique
Amriquedu
duSud
Sud
Mise au point des spcifications soufre
Mise au point des spcifications soufre
50-500ppm
50-500ppmhorizon
horizon2005-2010
2005-2010
Suppression de lessence plombe
Suppression de lessence plombe
(Prou, Vnzuela)
(Prou, Vnzuela)

Horizon 2005 2010 soufre

Horizon 2005 2010 soufre
500
500ppm,
ppm,voire
voire10
1050
50
ppm
dans
le
spays
avans
ppm dans le spays avans
Suppression de lessence
Suppression de lessence
plombe
plombe(Indonsie)
(Indonsie)

56

volution de la demande mondiale de produits

ptroliers - Mbd
1 Mbd 30.106 t/yr
Demande
78

76.72

Demande - MBD

76

76.01 76.38

74.79
73.1 73.5

74
72

70.69

70

68.66

68

65.75 65.58

66

63.57

64

66.23

66.83

67.53

64.34

62.25
62

60.31
1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002

Annes

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Demande

03-10-2.1

60

57

Raffinage mondial 2002 de ptrole brut (Mt/an)

Capacit

Consommation

Europe Orientale

531 168 +363

Europe Occidentale
Amrique du Nord

930 984 -54

735 757 - 22

Extrme-Orient
Ocanie

1010 992 +18

Proche-Orient

315 207 +108

Amrique Latine

417 296 -249

Afrique

Total Mondial

4098 3523 +575

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03-10-2.1

161 119 + 42

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TOTAL Refineries

Chine
tats-Unis

Canaries

Martinique
Sngal
Cte d'Ivoire
Vnzuela

Cameroun
Gabon
Zambie

04-03-2.3

Angola

Afrique du Sud

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TOTAL : leader europen du Raffinage-Marketing

3,000

Capacit de raffinage en
Europe en 2002 (kb/j)

2,500

TOTAL*
ExxonMobil Shell+DEA

2,000
1,500

TotalFina

ENI

Ventes de produits raffins

en Europe en 2002 (kb/j)

500Conoco-Phillips Chevron-Texaco
Statoil
KPI - Q8
800

1,200

Source: publications socits, estimations STD

* 45.3% CEPSA inclus

1,600

2,000

2,400
03-10-2.3

Repsol-YPF
Petrofina

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BP+Veba

Elf
BP
Total

1,000

400

Shell

60

Donnes conomiques

Quotations du brut ( la date du cours de 2004)

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Donnes conomiques

Quotations du brut (cette semaine)

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Donnes conomiques

Marges de raffinage ( la date du cours de 2004)

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Donnes conomiques

Marges de raffinage (cette semaine)

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Donnes conomiques

Marges de raffinage : volution au jour le jour

2004

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Donnes conomiques

Marges de raffinage : volution historique et dpendance

gographique
16
14
12

Premire guerre du golfe

$/BBL

10
8
6
4
2
0

Europe

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US Gulfcoast

Singapore

Source : Goldman Sachs / PetroFina

66

Donnes conomiques

Marges de raffinage : volution historique

Seconde guerre du golfe

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Donnes conomiques

Marges de raffinage : volution historique

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