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Refining-Petrochemicals-Chemicals-Engineering

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PURPOSE OF THE HYDROTREATMENT PROCESSES

I - CLEANING MEDIUM IN THE REFINING ACTIVITY ................................................................. 1

II - IMPACT OF THE SULPHUR CONTAINED IN PETROLEUM CUTS AND PRODUCTS........... 2

III - IMPACT OF NITROGEN CONTAINED IN PETROLEUM CUTS AND PRODUCTS ................. 3

IV - IMPACT OF THE OXYGEN CONTAINED IN PETROLEUM CUTS AND PRODUCTS ............ 4

V - IMPACT OF THE METALS CONTAINED IN PETROLEUM CUTS AND PRODUCTS ............. 5

VI - IMPACT OF THE UNSATURATED COMPOUNDS CONTAINED IN PETROLEUM CUTS


AND PRODUCTS ...................................................................................................................... 6

VII - QUALITY SPECIFICATIONS OF COMMERCIAL PRODUCTS ................................................ 7

VIII - CHARACTERISTICS OF PETROLEUM CUTS ......................................................................... 8

IX - WORLD MARKET FOR TRANSPORTATION FUEL - QUALITY TRENDS............................... 9

X - ALTERNATE TRANSPORTATION FUELS ............................................................................. 11

XI - MANAGEMENT OF HYDROTREATMENT PROCESSES IN THE REFINING SCHEME ....... 12

RA HDT - 00753_A_A - Rev. 3 09/02/2012


© 2012 - IFP Training
1

I- CLEANING THE MEDIUM IN THE REFINING ACTIVITY


Hydrotreating includes a lot of refining processes that aim at eliminating the undesired compounds present in
the petroleum cuts. They all use hydrogen to react with the impurities to be removed. In the refinery,
hydrogen is produced by the catalytic reforming unit. It may be concentrated in order to increase the
efficiency of the hydrotreatment processes. If the hydrogen balance is short, it is possible to benefit from
alternate sources: to import some H2 from a neighbouring plant or produce it thanks to a dedicated unit.

The impurities to be removed from petroleum are included in the structure of the hydrocarbon molecules.
Therefore all these processes need a solid catalyst to promote the cleaning chemical reactions.

The main impurities contained in crude oils are:

- sulfur
- nitrogen
- oxygen
- metals
- aromatic compounds to some extent

In addition to that, the cracking processes in the refinery generate certain amounts of unsaturated compounds
like:

- olefins
- diolefins
- acetylenic compounds

Thanks to the cleaning action of hydrogen, the pollutants are transformed into molecules that are easy to be
separated from the purified cut, the unsaturated bounds disappear, the metals are trapped on the solid
catalyst.

These impurities would largely impact the quality of the refined products and cause:

- atmospheric pollution

- bad smell of some commercial products

- color instability

- corrosion in the refinery or along the distribution circuit

- improper combustion

- polymerization leading to fouling phenomena

- catalyst poisoning in some refining processes or in the end use

00753_A_A © 2012 - IFP Training


2

II - IMPACT OF THE SULFUR CONTAINED IN PETROLEUM CUTS AND PRODUCTS


Some sulfur compounds are represented on the tables in the appendix 1 and 2. Sulfur is the impurity that has
the largest concentration in the crude oil. It ranges between 0.1% for the sweetest crude oils and
10% weight for the most sour ones. But the distribution of sulfur is not even along the boiling temperature
scale (appendices 3 and 4).

The potential consequences of sulfur in the commercial products are:

a - Atmospheric pollution

During the combustion of the products, the sulfur atoms react with the oxygen in the air and are transformed
into sulfur oxides SO2 and SO3. Sulfur trioxide SO3 is transformed into sulfuric acid H2SO4 with the humidity
of the atmosphere: it provokes then acidic rains damaging the environment.

b - Corrosion

Hydrogen sulphide and mercaptans cause corrosion in the refinery and also in the distribution circuit. Auto-
lubricated pumps are especially sensitive to this type of degradation, causing blockages.

c - Bad smell

Hydrogen sulphide H2S and mercaptans have a very strong odor that is quite unpleasant.

d - Catalyst poisoning in the refining activity

Sulfur is a reversible poison of the catalyst in the catalytic reformer. Sulfur is also a permanent poison of the
catalyst in the isomerization process.

e - Catalyst poisoning in the end-uses

The exhaust gas of any engine contains pollutants: unburned hydrocarbons, carbon monoxide CO and
nitrogen oxides NOX, like NO or NO2. In order to protect the environment, it is necessary to implement a
catalytic converter downstream the engine to clean these off-gases.

Sulfur is a poison for the catalyst used for cleaning the exhaust gas of the engines:

- sulfur in the gasoline is an inhibitor for the “three way” catalyst. This poisoning action is
reversible: it disappears when the spark engine is fed again with very low sulfur gasoline. A
study noticed 15% more pollutants in the exhaust gas when burning a 450 ppm sulfur
gasoline instead of a 50 ppm one. (appendix 7)

- sulfur in the diesel oil has a threefold impact:

• it is burnt into sulfur oxide SO2 that is converted into SO3 on the hot catalyst. This
phenomenon is harmful because it provokes an increase of particulate matters
emission

• furthermore sulfur poisons the noble metals (platinum, palladium or rhodium)


deposited on the catalyst

• in addition to that, sulfur is also a poison for the future “DeNOx” catalysts that will
convert NO into nitrogen N2

00753_A_A © 2012 - IFP Training


3

III - IMPACT OF NITROGEN CONTAINED IN PETROLEUM CUTS AND PRODUCTS


Nitrogen in the hydrocarbons is bounded inside the chemical structure of the molecules, as sulfur is. The
concentration of nitrogen in crude oils is much lower than sulfur, between 10 and 100 times less. Some typical
nitrogenated compounds are presented in the table in the appendix 8.

The potential drawbacks of nitrogen in the commercial products are the following ones:

a - Color instability

Color is not linked with performances of the commercial products. But it may darken during long time
storage, because of the formation of gums in the light products like gasoline, kerosene or gas oil. This is due
to the presence of aromatic rings containing a nitrogen atom of the indole type. Unsaturated poly-aromatic
rings may also be responsible for this kind of darkening phenomenon. Beyond 100 ppm nitrogen, the color is
most of the time unstable.

b - Basicity

Some nitrogen containing compounds have a medium or even strong basic character. They react thus with
acidic catalyst of some processes such as FCC (Fluid catalytic cracking), HCK (hydrocraking), catalytic
reformer or isomerization.

c - Foaming

The basic character of some of these compounds may give a more or less strong tendency to foaming
phenomena. It may thus increase the tendency to stabilize emulsions of water.

The table hereunder indicates that there is no clear correlation between sulfur content, nitrogen content and
acidity (linked to oxygen content) of crude oils.

Sulphur content (% Nitrogen content Acidity


Crude oil
mass) (ppm mass) (KOH mg/g)

Forcados 0.17 846 0.34

Djeno 0.27 2830 0.40

Bonny Light 0.14 986 0,27

Kuito 0.68 n.i. 2.1

Dubaï 2.1 1270 0.01

Brent 0.39 0.01

Troll 0.27 842 1.0

00753_A_A © 2012 - IFP Training


4

IV - IMPACT OF THE OXYGEN CONTAINED IN PETROLEUM CUTS AND PRODUCTS


Oxygen in the hydrocarbons is bounded inside the chemical structure of the molecules, as sulphur and
nitrogen are. The concentration of oxygen may be quite fair in some crude oils, but in any case lower than
sulphur concentration.

Some examples of compounds containing oxygen are represented hereunder.

• Organic acids

This kind of compound is characterized by the presence of an “acid group” –COOH.

O
R C
O H

Most of the oxygen atoms present in the crude oil are contained in the famous “Naphthenic acids” as shown
below.

O
C
OH
D CH 2208 C

• Phenolic compounds

These components are produced by cracking processes like FCC. They are characterized by an “alcohol
group” – OH branched on an aromatic ring.

Phenols

O H
D CH 157 D

The potential drawbacks of oxygen in the hydrocarbons are:

a- the corrosiveness of naphthenic acids that decompose around 250°C and form corrosive
components in the units of the refinery

b- these compounds form also water in the presence of hydrogen in some catalytic processes
like catalytic reformer or isomerization. The water is a poison for these catalysts

The concentration of these acidic compounds is measured in the crude oil by neutralization with potash. The
crude oils coming from the Guinea Golf in Africa contain quite a large quantity of naphthenic acids, as shown
in the previous table.

Acidity = mg of Potash per gram of crude.

00753_A_A © 2012 - IFP Training


5

V- IMPACT OF THE METALS CONTAINED IN PETROLEUM CUTS AND PRODUCTS


The “organic metals” encountered in the crude oil are Nickel and Vanadium. Their concentration, presented
hereunder, is different from one crude oil to an other one.

origin Nickel (ppm) Vanadium (ppm) Sp. Gravity


FOROZAN (Iran) 12 38 30.6
ZAKUM lower (A. Dhabi) 0.4 0.5 40.2
DUBAÏ (Dhubaï) 13 80 31.2
BRENT (U.K.) 2 7 38.1
EKOFISK (Norway) 3 1.5 37.5
KUITO (Angola) 45 42 19
GIRASOL (Angola) 8 4 31
BONNY Light (Nigeria) 3 0.4 35.4
BEKAPAÏ (Indonesia) 0.4 0 43.2

Metals are trapped in very large molecular structures called “resins” and “asphaltenes”. These molecules are
very heavy, very aromatic and non-volatile. They are concentrated in the heaviest cut: the vacuum residue.
But heavy VGO may contain some resins. An example of an asphaltene molecule is given in appendix 9.

Asphaltenes are defined as petroleum fractions insoluble in cold n-heptane but soluble in hot boiling
toluene. Resins are less heavy than asphaltenes: they peptise the asphaltenic compounds in the oily
environment. Resins are aromatic compounds and contain also a large part of the metals: between one and
two thirds. As to be seen in the example above, the metals are linked most of the time to heteroatoms.

Some crude oils contain also a very small amount of Arsenic or Mercury in the structure of the hydrocarbon
molecules, even in the light cuts like gasoline or kerosene. The concentration is rather a few ppb.
+
In addition to “organic metals” there are some “inorganic metals”, mainly sodium in the ionic form Na : it is
part of sodium chloride from the salty water in the crude oil.

The potential consequences of metals in the petroleum cuts are :

a - Ashes

In the boilers or other industrial furnaces, the burning of heavy fuels generates ashes that contain the metal
oxides. They deposit on tubes suspensions causing corrosion and breakage.

b - Catalyst poisoning

The metals deposit on the catalyst surface in HCK, FCC or RCC processes. They may poison the active sites,
block the smallest pores and weaken the mechanical resistance of the catalyst. These metals are the main
obstacle to the catalytic conversion of residues.

c - Coking phenomena

Sodium favors the cocking phenomena in the tubes of the furnaces at very high temperatures as in the
visbreaker or coker units.

00753_A_A © 2012 - IFP Training


6

VI - IMPACT OF THE UNSATURATED COMPOUNDS CONTAINED IN PETROLEUM CUTS


AND PRODUCTS
Unsaturated compounds in the crude oil are aromatics, as presented in the appendix 10. But the cracking
processes like FCC, visbreaker or coker and Steam cracker (Ethylene plant) generate a lot of olefins,
diolefins and acetylenic compounds as presented in the appendix 11. Refer also to appendix 12.

Two methods may characterize the olefin or diolefin content of the feed:
- the “Bromine Index” (ASTM D1159) corresponds to the total concentration of olefins and
diolefins. Bromine combines with the double bounds of olefins and with one double bound of
the diolefins. The “Bromine Index” is the number of grams of bromine fixed by 100 grams of
sample to be measured.
- the M.A.V. (Maleic Anhydride Value) corresponds to the concentration of diolefins only. The
reactant combines only with the diolefins. The result of the test indicates the mg of maleic
anhydride fixed by 1 gram of sample.

The “Diene Value” is equivalent to the M.A.V. It is calculated as follows:

M.A.V.
D.V. =
3,86

It is the number of grams of Iodide equivalent to the quantity of maleic anhydride reacting with 100 grams of
sample.

Cracked cuts Maleic Anhydrid Bromine Index


Value
FCC gasoline — 40
Coker gasoline 15 75
Pyrolisys gasoline 25 65
LCO = FCC gas oil — 15
Coker gas oil — 54
Visbreaker gas oil — 15

The potential consequences of unsaturated compounds in the hydrocarbon products are manifold:

- diolefins are highly unstable and may form gums leading to fouling phenomena and
blockage
- butadiene in the C4 cut of the FCC is a diolefin disturbing the proper operation of alkylation
- olefins in the gas oil cuts may cause color instability and lower the Cetane Index
- benzene content in the gasoline is limited to a low value: 1%
- aromatic compounds worsen the smoke point of the Jet A1 and the Cetane Index of gas oil
cuts (appendix 12)
- heavy polycyclic aromatics induce:
• particulate matters in the off gas of diesel engines
• soot in flue gases of heavy fuels
• coke formation in the cracking processes

00753_A_A © 2012 - IFP Training


7

VII - QUALITY SPECIFICATIONS OF COMMERCIAL PRODUCTS


Commercial products have to cope with certain quality specifications linked with their end uses.

Hydrotreatment processes improve their quality in relationship with combustion, atmospheric pollution,
corrosion, stability and chemical nature.

Appendix 13 presents the quality specifications for gasoline.

Appendix 14 for Jet A1.

Appendix 15 for Road diesel oil.

Appendix 16 for Heating oil.

The signification of these tests is given hereunder:

- RON (Research Octane Number) and MON (Motor Octane Number) are related with proper
combustion in a spark engine

- Smoke point and Calorific value are related with combustion in a turbine engine for jets

- ASTM CN (ASTM Cetane Number) and CCN (Calculated Cetane Number) are related to
proper combustion in a diesel engine

- sulfur content is related with pollution prevention

- benzene is threatening health. Aromatic compounds and olefins as well, but to a lower
extent

- polyaromatics content is in relationship with particulate matters emission

- copper strip test and silver tarnish test are in relationship with corrosion

- existing gums, Thermal stability and Oxidation stability are related to fouling phenomena

00753_A_A © 2012 - IFP Training


8

VIII - CHARACTERISTICS OF PETROLEUM CUTS


In parallel the elaboration of bases to be blended into commercial products and that have to meet quality
specifications, the refiner has to purify some cuts before processing. Most of the time, the catalyst itself
imposes the quality criteria to the feed.

The table hereunder gives some examples of feed quality for widespread processes.

Quality Catalytic reforming Isomerization Alkylation

Platinum on Platinum on Liquid acid


Catalyst
chlorinated alumina chlorinated alumina (HF or H2SO4)

Sulfur (ppm) < 0.3 to 1) 5 < 20


Nitrogen (ppm) <1 < 1* <1
Oxygen (ppm) <1 < 1*
(organic)
Water (ppm) <4 < 0.1* < 20

Olefins as low as possible < 1%


Diolefins < 100 ppm as low as possible < 1000 ppm
Benzene — < 7% —

Metals < 20 ppb* no metals no metals

The tables in appendices 5 and 6 give a hint about typical sulfur concentrations in cracked cuts.

00753_A_A © 2012 - IFP Training


9

IX - WORLD MARKET FOR TRANSPORTATION FUEL - QUALITY TRENDS

The future is:

- ultra low or near zero sulfur distillate fuels

- low or near zero emissions from ultra-modern-and-catalyst systems

The time frame for implementation of ultra-low sulfur fuels is different in the various areas in the world; as
shown on the table hereunder (according to World Diesel 2003, a supplement to World Refining).

Year 2005 2006 2008 2010

Countries Western Europe North America, Rest of the world China, India, Burma,
incl. Ukrainia and Mexico, Argentina, Bangladesh
Balkan region, Australia, South
Japan, Sri-Lanka, Korea
Hong Kong

But the threshold is not the same all around the world:

- Europe is targeting 50 ppm for 2005 and 10 ppm for 2009

- North America 15 ppm for 2006 with 80 % availability required (100% in 2010)

- Japan intends to convert diesel oil to a 50 ppm sulfur in 2006 and down to 10 ppm ULSD by
2009

Many countries where the “green pressure” is strong, encourage the distribution of low sulfur fuels in advance
by means of tax incentives.

North America is facing an additional challenge: phasing out of MTBE.

Other fuels like diesel for marine, locomotive, agriculture, stationary power, mining activities will have to face
the same kind of low sulfur challenges. Desulfurization of jet fuel is also being considered by refiners for
flexibility purposes and by regulators as well. Reduction of particulate emissions is also being studied for jet
fuel.

00753_A_A © 2012 - IFP Training


10

Europe and North America seem to consider a serious drop of sulfur in the heavy bunker fuel used by the
largest ships, down to 1% weight, in sulfur emission control areas today and decrease at 0.1% weight in 2015.

Starting from 2012, the heavy fuel used in global areas, contains 3.5% wt of sulfur for 4.5% wt before.
According to the MARPOL convention, defined by the International Maritime Organization (IMO), the sulfur
content of heavy fuel used in global areas will be reduced at 0.5% weight in 2020 (see figure below).

Sulfur Emission Control Areas (SECA)

1.5 wt% 1 wt% 0.1 wt%

Current 2010 2012 2015 2018 2020 2025

4.5 wt% 3.5 wt% 0.5 wt%


Review to assess
sufficient if not Final adoption of
availability of 0.5% 0.5 wt% deferred

D ANA 3015 A
sulfur FO
Global Areas From IFQC 2009

An other issue is the competition of various alternate fuels and their impact on the environment.

00753_A_A © 2012 - IFP Training


11

X- ALTERNATE TRANSPORTATION FUELS


The alternate fuels are numerous. The main ones are: gasoline, gas oil, LPG’s, methanol, natural gas, bio
fuels, GTL (Gas To Liquid) fuels and hydrogen. The situation now in the world is represented on the drawing
below. It stresses the fact that diesel oil and gasoline represent 98% of the world consumption.
1577 MM toe* Alternative fuels 1.7%

Diesel LPG
38%

EtOH
Gasoline

D PCD 1616 A
Natural gas
60% Bio-diesel
(including MTBE) ETBE

* Mm toe = Millions of Tons of crude Oil Equivalent

The ratio between gasoline and gas oil is different from country to country, as presented in the table below.

Diesel oil consumption


Diesel/gasoline ratio
Country (million bpd)
year 1990/2010
year 1990/2010

USA 3 / 4.5 0.5 / 0.5


Western Europe 4.5 / 5.5 1.5 / 2.1
India 0.5 / 1 4.7 / 4.7
Asia Pacific 3.5 / 8.5 1.7 / 1.7

To be complete, it is necessary to consider the whole quantity of CO2 generated by the complete process
from upstream at the production well to downstream end use. The table hereunder compares the different
vehicle fuels.

Well to Wheel CO2 emission


Vehicle fuel
(kg CO2 per 100 km)

CNG (Compressed Natural Gas) 14.9


Diesel oil (direct injection technology) 16.3
LPG 16.6
DME (Dimethylether) 17.7
Gasoline (direct injection technology) 19.1
GTL diesel oil 21.1

Diesel oil is a fuel that is close to the top level among the hydrocarbon fuels. The strong tendency for the
European car market to switch from gasoline to diesel engines is profitable as far as Green House Gas
emission is concerned. This assumes the use on a large scale of catalysts for particulate matter trapping and
“DeNOx” depolluting action.
Compressed hydrogen seems at first to be less polluting than the others do. But overall CO2 balance includes
the energy consumption necessary to produce hydrogen on a large scale: this point is a major drawback
for the extensive use of this type of fuel.

00753_A_A © 2012 - IFP Training


12

XI - MANAGEMENT OF HYDROTREATMENT PROCESSES IN THE REFINING SCHEME


The units that need hydrogen to run are quite numerous:

- hydrotreatment for gasolines


- hydrotreatment for kerosene and gas oil cuts
- isomerization
- FCC gasoline desulfurization
- VGO hydrotreatment
- pyrolysis gasoline hydrotreatment
- atmospheric residue desulfurization

In the long term many refiners will also have to implement hydrocrackers and heavy cuts hydroconversion
units.

Hydrogen is a very expensive chemical utility and there is hardly any economical possibility to store it.
Therefore it is necessary to manage the hydrogen balance very seriously.

Many non-capital intensive means are at hand for the management of the hydrogen balance:

- the flexibility of the catalytic reformer which operation may be focused on hydrogen generation
exactly as on octane production
- the careful programming of the crude oil supply and the production of the refinery, taking into
account the situation of the semi-regenerative cat. Reformer catalyst and the cycle length of the
catalyst
- the proper operation of the hydrotreatment processes with the help of the calculated Hydrogen
Partial pressure
- the implementation of process control techniques focusing on the real time effect of hydrogen
on the quality of the treated products
- the changing of the catalyst to a more efficient one
- the purification of the hydrogen in the FCC fuel gas by means of permeation membranes or PSA
unit
- the import of additional hydrogen from an ethylene plant in the neighborhood
- the segregation of various gases having a different concentration of hydrogen

The implementation of a dedicated hydrogen production unit as Steam Reformer or POX is most of the
time necessary for standing alone refineries as soon as the following units are foreseen:

- hydrotreatment unit for VGO


- VGO Hydrocracking
- residue hydrotreatment or hydroconversion

00753_A_A © 2012 - IFP Training


Refining-Petrochemicals-Chemicals-Engineering
———

PURPOSE OF THE HYDROTREATMENT PROCESSES

— Appendices —

Appendix 1: MAIN PROPERTIES OF TYPICAL SATURATED SULFUR COMPOUNDS


Appendix 2: MAIN PROPERTIES OF TYPICAL UNSATURATED SULFUR COMPOUNDS
Appendix 3: SULFUR DISTRIBUTION - Topping
Appendix 4: DISTRIBUTION OF SULFUR COMPOUNDS IN PETROLEUM CUTS
Appendix 5: SULFUR DISTRIBUTION - FCC
Appendix 6: SULFUR DISTRIBUTION - Visbreaker
Appendix 7: SIMPLIFIED SCHEME OF A THREE-WAY CATALYTIC CONVERTER SYSTEM
+ λ PROBE
Appendix 8: MAIN PROPERTIES OF TYPICAL NITROGENATED COMPOUNDS
Appendix 9: STRUCTURE OF THE RESIDUE CUT
Appendix 10: Hydrocarbons - AROMATICS
Appendix 11: Hydrocarbons - OLEFINS and DIOLEFINS
Appendix 12: THE DIFFERENT TYPES OF HYDROCARBONS
Appendix 13: PREMIUM GASOLINE
Appendix 14: JET A1
Appendix 15: ROAD DIESEL OIL
Appendix 16: HEATING OIL

RA HDT - 00753_A_A - Rev. 3 13/02/2012


© 2012 - IFP Training
— Appendix 1 —
MAIN PROPERTIES OF TYPICAL
SATURATED SULFUR COMPOUNDS

HYDROGEN SULFIDE H 2S

bp = – 60°C
H S H
gaseous at atmospheric pressure
corrosive
very toxic

— Examples —
MERCAPTANS CH3SH
H Methyl mercaptan
bp = + 6°C
H C S H
H

H H
C2H5SH
Ethyl mercaptan
H C C S H bp = 35°C
H H

acid products
disagreable odor

— Examples —

SULFIDES, DISULFIDES
C2H6S
H H
Dimethyl sulfide
H C S C H
(DMS)
bp = 37°C
H H

H H C 2H 6S 2

H C S S C H
Dimethyl disulfide bp = 109.6°C
H H (DMDS)
non acid products
usually no disagreable odor
unstable at high temperatures; broken down into mercaptides
D CH 137 E

© 2012
2011 - IFP Training
MAIN PROPERTIES OF TYPICAL
UNSATURED SULFUR COMPOUNDS
— Appendix 2 —

THIOPHENIC COMPOUNDS — Examples —


C4H4S
H H
C C Thiophene
bp = 84 °C
C C
H H
S
H H C5H6S
C H 3 methyl thiophene
H
C C
bp = 115 °C
C C
H H
S
BENZOTHIOPHENIC — Examples —
H C8H6S
COMPOUNDS
C H Benzothiophene
H C C C —mp
Examples
= 30 °C —
C C C —bp
Examples
= 220 °C —
H
C S
H

H H H C9H8S
Methyl benzothiophene
C C H
H
C C C
bp = 220-260°C
C C C
H
C S
H

DIBENZOTHIOPHENIC — Examples —
COMPOUNDS H H
C12 H8S
C C H
Dibenzothiophene (DBT)
H C C C C
bp = 332 °C
C C C C
H
C C H

H
S H

H H H H
C13 H10 S
C C
Methyldibenzothiophene (MDBT)
H C H
C C C C
bp = 335-365 °C
C C C C
H
C C H

H
S H

H H H H H H C14 H12 S
C C DiMethyldibenzothiophene
H
C C H
C C C C (DMDBT)

C C C C bp = 363-380 °C
D CH 137 F

H
C C H

H
S H

© 2012
2011 - IFP Training
SULFUR DISTRIBUTION
— Topping —

— Appendix 3 —

S concentration S distribution Concentration


Cut yield
in the cut % mass of of mercaptans
% mass
% mass S in feed in S cut

GAS 0.2 1.70 0.17 0


PROPANE 0.5 1.08 0.27 0
BUTANE 1.8 1.11 1.00 100
LIGHT GASOLINE 9.3 0.034 0.16 78
HEAVY GASOLINE 9.7 0.412 2.00 46

NAPHTHA 6.0 0.167 0.5 27


TOPPING

KEROSENE 7.5 0.3 1.2 9


GAS OIL 24.0 1.17 14.0 2.2
DISTILLATE 6.0 1.90 5.7 -

CRUDE
OIL

%S=2

A RESIDUE 35.00 4.29 75.00 -

100.00 100.00
D PCD 405 C

© 2012
2011 - IFP Training
• R S H M ercaptans R. R' : alkyl
CH3 : methyl
Sulfides C2H5 : ethyl
DISTRIBUTION OF SULFUR COMPOUNDS
• R S R'
C3H7 : propyl IN PETROLEUM CUTS
• R R'
Triophenic compounds C4H9 : butyl
S etc. — Appendix 4 —
R R
• Benzothiophenic
S R' compounds Straight run naphtha contains mainly mercaptans (RSH),
sulfides (RSR) and derivated from triophenic compounds.
R R'
• Dibenzothiophenic Gas oil cuts contain a big part of benzothiophenic and
S compounds dibenzothiophenic compounds. These aromatic compounds
R are difficult to desulfurize.

For a given crude oil, the heaviest the cut is, the most
CRUDE OIL NAPHTHA KEROSENE GAS OIL
VACUUM
RESIDUE important is the sulfur content.
GASOIL

The sulfur content in gas oil cuts is usually close to the


RSH
sulfur content in the crude oil itself.

DISTRIBUTION '
S -R
OF R-
SULFUR
COMPOUNDS
R

S
SULFUR
CONTENT S
(weight %)

Example 1. 2 0.02 0.2 0.9 1.8 2.9

Concentration

D CH 2013 H
range 0.1 to 3 0.01 to 0.1 0.1 to 0.5 0.5 to 2 1 to 3 2 to 5

© 2012 - IFP Training


SULFUR DISTRIBUTION
— FCC —

— Appendix 5 —

S concentration S distribution Concentration


Cut yield
in the cut % mass of of mercaptans S
% mass
% mass S from feed in the cut

GAS 5.35 7.89 23.44 0


C3 CUT 5.89 7.29 25.56 0
C4 CUT 10.17 0.078 0.44 99.9
LIGHT CAT NAPHTHA 35.12 0.098 1.92 10.0
HEAVY CAT NAPHTHA 5.25 0.394 1.15 25.0

LCO 18.63 2.00 20.37 0.3


REACTOR
EFFLUENT F
% S = 1.8 C
C HCO 12.42 2.06 14.24 1.0

SLURRY 7.17 3.98 15.88 -

100.00 100.00
D PCD 406 D

© 2012
2011 - IFP Training
SULFUR DISTRIBUTION
— Visbreaker —

— Appendix 6 —

S concentration S distribution Concentration


Cut yield
in the cut % mass of of mercaptans
% mass
% mass S in feed in S cut

GAS 4.3 6.24 6.25 0

WILD 7.8 0.84 1.53 -


GASOLINE

V
I
S
FEED B
R CRACKED 14.4 1.75 5.87 -
% S = 4.3 GAZOLE
E
A
K
E
R

RESIDUE 73.5 5.04 86.35 -

100.00 100.00
D PCD 407 C

© 2012
2011 - IFP Training
SIMPLIFIED SCHEME OF A THREE-WAY CATALYTIC CONVERTER
SYSTEM + l PROBE

— Appendix 7 —

Air flow rate


Throttle

Air

Gasoline
Injector
Gasoline flow rate

Possible EGR
ENGINE CALCULATOR
(EGR : Exhaust gas
recirculation) Oxygen content in the
exhaust gas

l probe
To catalytic converter
(oxygen content)

Stainless Ceramic structure


steel casing

Exhaust
gases Thermal-expandable Covered by alumina
felt seal protecting the + cerium oxide
ceramic structure + precious metals
(2 to 3 g)
D MOTE 016 C

© 2012
2011 - IFP Training
MAIN PROPERTIES OF TYPICAL NITROGENATED COMPOUNDS

— Appendix 8 —

AMINES
Characterised by a strait or branched carbon chain

D CH 2258 B
linked to a nitrogen atom. There may be one, two or
even three carbon chain. Their concentration in R NH2
hydrocarbons is usually low. Their reactivity is quite
large

ANILINES
Anilines are characterised by a nitrogen atom linked to a
carbon atom in an aromatic ring. Anilines are highly
basic.

D CH 2259 A
NH2

PYRROLS
Pyrrolic compounds central motif is a five atoms
unsaturated ring with four carbon atoms and a nitrogen
one. This structure is similar to the thiophene one. The
N
D CH 2256 A

free electrons of the nitrogen atom take part in the


unsaturation resonance of the ring: the basicity of this H
type of molecule is low.

INDOLS
Indolic compounds include two adjacent rings: a pyrrolic
D CH 2013 D

N
one and a benzene ring. This structure is to be
compared with benzothiophene. H

PYRIDINES
Pyridines are built around a six atom ring: 5 carbon
D CH 2257 A

atoms and a nitrogen one. Pyridines are strongly basic


compounds.
N

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© 2012 - IFP Training
STRUCTURE OF THE RESIDUE CUT — Appendix 9 —

Example of the structure


Constituents of the residue
of an asphaltene molecule

Oil Sulfur bridge


Asphaltene

Resin
S S

D CH 141 B
Vacuum residues Arab Arab Bachaquero Kuwait
light heavy
Crude yield (% wt) 18.55 35 59 21 Aliphatic N
O
Density at 25°C 1.031 1.032 1.023 1.019 bond
N -V- N
Viscosity at 100°C 1130 3080 9500 2500 Aromatic N
Sulfur (% wt) 4.2 5.1 3.34 4.77 sheet S
Nitrogen (ppm weight) 3700 4700 6500 4000
Conradson carbon residue (% weight) 25.7 22.3 19.4 19.8
Porphyrin
Asphaltene content (% weight) 6.9 14.2 10.3 4.9
Metals content Ni + V Ni + V Ni: 82 ppm Ni: 25 ppm

D CH 1148 C
102 ppm 173 ppm V: 614 ppm V: 103 ppm

© 2012 - IFP Training


Hydrocarbons
— Appendix 10 —
— Aromatics —

bp = 80°C
C6 15
sp.gr = 0.884
4

Benzene C 6H6

C7 bp = 110.6°C
15
sp.gr = 0.871
4

Toluene C 7H8

C8

Orthoxylene C 8H10 Metaxylene C 8H10 Paraxylene C 8H10 Ethylbenzene C 8H10


bp = 144.5°C bp = 139.2°C bp = 138.1°C bp = 136.2°C
15 15 15 15
sp.gr 4 = 0.884 sp.gr 4 = 0.868 sp.gr 4 = 0.868 sp.gr 4 = 0.871

C10 n-Butylbenzene C 10H14


bp = 183.3°C
Naphtalene C 10H8 15
sp.gr 4 = 0.864
bp = 218°C

C14 n-Octylbenzene C14H22


bp = 264°C
D CH 135 B

Anthracene C 14 H10 25
sp.gr 4 = 1.250 Tmelting = 215°C
bp = 340°C
© 2012
2011 - IFP Training
Hydrocarbons
— Appendix 11 —
— OLEFINS and DIOLEFINS —
— Alcenes and dialcenes —

C2 Ethylene C2H4
bp = -103.7°C

C3 Propylene C4H8
bp = -47.7°C

Butene 1 C4H8
C4 bp = -6.3°C
Isobutene C4H8
bp = -6.8°C

Butene 2 C4H8 Butadiene 1-3 C4H6


bp = -4.4°C

Pentene 2 C5H10

C5
Cyclopentene C5H8
Isoprene C5H8
bp = 44.2°C

C6 Hexene 1 C6H12
bp = 62.8°C
D CH 136 B

Cyclohexene C6H10

© 2012
2011 - IFP Training
THE DIFFERENT TYPES OF HYDROCARBONS – Appendix 12 –

SATURATED HYDROCARBONS UNSATURATED HYDROCARBONS


without multiple bounds with double and benzenic bonds

Carbon atoms in Molecules with Hydrocarbons with Carbon atoms in


— Chain structure — — Cycles — — Benzenic cycles — — Chain structure —
1 double bond

PARAFFINS NAPHTHENES AROMATICS OLEFINS

Straight chain Branched chain 2 doubles bonds

N-PARAFFINS ISOPARAFFINS CYCLOPARAFFINS DIOLEFINS


Existing in crude oil
— Example —

C C C C C C C C
C C C C C C Olefin C C C C C
C C C C
C C C C C C C C Diolefin C C C C
C C C C C

Liquid density low low medium high low


Cold flow prop. weak generally good enough generally good generally good —
Gasoline
Combustion

weak good medium very good good enough


engine
Diesel
very good weak medium very weak weak
engine
Hydrogen
content or high high medium low medium

D CHI 111 B
H/C ratio

Storage stability good good good good very weak

© 2012 - IFP Training


PREMIUM GASOLINE

— Appendix 13 —

European Year Year Year Since Year


specifications 1999 2000 2005 2009

RON mini 95 idem idem


MON mini 85

ppm mass < 500 < 150 < 50 < 10


sulfur

% vol. benzene 5 1 1 1
% vol. aromatics — < 42 < 35 < 35
% vol. olefins — ≤ 18 ≤ 18 ≤ 18
% mass oxygen 2.8 2.7 2.7 2.7

Copper strip (3 h at 50°C) 1 max 1 max 1 max 1 max

Existing gum content 5 5 5 5


(mg/100 cm3)
Oxidation stability ≥ 360 ≥ 360 ≥ 360 ≥ 360
(min)

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© 2012 - IFP Training
JET A1

— Appendix 14 —

Since
European Year Year Year
Year Notices
specifications 1999 2000 2005
2009

Smoke point (mm) ≥ 25 ≥ 25 ≥ 25 ≥ 25


Calorific value (MJ/kg) ≥ 42.8 ≥ 42.8 ≥ 42.8 ≥ 42.8

Sulfur (% mass) ≤ 0.3 ≤ 0.3 ≤ 0.3

Copper strip 1 max 1 max 1 max 1 max 2 h at 100°C


Silver tarnish test 2 max 2 max 2 max 2 max 4 h at 50°C

Thermal stability 3 max 3 max 3 max 3 max at 260°C


(cotation tube) ∆P ≤ 25 mmHg
Existing gum content ≤7 ≤7 ≤7 ≤7
(mg/100 cm3)
Cotation interface
Water reaction 70 to 85 70 to 85 70 to 85 70 to 85
Microseparatometer

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© 2012 - IFP Training
ROAD DIESEL OIL

— Appendix 15 —

Year Year Year Since


1999 2000 2005 Year
2009

Cetane index (Measured Cetane Number) ≥ 49 ≥ 49 ≥ 51 ≥ 51


Calculated Cetane Number ≥ 46 ≥ 46
Conradson residue ≤ 0.3 ≤ 0.3 ≤ 0.3 ≤ 0.3
(% mass on 10% heaviest)

Sulfur (ppm mass) 500 350 50 10

Aromatics (%) — — – –
Polyaromatics (%) — < 11 < 11 <8

Oxidation stability (g/m3) ≤ 25 ≤ 25 ≤ 25 ≤ 25


Water content (mg/kg) ≤ 200 ≤ 200 ≤ 200 ≤ 200

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© 2012 - IFP Training
HEATING OIL

— Appendix 16 —

European Year Year Year Since Year


specifications 1999 2000 2005 2008

Cetane index ≥ 40 ≥ 40 ≥ 40 ≥ 40

Conradson residue ≤ 0.3 ≤ 0.3 ≤ 0.3 ≤ 0.3


(% mass on 10%
heaviest)

Sulfur content (%) 0.2 0.2 0.2 0.1

Oxidation stability ≤ 25 ≤ 25 ≤ 25 ≤ 25
(g/m3)

Water content ≤ 200 ≤ 200 ≤ 200 ≤ 200


(mg/kg)

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© 2012 - IFP Training

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