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01 - Purpose of Hydrotreatment Processes - 00753 - A - A PDF
01 - Purpose of Hydrotreatment Processes - 00753 - A - A PDF
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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.
- 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
- color instability
- improper combustion
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.
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.
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)
• 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
• in addition to that, sulfur is also a poison for the future “DeNOx” catalysts that will
convert NO into nitrogen N2
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.
• Organic acids
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
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.
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.
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.
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.
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.
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
Hydrotreatment processes improve their quality in relationship with combustion, atmospheric pollution,
corrosion, stability and chemical nature.
- 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
- benzene is threatening health. Aromatic compounds and olefins as well, but to a lower
extent
- copper strip test and silver tarnish test are in relationship with corrosion
- existing gums, Thermal stability and Oxidation stability are related to fouling phenomena
The table hereunder gives some examples of feed quality for widespread processes.
The tables in appendices 5 and 6 give a hint about typical sulfur concentrations in cracked cuts.
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).
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:
- 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.
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.
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).
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.
Diesel LPG
38%
EtOH
Gasoline
D PCD 1616 A
Natural gas
60% Bio-diesel
(including MTBE) ETBE
The ratio between gasoline and gas oil is different from country to country, as presented in the table below.
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.
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.
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:
— Appendices —
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 —
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 —
CRUDE
OIL
%S=2
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
DISTRIBUTION '
S -R
OF R-
SULFUR
COMPOUNDS
R
S
SULFUR
CONTENT S
(weight %)
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
— Appendix 5 —
100.00 100.00
D PCD 406 D
© 2012
2011 - IFP Training
SULFUR DISTRIBUTION
— Visbreaker —
— Appendix 6 —
V
I
S
FEED B
R CRACKED 14.4 1.75 5.87 -
% S = 4.3 GAZOLE
E
A
K
E
R
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
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)
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
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
00753_A_A
© 2012 - IFP Training
STRUCTURE OF THE RESIDUE CUT — Appendix 9 —
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
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
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
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 –
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
D CHI 111 B
H/C ratio
— Appendix 13 —
% 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
00753_A_A
© 2012 - IFP Training
JET A1
— Appendix 14 —
Since
European Year Year Year
Year Notices
specifications 1999 2000 2005
2009
00753_A_A
© 2012 - IFP Training
ROAD DIESEL OIL
— Appendix 15 —
Aromatics (%) — — – –
Polyaromatics (%) — < 11 < 11 <8
00753_A_A
© 2012 - IFP Training
HEATING OIL
— Appendix 16 —
Cetane index ≥ 40 ≥ 40 ≥ 40 ≥ 40
Oxidation stability ≤ 25 ≤ 25 ≤ 25 ≤ 25
(g/m3)
00753_A_A
© 2012 - IFP Training