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I - HYDROREFINING PROCESSES
APPENDICES
The term hydrorefining covers all the processes used to eliminate the undesirable compounds present in
petroleum cuts by means of catalytic treating in the presence of hydrogen.
The main impurities that have to be removed are sulfur, nitrogen and oxygen compounds, metals and
unsaturated hydrocarbons such as diolefins, olefins and aromatics.
Hydrorefining units are required in view of the presence of these impurities, sometimes in large proportions, in
petroleum cuts and of the number of disadvantages that they involve.
1- SULFUR COMPOUNDS
Present in the form of mercaptans, sulfides, thiophenic and benzothiophenic compounds, sulfur
compounds are primarily concerned by hydrorefining processes.
They cause atmospheric pollution by their combustion products (SO2 and SO3 ) and corrosion
(H 2 S, RSH, SO3, etc.). They often have an unpleasant smell (H2S, mercaptans), are poisons for a
number of catalysts (reforming, isomerization, etc.).
Sulfur is removed by chemical combination with hydrogen in the presence of a suitable catalyst.
Hydrodesulfurization — S — + H2 H 2 S hydrogen
H.D.S. sulfide
The reaction yields volatile H2S which is easily separated from the treated fraction.
The general characteristics of HDS reactions may be illustrated by the following examples.
H H
C C
2- NITROGEN COMPOUNDS
Nitrogen compounds are present in much smaller quantities than sulfur compounds. Nitrogen content
is usually 10 to 100 times lower than that of sulfur.
Some nitrogen compounds existing in heavy cuts have a very pronounced alkaline nature and,
consequently poison the acidic function of catalysts (FCC, hydrocracking).
Hydrodenitrogenation — N — + H2 NH3
H.D.N. | ammonia
In short, nitrogen removal reactions are however more difficult to obtain than sulfur removal
reactions.
3- OXYGEN COMPOUNDS
These compounds are present in significant amounts in some crude oils in the form of naphthenic
acids which are particularly corrosive. Phenols can also be encountered in catalytic cracking effluents,
for example.
Hydrodeoxygenation — O — + H2 H 2 O water
H.D.O.
It produces water separated at liquid state by settling. In addition it has similar characteristics to sulfur
and nitrogen removal.
4- METALS
Residual heavy fractions contain organometallic compounds within asphaltenic structures in which two
metals, nickel and vanadium in particular, may be found. These metals constitute the main obstacle
with regard to catalytic conversions of residues or high conversion. In fact, they are severe poisons
for the catalysts used in these processes.
An other source of metals in the residues is mineral impurities such as sodium salts.
Moreover, other metals (mainly arsenic, lead, copper, ...) can be found in some crude oils (even in the
distillable cuts).
Hydrodemetallization (HDM) reactions consist of the destruction of organometallic molecules and the
metal trapping on the catalysts surface.
For example, for a vacuum residue containing 400 ppm of metals (400 g/t) with a flow rate of 100 t/h
there is a loss of 40 kg/h of metals that deposits on the catalysts, assuming total hydrodemetallization.
It is obvious in these conditions that the operation remains possible as long as the catalytic mass has
not reached its metal saturation. This is usually limited to 35-40% of the catalytic mass used and is
called capture ratio.
The hydrodemetallization (HDM) reaction is a complex reaction which makes difficult the
removal of impurities from residual feedstocks. The processes require:
– severe operating conditions
– large amount of catalyst
– new reactors technologies to remove low activity high metals catalyst while the unit is on
stream.
5- UNSATURATED COMPOUNDS
Unsaturated compounds are present in petroleum fractions or in cracked products and are responsible
for several problems, for example:
– Diolefins are unstable compounds likely to produce gums in automotive gasolines
– Olefins which are present in gas-oils are responsible for stability problems and have a
negative effect on the cetane number
– Aromatics desirable in automotive gasolines are, on the contrary, undesirable in jet fuel
(smoke point) and in diesel oil (cetane number)
Further, heavy aromatic compounds (polyaromatics) present in vacuum gasoils and residues are
unaffected by cracking reactions i.e. conversion.
diolefin C 5 H 8 olefin C 5 H 10
An initial first hydrogenation step permits the hydrogenation of every other double bond and
consequently the conversion of diolefins into olefins. This first reaction is sufficient to stabilize some
gasolines.
olefin paraffin
A complementary hydrogenation step produces paraffins. It takes place for example in the case of the
treatment of cracked gas oils.
Aromatics hydrogenation
C C
C—C C—C
+ H2
C—C—C C—C—C
C—C C—C
D CH 1011 B
Polyaromatic Mixed molecule N-A
C22 H26 C22 H32
Partial aromatic hydrogenation is a very useful reaction because it allows the conversion of aromatic
cycles ("uncrackable") into naphthenic rings which can then be easily cracked as far as the carbon-
carbon bonds present in the ring are concerned.
• hydrogen-consuming
• very exothermic
• relatively easy for diolefins and olefins
• difficult for aromatics especially when the number of adjoined rings is high
2- HYDROREFINING CATALYSTS
Hydrorefining catalysts are composed of a porous alumina with a coating of metal oxides. In an
operating unit the latter are rapidly converted into metal sulfides which are the active chemical
compounds that promote the desired conversions.
The metals in the oxides used vary according to the type of reaction that is desired. They are generally
used in pairs, for instance:
– cobalt and molybdene for desulfurization. The corresponding oxides give this type of
catalyst a blue color (Co – Mo catalysts).
– nickel and molybdene for denitrogenation and hydrogenation (Ni – Mo catalysts). Their
oxides are green.
These catalysts are generally small cylinders 2 to 3 mm in diameter. The quantities used depend on
how difficult it is to produce the reaction. They are therefore used in larger quantities for desulfurization
of heavy feeds than of light feeds.
Coke is the main poison for these catalysts. Inevitably, it is gradually deposited on the catalyst surface
and this involves regular regenerations by which the coke is removed by controlled combustion, as in
catalytic reforming.
The feed is blended with the hydrogen-rich gas then heated to the reaction temperature by heat
exchangers and then by a furnace.
Following this operation it goes into the reactor, in the vapor state in the case of a light cut, in a liquid-
vapor mixture in the case of a heavy cut. The exothermic nature of the reaction results in a rise in
temperature and in some cases it may be necessary to quench it with a cold fluid to cool the mixture.
– light products resulting from the breakdown of impurities. The removal of sulfur,
nitrogen, etc., leads to the destruction of a number of heavy molecules and the
production of much lighter fractions;
– a hydrorefined product with the same volatility as the feed but with improved
characteristics.
SEPARATION
Light
products
SECTION
Hydrorefining
catalyst
HYDROREFINED
PRODUCT
Feed/effluent
EXCHANGER
HYDROGEN
D PCD 483 B
RICH
FEED GAS
This generally concerns the overhead cut from atmospheric distillation. The purpose is to remove
sulfur from the liquefied petroleum gas and light gasoline and to remove the catalytic reforming
catalyst poisons present in the heavy gasoline.
• Hydrosweetening of kerosene
The objective of this process is to eliminate mercaptans from the kerosene cut to produce Jet A1.
This is the most important use of the process in refineries. The objective is to meet the sulfur
specifications on diesel fuel and home-heating oil. It is covered in detail hereafter.
• Hydrodesulfurization of VGOs
It reduces their sulfur, nitrogen and metal content before they are treated in a conversion unit (for
example, FCC), or it reduces their sulfur content before they join the fuel pool. In addition, this
operation constitutes the first step of the hydrocracking process.
• Severe hydrotreating of paraffins, waxes and white oils to give them suitable characteristics
for the pharmaceutical or food specifications.
To stabilize it and make it suitable for incorporation in the refinery gasoline pool.
The table below shows the ratio of crude oil sulfur content to gas oil cut sulfur content.
Since most of the refinery supplies are MS and HS crudes, those refineries require large capacities for
gas oil hydrodesulfurization units and more especially as cracked products are now added to straight-
run fractions.
For example, the table below shows the characteristics of these products.
15 0.930 0.845
sp.gr4
Cetane number 15 to 25 35 to 45
Composition
(vol%)
P 0 10
O 3 20
N 27 40
A 70 30
a - Desulfurization rate
To obtain a gas oil pool with an average sulfur content of less than specification values, the
desulfurization process is applied intensively to only a fraction of the gas oil cuts. Preference is
generally given to the high sulfur content cuts which are submitted to a relatively-high rate of
desulfurization. The rate of desulfurization is defined as the ratio of removed sulfur to initial sulfur and
is more or less equal to the variation in S% (∆S%) divided by the initial sulfur %.
∆S%
Desulfurization rate ≈
initial S%
For the desulfurization of gas oil, until recently the desulfurization rate was in the range of 90-95%. To
meet the new sulfur specs, the new rates had to be increased to 95-98% depending upon the sulfur
content of the feeds to be treated.
• T HE REACTOR
A typical HDS reactor configuration is shown in Figures 4 and 5. It is designed to ensure the
best possible distribution of the two phase flow mixture throughout the reactor section.
Approximately 50 to 150 tons of catalyst are used for a feed rate of 100 t/h, depending upon the
requirements.
• REACTION TEMPERATURE
The temperature is generally between 340 and 370°C at the reactor inlet. Due to the
exothermic effect, the outlet temperature is higher than the inlet temperature, and this might
lead to coke formation or heavy products production changing the product color.
When exothermicity tends to be high, the modern reactors are equipped with a quench
injection of a cold product (generally a gas stream rich in hydrogen) directly into the reactor.
This implies to have 2 or more catalyst beds to insert the injections in between.
The temperature is regulated by means of the furnace, upstream of the reactor, to obtain the
desired rate to hydrodesulfurization. To compensate for the drop in catalyst activity the reaction
temperature has to be progressively increased.
Pressure, particularly hydrogen pressure, are positive factors for hydrodesulfurization and
hydrogenation. Moreover, hydrogen pressure limits coke formation.
The heavier the cut, the higher the required pressure. Gas oil HDS units generally operate at
around 60 bars. The dilution with hydrogen through the H2 recycle gas and make up
corresponds to about 150 Nm 3 H2 per m3 of liquid feed. Hydrogen consumption is generally
between 0.3 and 0.8 wt% of the feed.
c - Separation section
The reactor effluent is cooled down and partially condensed before entering the separation section
which generally consists of:
– a LP (10 bars) separator drum which separates the liquid and vapor phases obtained
by the expansion of the liquid from the HP drum. The gas chiefly contains hydrogen,
light hydrocarbons and a large proportion of the hydrogen sulfide produced during the
reaction
– a gas oil steam stripper for removing the light hydrocarbons and the residual H2 S
from the cut treated. The gas oil is withdrawn from the bottom of the column and the
operation is controlled by the gas oil flash point
– a vacuum-dryer to remove water adsorbed in the hot gas oil in the stripper
3- YIELDS - PRODUCTS
This sulfur reduction is going to require to revamp existing gasoil hydrodesulfurization units. To produce
ULSD it is necessary to have a minimum hydrogen partial pressure to remove the sulfur compounds
that are the most difficult to desulfurize and protect the catalyst. The deep desulfurization generally
increases the hydrogen make-up requirements, and increases the naphtha and H2S production.
– higher purity hydrogen or modification of the hydrogen rich gas network to maximize the
hydrogen purity to the HDS
– install wash water injection equipment to wash precipitated ammonia salts at the air cooler
_ Maximize capacity as all gas oil feedstocks have to be desulfurized to meet the 10 ppm
spec.
– Adjust feed end-point as sulfur in the higher boiling range is harder to convert
These modifications will be a function of the refinery configuration and feedstock characteristics.