Preface

I Introduction
Hydrotreating is a general term applied to processes where a
feed stock is enhanced in some manner by passing it over a
catalyst in the presence of hydrogen.
The terms hydrotreating, hydroprocessing, and hydrocracking
are used rather loosely in industry because, in the process
hydrotreating and hydrocracking both cracking and treating
occur simultaneously, Hydrotreating refers to relatively mild
catalytic operation whose primary is to achieve certain goals
without any change in the boiling range for the feed.
Hydrocracking refers to processes whose primary purpose is
to reduce the boiling range and in most the feed is converted
to products with boiling ranges lower than that of the feed.
Hydrotreating and hydrocracking are known as
hydroprocessing.
Benefits by purifying petroleum fractions through hydrogen
processing have been known since the early 1930's where
early commercial hydrogen treating units were installed by
Esso standard oil Co. in the 1930's , but because of a lack of
cheap hydrogen and high pressures formerly required the
process did not developed commercially.
The advent of catalytic reforming in the 1940's which made
inexpensive hydrogen rich off-gas available, encouraged

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hydrogen processing development and as a result World War II

plants were pioneered by Humble oil and refining co.
Heavy growth hydrogen treating commenced in the middle
1950's and has spread through the entire petroleum refining
industry because of available of hydrogen sources and
operating pressure requirements were reduced through
advances in catalyst technology.
Today hydrotreating capacity represents nearly 50% of the
total refinery capacity as shown in figure 1

Figure 1: Hydrotreating units in modern refineries

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II Purpose of the process

The most commercial applications of hydrogen treating in
petroleum refineries for petroleum products which produced
from units like distillation {atmospheric & vacuum}, cracking
{thermal, catalytic and hydro} and coking have been directed
toward,
1-Improvement of product quality.
2- Removal of catalyst poisoning contaminates.
3- Protecting the environment in the hydro fining coking
process stream.
These objectives can be achieved by
1- Removal of impurities and contaminants from feeds for
other processing and conversion units in the refinery
(isomerization, reforming, catalytic cracking, and
hydrocracking) whose catalysts are sensitive to impurities
such as sulfur for metallic catalyst, nitrogen for acid catalyst
and metals for all types.
As known crude oil naturally contains impurities, particularly
sulfur, nitrogen, metals such as nickel, vanadium and
sometimes oxygen. These impurities are an integral part of
various heteroatomic compounds, whose nature and amount
depend greatly on the origin of crude. As a general rule, the
impurity content increases after distillation from the light cuts
to heavy cuts, table 1 show these impurities and their amounts
in different cuts.
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Impurities

Source

Ni, V

Crude

As
Hg
NaCl

Fe

Cl

Si
Pb
Co/Co2

Main cut Catalyst poison

Distillates Strong deposit

residues inside catalyst and
plugging
Crude
All
Strong deposit at
top of reactor
Crude
Naphtha Slight only slightly
retained
Crude
Residues Strong,deposit at
top of reactor,
generates pressure
loss
Crude and
All
Slight,deposit at
corrosion
top of
reactor,generates
pressure loss
Solvents
Very slight,
and
promotes coking
recycled
and corrosion
slops
AntiDistillates Very slight, deposit
foaming
inside catalyst and
agents
plugging
Recycled
Gasoline Strong, deposit at
gasoline
top of bed
Hydrogen
All
Very slight,
make up
formation of
carbonyl Ni,Co,Fe
at low temperature

Maximum
content(%wt)
10
30 40
0.2 2
traces
1
1

0.1 0.5

5 - 10
0.1 1.5

<0.05%vol

Table1: Impurities in petroleum cuts

2- Decrease the content of olefins and aromatics through

saturation reactions to increase the quality of products.
On the other hand it is accompanied by hydrogenation of
unsaturated compounds and cracking of petroleum feed stocks
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to lower molecular hydrocarbon play an important role in

refinery.
Hydrotreating is often justified for reasons other than the
production of superior fuels. Waste disposal problems caused
by mercaptans, phenols and thiopenes are almost eliminated.
Corrosion problems from sulfur, cyanides and organic acids
are reduced.
Hydrotreating also leads the way to sulfur recovery and
subsequent reduction of air pollution by sulfur acid gases.

III Process involves

1 Hydrodesulfurization (HDS)
Sulfur is converted to hydrogen sulfide (H2S).
Added hydrogen breaks carbon-sulfur bonds & saturates
remaining hydrocarbon chains,
It also creates some light ends.
Heavier distillates make more light ends from breaking more
complex sulfur molecules.
Form of sulfur bonds
Sulfur in naphtha generally mercaptans (thiols) & sulfides.
In heavier feeds, more sulfur as disulphides & thiopenes.

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2 Hydrodenitrogention (HDN)
Nitrogen is converted to ammonia (NH3).
Pyridines & pyrroles are nitrogen containing compounds.
Nitrogen removal minor in naphtha hydrotreating.
As the feeds become heavier, denitrogenation becomes more
significant, such as in heavy distillate and gas oil.
Nitrogen removal requires about four times as much
hydrogen as the equivalent sulfur removal.
3 Hydrodeoxigenation (HDO)
Oxygen converted to water (H2O).
Examples of oxygen containing compounds are phenols and
peroxides.
Like nitrogen removal, oxygen removal is minor in naphtha
hydrotreating but significant in heavy distillate hydrotreating.
Oxygen requires about two times as much hydrogenas the
equivalent sulfur removal.
4 Hydrogenation (HDY)
4-1 Saturation of Hydrocarbons {olefins}
Olefins are saturated to form light hydrocarbons.
Consumption stoichiometric with one hydrogen molecule
added for each double bond
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Olefins are prevalent in cracked streams such as naphtha

streams from a coker or visbreaker, catalytic cracker cycle oil,
and catalytic cracker gasoline.
Selective catalysts are available for use in hydrotreating
catalytic cracking gasoline for sulfur removal yet not saturate
olefins, thus maintaining high octane ratings.
4-2 Saturation of Hydrocarbons {aromatics}
Aromatic rings are hydrogenated to cycloparaffins
(naphthenes).
This is a severe operation and the hydrogen consumption is a
strong function of the complexity of the aromatics.
Ring saturation arises in heavy distillate hydrotreating, gas
oil hydrotreating, and hydrocracking.
5 Metals Removal {hydrodemetallation (HDM)}
* Feed may contain metals like Vanadium, Nickel
Metals deposited directly on the catalysts
Excess metals reduce catalyst activity & promote
dehydrogenation.
Produce coke & hydrogen
Metals removal important in gas oil hydrotreating.
6 Other Contaminants
Organic chlorides and other halides are converted to
hydrogen chlorides, fluorides...
These are usually present in small amounts and the hydrogen
usage per molecule is similar to desulfurization.
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IV Hydrogen sources
1 Catalytic Reformer
The most important source of hydrogen for the refiner
Typically 90 vol. % from a continuously regenerated
reformer & 80 vol. % from semi-continuously regenerated
reformer
Approximately 50 psig

2 FCCU Off gas

Typically 5 vol. % hydrogen with methane, ethane &
propane
Several methods for recovery can be combined
Cryogenic
Pressure swing adsorption
Membrane separation

3 Steam-Methane Reforming
Most common method of manufacturing hydrogen
Methane, ethane, or heavy components reformed to
hydrogen, carbon dioxide, & water in a series of three
reactions
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methane catalytically reacts to form hydrogen and carbon

monoxide in an exothermic reaction
Carbon monoxide shifted with steam to form additional
hydrogen & carbon dioxide in an endothermic reaction
Carbon dioxide removed using one of several absorption
processes
Trace amounts of carbon monoxide & carbon dioxide
removed by exothermically reacting with hydrogen to form
methane & water
Hydrogen purity typically 90 to 95 vol. %
* This reaction takes place over a nickel promoted catalyst at
approximately 800oC.

4 Synthesis Gas
Partial oxidation (gasification) of heavy resid feed
Water-gas shift technology from asphalts, resids, & other
very heavy liquid or coal slurry
Synthesis gas will contain equal volumes of carbon
monoxide & hydrogen with about 5 vol. % carbon dioxide &
smaller volumes of methane, nitrogen, water & sulfur
Hydrogen recovered normally by:
pressure swing adsorption
membrane separation
Advantages & disadvantages
More expensive than steam reforming

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Can destroy a variety of polluted streams & low quality by

product streams

V Hydrogen consuming
The typical refinery runs at a hydrogen deficit
With hydroprotreting becoming more prevalent, this
deficit will increase
As hydroprotreting progresses in severity, the hydrogen
demands increase dramatically
Hydrogen Usage Typical Path of
Fed directly to the hydrotreaters for desulfurization of
naphtha & distillates, kerosene, jet fuel, diesel & home heating
oil
Desulfurization consumes 100 to 200 scf/barrel feed,
about half the hydrogen available from the reformer
Remainder used for gas oil hydrotreating & hydrocracking
Require additional hydrogen
When hydrogen concentration has been depleted, the residue
is either used for fuel gas or sent to a unit for hydrogen
recovery
Recovery operations often done by a third party

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Hydrotreating Chemistry & Hydrogen Consumption

Amount of hydrogen consumed is a function of bonds broken
& hydrogen lost with products
Published correlations for hydrogen consumption are weak
To some extent, data can be correlated in terms of sulfur
level & percent removal
Chemical consumption due to hydrogenation reactions which
are generally exothermic
Management of the heat of reaction important to safety
& operating stability of unit.

Figure 2: Hydrogen consumption by different cuts.

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Figure 3: Flow sheet for hydrotreating unit.

Figure 4: Hydrotreater in a refinery.

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