Chemistry and

technology of petroleum
By Dr. Dang Saebea
Hydroconversion
Introduction
Hydroconversion is a term used to describe all different processes in
which hydrocarbon reacts with hydrogen.
To describe the process of the removal of sulphur,
nitrogen and metal impurities in the feedstock by
hydrogen in the presence of a catalyst.
Hydrotreating
The process of catalytic cracking of feedstock to
products with lower boiling points by reacting
them with hydrogen.
Hydrocracking
Hydrogenation
aromatics are saturated by hydrogen to the
corresponding naphthenes.
Hydrotreating

Objectives of Hydrotreating
1. Removing impurities, such as sulphur, nitrogen and
oxygen for the control of a final product
specification or for the preparation of feed for
further processing.

2. Removal of metals, usually in a separate guard
catalytic reactor when the organo-metallic
compounds are hydrogenated and decomposed,
resulting in metal deposition on the catalyst pores.

3. Saturation of olefins and their unstable compounds.


Role of Hydrotreating

Role of hydrotreating (HT) in the refinery
HT are located before
the reformer,
hydrocracker and FCC
They are also
needed to adjust the
final product
specification for
various streams,
such as light naphtha,
kerosene and low
sulphur fuel oils
(LSFOs).
Main role of hydrotreating
1. Meeting finished product specification.
Kerosene, gas oil and lube oil desulphurization.
Olefin saturation for stability improvement.
Nitrogen removal.
De-aromatization for kerosene to improve cetane
number.

Cetane number is the percentage of pure cetane in a
blend of cetane and alpha-methyl-naphthalene. The latter
matches the ignition quality of kerosene sample.
2. Feed preparation for downstream units:
Naphtha is hydrotreated for removal of metal and
sulphur.
Sulphur, metal, polyaromatics and Conradson carbon
removal from vacuum gas oil (VGO) to be used as FCC
feed.
Pretreatment of hydrocracking feed to reduce sulphur,
nitrogen and aromatics.

Main role of hydrotreating
Hydrotreating reactions
1. Desulphurization
a. Mercaptanes:
b. Sulphides:
c. Disulphides:
d. Thiophenes:
2. Denitrogenation
a. Pyrrole:
b. Pyridine:
3. Deoxidation
a. Phenol:
b. Peroxides:
4. Hydrogenation of chlorides
5. Hydrogenation of olefins
6. Hydrogenation of aromatics
7. Hydrogenation of organo-metallic compounds
and deposition of metals
Vanadium deposited as vanadium sulphide (V2S3)
8. Coke formation by the chemical condensation
of polynuclear radicals
Hydrotreating Processes

1. The liquid feed is mixed with hydrogen and fed into a
heater and then fed into a fixed bed catalytic reactor.
2. The effluent is cooled and hydrogen-rich gas is separated
using a high pressure separator.

The main elements
of a hydrotreating
process
Hydrotreating Processes

3. Before the hydrogen is recycled, hydrogen sulphide can
be removed using an amine scrubber.
4. Some of the recycle gas is also purged
- To prevent the accumulation of light hydrocarbons
(C1C4)
- To control hydrogen partial pressure.

Hydrotreating Processes

5. The liquid effluent for the reactor is introduced to a
fractionator for product separation.

1. Naphtha Hydrotreating


To remove the impurities so that the hydrotreated
naphtha can be introduced to the catalytic reformer.

The expensive platinum based catalyst used in the
reformer is sensitive to poisoning by such impurities.

1. Naphtha Hydrotreating

a feed heater
reactor
high and low
pressure separators
recycle compressor
treated naphtha
fractionator.
1. Naphtha Hydrotreating

H
2
S scrubber
A catalyst of CoMo on alumina
is used.
2. Middle Distillates Hydrotreating


Middle distillate is mainly composed of saturated
paraffins and also some aromatics which include simple
compounds with up to three aromatic rings.

Kerosene, jet fuel oil and diesel fuel are all derived from
middle distillate fractions.


2. Middle Distillates Hydrotreating

A hydrogen sulphide
scrubber and a gas
purging are usually
used to improve the
quality of recycled
hydrogen.
3. Atmospheric Residue Desulphurization

atmospheric residue has a sulphur content and metals
(Ni + V).

The purpose of this process is to remove most of the
metals and reduce sulphur content in the product to less
than 0.5 wt%.

3. Atmospheric Residue Desulphurization
1. The feed is introduced into the heater where steam is injected (to
prevent coking) to a temperature below 371 C.

T<371 C
3. Atmospheric Residue Desulphurization
2. The heated recycled hydrogen is
mixed with feed and together,
they are introduced into a guard
reactor.

3. The stream leaving the guard
reactor is quenched with cold
recycle hydrogen and introduced
to the first of the three fixed bed
reactors.




contains a hydrogenation catalyst similar
to that in the main reactor but usually
cheaper.
The main reactions of
hydrodemetallization,
hydrodesulphurization,
denitrogenation and aromatic
hydrogenation take place in the
reactors.
3. Atmospheric Residue Desulphurization
4. The flow diagram also contains high and low pressure separators,
recycled hydrogen stream with online amine treatment and purge.
5. The liquid stream from the separators are send to a fractionator to
produce naphtha, diesel and low sulphur fuel oil (LSFO).

Reactor
The catalyst should have wide
pores to avoid plugging due to
metal deposition.
Due to the fast deactivation of
this catalyst, usually two
reactors are used and the
catalyst is changed in one of
them while the other reactor is
still online.
Three to four reactors are
usually used with different
combinations of catalysts to
achieve desired objectives.



Hydrogen requirements for
hydrotreating are classified into:

(1) Chemical requirement:

This is the amount of hydrogen required to remove
impurities such as sulphur, oxygen, nitrogen, olefins
and organometalic compounds, according to the
stoichiometry of these reactions.

Sometimes, it might be required to convert aromatics
and naphthenes to corresponding paraffins.
Hydrogen requirements for
hydrotreating are classified into:

(2) Hydrogen lost due to the dissolution of hydrogen in the
hydrocarbons treated.

(3) Amount of hydrogen lost with the purging of light
hydrocarbons (C1C4) and hydrogen sulphide (if not
removed by amine treatment).
Make-up Hydrogen
A certain hydrogen partial pressure should be maintained
in the reactors by recycling un-reacted hydrogen and
adding a make-up hydrogen to compensate for the
amount consumed.

The make-up hydrogen can be calculated by the following
expression
Operating Conditions

The operating conditions of the hydrotreating
processes
pressure
temperature
catalyst loading
feed flow rate
hydrogen partial pressure
Operating Conditions

Increasing hydrogen partial pressure improves the
removal of sulphur and nitrogen compounds and
reduces coke formation.

Higher temperatures will increase the reaction rate
constant and improve the kinetics. However, excessive
temperatures will lead to thermal cracking and coke
formation.

The space velocity is the reverse of reactor residence
time (y). High space velocity results in low
conversion, low hydrogen consumption and low coke
formation.
The range of operating conditions for
hydrotreating of different feed fractions
Hydrocracking
Hydrocracking is a catalytic hydrogenation process in which high
molecular weight feedstocks are converted and hydrogenated to
lower molecular weight products.

The catalyst used in hydrocracking is a bifunctional one. It is
composed of a metallic part, which promotes hydrogenation, and an
acid part, which promotes cracking.

Hydrogenation removes impurities in the feed such as sulphur,
nitrogen and metals.

Cracking will break bonds, and the resulting unsaturated products
are consequently hydrogenated into stable compounds.

Role of Hydrocracking in the Refinery

It is mainly used to produce
middle distillates of low
sulphur content such as
kerosene and diesel.

If mild hydrocracking is used,
a LSFO can be produced.

It has been used to remove
wax by catalytic dewaxing and
for aromatic removal by
hydrogen saturation.

This has been applied to the
lube oil plants and is gradually
replacing the old solvent
dewaxing and aromatic solvent
extraction.

Feeds and Products

VGO is the main feed for hydrocrakers
Hydrocracking Chemistry
1. Alkane hydrocracking
2. Hydrodealkylation
3. Ring opening
4. Hydroisomerization
5. Polynuclear aromatics hydrocracking
Hydrocracking Catalysts

The cracking function is provided by an acidic support,
whereas the hydrogenationdehydrogenation function is
provided by active metals.
Hydrocracking Processes

The following factors can affect operation (product quality),
yield (quantity), and the total economics of the process:
1. Process configuration: one stage (once-through or recycle) or
two stages
2. Catalyst type
3. Operating condition (depends on process objective)
- Conversion level
- Maximization of certain product
- Product quality
- Catalyst cycle
- Partial hydrogen pressure
- Liquid hourly space velocity
- Feed/hydrogen recycle ratio


Process Configuration

Simplified flow
diagram of one-stage
hydrocracking
process with and
without recycle
In commercial hydrocrackers, a conversion of 4080% of the feed can
be achieved.
However if high conversion is required the product from the bottom of
the distillation tower is recycled back to the reactor for complete
conversion.
This configuration can be used to maximize a diesel product, and it
employs an amorphous catalyst.
Process Configuration

Conventional two-
stage hydrocracker
The effluent from the first stage reactor is sent to a separator and fractionator.
The fractionator bottoms are sent to the second reactor.
The catalyst in the first
stage has a high
hydrogenation/acidity
ratio, causing sulphur
and nitrogen removal
In the second reactor, the
catalyst used is of a low
hydrogenation/acidity
ratio in which naphtha
production is maximized

A hydrotreatment reactor may be added before the first hydrocracker
to help in removing sulphur and nitrogen compounds from the feed.

Since H
2
S and NH
3
are separated before entering the second
hydrocracker, this allows the selection of special catalysts in the
second reactor without the poisoning effect of sour gases.

The two-stage configuration offers more flexibility than the single
stage scheme. It is better suited for heavy feedstocks

Two-stage hydrocracking
The End