COLLEGE OF ENGINEERING

DEPARTMENT OF PETROLEUM AND CHEMICAL

ENGINEERING
COURSE NAME: PETROLEUM REFINING OPERATIONS
FALL SEMESTER

Hydrotreating
PRESENTED BY ENG. JAMIL MAHFOUD
Hydrotreating
 Introduction
Hydrotreating achieves the following objectives:
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 (naphtha reformer feed and FCC feed).
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:
Hydrotreating units are needed in the refinery to clean streams from
material such as sulphur, nitrogen or metals harmful to the catalysts. That is
why they are located before the reformer, hydrocracker and FCC as shown in
the previous scheme. They are also needed to adjust the final product
specification for various streams, such as light naphtha, kerosene and low
sulphur fuel oils (LSFOs).
 Chemistry
Petroleum fraction contains foreign elements, such as S, N, O, and Cl, which
can be removed by hydrotreating. Hydrotreating is also used to transform
unsaturated compounds to the corresponding saturated hydrocarbons.
Hydrotreating reactions can be classified as follows:
1. Desulphurization:
2. Denitrogenation:
a. Mercaptanes: RSH + H2 → RH + H2S
a. Pyrrole: C4H4NH + 4H2 → C4H10 + NH3
b. Sulphides: R2S + 2H2 → 2RH + H2S
b. Pyridine: C5H5N + 5H2 → C5H12 + NH3
c. Disulphides: (RS)2 + 3H2 → 2RH + 2H2S
3. Deoxidation:
a. Phenol: C6H5OH + H2 → C6H6 + H2O
d. Thiophenes:
b. Peroxides: C7H13OOH + 3H2 → C7H16 + 2H2O

4. Hydrogenation:
a. Chlorides: RCl + H2 → RH + HCl
b. Olefins: C5H10 + H2 → C5H12
c. Aromatics: C6H6 + 3H2 → Cyclohexane
Naphthalene + H2 → Tetraline
 Catalyst
The hydrotreating catalyst is a porous alumina matrix impregnated with
combinations of cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W).
The catalysts mainly have pores with a great surface area.
Table 1: Reactivities of hydrotreating catalysts:

Co–Mo catalysts are used when higher activity is required for removal of
Sulphur compounds while Ni–Mo catalysts are chosen when higher activity is
required for the saturation of polynuclear aromatic compounds or for the
removal of nitrogen. Ni–W catalysts are chosen only when very high activity
aromatic saturation is required.
 Sulphur components
The sulphur level in oil streams depends on the sulphur content in crude oil. According to
Schlumberger, a crude oil is classified to be sour if it has a concentration of more than 0.5% of
sulphur compounds.
 Environmental

 Human health:
Sulphur dioxide (SO2) is a harmful substance in gaseous form that
emits a bad smell. This substance is produced in the atmosphere as a
result of the following reaction:
S + O2 → SO2
Sulphur dioxide is in principal released by industrial operations that
encounter sulphur components in the composition of reactants and
products. Power generation and transportation tools are two primary
sources of SO2 emission in the atmosphere. The impact of such
emission is very dangerous on human health especially for people
exposed to SO2 for 10-15 minutes which can cause serious cough and a
pressure feeling on the chest with a difficulty in breathing.
 Acid rain
Moreover, acid rain is primary caused by the availability of SO2 in the air
where the pH of water decreases from its normal value 7 to a lower value,
hence water acidity increases carrying with it a series of catastrophic effects.
To begin with, water acidity increases by the release of hydrogen ions (H+) in
water. This process is initiated as follows:
SO2 (g) + ½ O2 → SO3 (g)
SO3 (g) + H2O → H2SO4 A strong acid known as sulphuric acid
H2SO4 is capable for further separation in order to provide H+ and HSO4- that
is also able to give another H+ cation and SO42- anion.
H2SO4 → HSO4- + H+
HSO4- → SO42- + H+
The result of the reactions listed above is that the concentration of hydrogen
ions in rainwater increases sharply reaching a destructive level on buildings,
natural resources and human life. Marble and limestone are materials
composed from calcium carbonate (CaCO3) and it’s widely used in the
construction of monuments and buildings.
 Impacts
During acid rain, H2SO4 dissolves CaCO3 in this form:
CaCO3 (S) + H2SO4 (aq) → Ca2+(aq) + SO42- (aq) + H2O + CO2
The reaction between CaCO3 and H2SO4 can have a dramatic effect on statues,
pillars and buildings that have lasted for thousands of years, hence the destruction
of a valuable historical memory. Acid rain has also an impact on metals where
sulphuric acid can cause metals corrosion under the following process:
M + H2SO4 (aq) → MSO4 (aq) + 2H+
Fresh water can also be contaminated by acid
rain where lot of lakes became very acidic and
an unfavourable place for animal survival. Add
to that, many forests like Spruce forest in USA
and Bavarian forest in Germany were highly
affected by acid rain that can be transmitted
from the country that emits high level of
sulphur dioxide to other countries through
wind currents.
 Naphtha
Naphtha is basically a hydrocarbon mixture of paraffins,
olefins, aromatics and impurities like sulphur elements. The
percentage of naphtha components differs for light and
heavy naphtha. Light naphtha or straight run naphtha
(SRN) is also named as paraffinic hydrocarbon due to the
high percentage of paraffin in its composition. However,
the concentration of olefins and aromatics is very low
where the average boiling point consists between 25-95oC
with lower sulphur content than heavy naphtha feed. Long
chain hydrocarbon and complex sulphur elements increase
the viscosity and boiling point range of heavy feeds that
require additional heat for the treatment of such viscous oil
streams.
 Flow scheme

(200-350oC)
 Points
 The major aim of SRN hydrotreating is the removal of impurities to
prepare the feed for catalytic reforming where saturation reactions may
also take place.
 The type of catalyst used “CoMo” is mainly designed for HDS process
while expansive catalysts used in catalytic reforming is more effective for
conversion reactions of olefins and aromatics into valuable products.
 The operating conditions used in SRN hydro-treating aren’t always severe
enough to saturate all olefins and aromatics that require more wild
conditions used in hydrocracking process.

 It’s undesirable to convert all olefins in the feed in order to preserve a

high octane number for fuel products obtained.
 Reactor type
There are many types of
catalytic hydrotreating reactors
as the figure shows. Ebullated
bed reactor (EBR) and slurry
bed reactor (SBR) have a minor
use in hydrotreating process
due to the complexibility of
the reactor design and many
other difficulties. EBR and SBR
are mainly used to process heavy crude oil feed that contain a big
concentration of asphaltene and metals. However, moving bed reactor (MBR)
and fixed bed reactor (FBR) are the most common reactors used for
hydrotreating. Many reasons such a the simplicity of the reactor design, the
low cost of operating conditions and the flexibility of catalyst handling in the
reactor bed made the use of MBR and FBR very efficient and economical for
treating naphtha feed.
 FBR
Catalytic fixed bed reactor is being applied in commercial hydrotreating
operations since the early 1800s during the discovery and progression of solid
catalysts that made FBR as the dominant type. Over the years, scientists and
engineers developed many different designs under two main categories:
1. Non adiabatic: This type of reactor is ideal in case we have high
endothermic or exothermic reactions where heat generation or
consumption take place. In this case, the design of the reactor should
include internal tubes for heat transfer using a cold/hot liquid or vapor
stream.
2. Adiabatic: In this type of reactor, there is no heat exchange with the
surrounding when reactions take place. It is a superior choice over non-
adiabatic reactor if the selection and conversion rate are acceptable. In
addition, the operating costs are less expansive because there is no need
to have big reactor volume for heat exchangers inside the reactor.
 Quenching
In order to avoid the use of a large reactor
volume with high cost, it is often desirable
to apply a quenching system for 3 adiabatic
FBRs in series with considerable size as the
figure shows. Naphtha feed and hydrogen
stream flow together through the bed
where HDS and hydrogenation reactions are
exothermic and release lot of heat Tout that
need to be handled. At this stage, it is
required to inject a cold liquid or vapor such
as H2 stream having a temperature of TQ .
Once H2 stream is mixed with the first FBR
products Tout in quench zone, the
temperature cools down in the inlet of the
second FBR Tin= Tfeed as the temperature
profile shown.
 Stream phases
There are two types of system, single phase or multiphase system.
In light naphtha hydrotreating process, all hydrocarbon stream is
in vapour phase after increasing the feed temperature Tf to reach
the temperature of the reactor Tr. Nevertheless, the boiling point
temperature of dibenzothiophene and its substitutes is extremely
high and can reach up to (365oC) for 4,6
dimethyldibenzothiophene. As a result, a high concentration of
dibenzothiophene might create a liquid phase in the system in
combination with the vapor phase of light naphtha components.
As we already mentioned before, catalyst particles are in solid
form, therefore SRN hydro-treating occurs in heterogeneous
system with 2 possible combinations:
• Gas + solid.
• Gas + liquid + solid.
Both combinations operate under steady state conditions in a
continuous system. However, gas + solid combination follows a
plug flow regime while the second combination takes place in a
trickle bed reactor with an immobile catalyst bed.
 TBR
The energy costs for vaporizing the feed and cooling the reactor products in trickle
bed are considerably less expansive than 2 phase reactor. For that reason,
hydrotreating process often desires TBR even though the process is feasible with
vapor + solid combination. In this case, gas and liquid move together in a co-current
flow through a 10-30 m height TBR column equiped with solid catalyst pellets that are
distributed over various fixed beds. After certain time, the catalyst will be saturated
in H2S components which creates in return an inhibition side effect that limit the
removal of the last ppm of sulfur. In counter-current flow, this problem can be
avoided but its use is limited for large catalyst particles and high velocity flow.
Liquid phase progresses over the catalyst bed in
rivulet or film flow where wetting and irrigation
conditions of the catalyst particles have an
important role in the distribution of liquid stream
over the bed. If the catalyst particles are not ideally
irrigated, liquid phase will follow certain specific
paths in the catalyst bed and as a result a great part
of the bed will not be used and wasted.
 Flow pattern
If the hydrocarbon stream velocity is very low, liquid phase will also flow
separately from gas phase as figure (b) shows. This phenomena is know as
the maldistribution of liquid phase over the catalyst bed which in return
affects the overall conversion of naphtha hydrotreating process. This
incident lead to an incomplete utilization of the catalyst.
 Process variables
H2 partial pressure:
Reactor design often determines the pressure limits of the hydrotreating
process where inlet hydrogen pressure Pin is calculated using the following
formula:
Pin= nH2 * PT where nH2 is the mole fraction of H2 of the recovered gas
PT is the total pressure
One of the main objectives of H2 partial pressure is to minimize the
probability of coke formation if heavy hydrocarbon feed is processed. For
pressure values below the required one, coke is formed especially in feeds
with high olefinic concentration. The deactivation rate of catalyst increases
with low pressure due to coke formation on catalyst surface which decrease
the utilization of the whole bed. Despite that most refineries tend to
operate with the highest partial pressure possible, there is a certain design
limits that should not be exceeded in order to prevent any reactor damage
that often occurs.
 Process variables
The main advantages for operating with high partial pressure are the
following:
• Prevention of coke formation
• The ability to process and handle heavy feeds
• The increase of catalyst longetivity
• Optimum use of catalyst bed
• Better conversion rate
• Better products quality
In order to guarantee all the advantages listed before, it’s very crucial to
control pressure variations of Naphtha hydrotreating. The main way to rise
partial pressure is through the increase of hydrogen ratio in recycle gas
obtained by the following formula:
 Hydrogen availability
The availability of hydrogen in hydrotreating process is very important for
the removal of impurities and for the hydrogenation of unsaturated
compounds. Therefore, H2 consumption and recycle are two factors that
should be always highlighted and well controlled
 Temperature
In general, process selectivity is controlled by reactor temperature since
each feed is characterised by a specific boiling point range, therefore
temperature controls the type of components that can be separated from
the hydrocarbon feed. It is often desirable to increase the temperature in
order to enhance the rate of HDS reactions in the reactor. Regardless of that
the type of feed and the reactor
design are two limiting factors of
such increase especially that for
very high temperature values,
hydrocarbon components will be
cracked into small molecular
weight components which affect
the yield of the system.
Thanks for your attention