Chapter 9

Hydrotreating

PROCESSES
TERMS USED LOOSELY IN INDUSTRY:
HYDROTREATING
HYDROPROCESSING
HYDROCRACKING
HYDRODESULFURIZATION

 Hydrotreating is a mild operation

whose primary purpose is to saturate
olefins or reduce the sulfur or
nitrogen content(not to change the
boiling range) of the feed.
Hydrocracking refers to processes
whose primary purpose is to reduce
the boiling range in which most of the
feed is converted to products with
lower boiling ranges.
Hydroprocessing comes in between
the other two; it contains sulfur or
nitrogen removal and a change in the
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boiling range.

Hydrotreating
Hydrotreating is applied to a wide
range of feed stocks, from naphtha
to reduced crude.
It is a process to catalytically
stabilize petroleum products by:
Converting olefins to paraffin's
Or remove objectionable
elements(sulfur, nitrogen, oxygen,
halides, trace metals, etc) from
products or feed stocks by reacting
them with hydrogen
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For environmental objectives, it may

be necessary to hydrogenate aromatic
rings to paraffin's.
There are about 30 hydrotreating
processes available and most of them
have essentially the same process flow
for a given application.
When the process is employed
specifically for sulfur removal it is
called hydrodesulfurization.
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Hydrodesulfurization

Hydrodesulfurization
Oil Process
feed is mixed with hydrogenrich gas either before or after it is
preheated to the proper reactor
inlet temperature (between 500
& 800F (260 & 427C). It should
be below 800F to minimize
cracking.
In the presence of the metaloxide catalyst, the hydrogen
reacts with the oil to produce
hydrogen sulfide, ammonia,
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 The metals remain on the surface of

the catalyst, and the other products
leave the reactor with the oilhydrogen stream.
The reactor effluent is cooled before
separating the oil from the hydrogenrich gas.
The oil is stripped of any remaining
hydrogen sulfide and light ends in a
stripper.
The gas may be treated to remove
hydrogen sulfide and ammonia, then
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Hydrotreating
catalysts
Catalysts
developed for

hydrotreating include tungsten and

molybdenum sulfides on alumina
[Hydrogenating catalyst].
Their properties are modified by
adding either cobalt or nickel
sulfides.
Other hydrogenating catalyst :
nickel sulfide, nickel
thiomolybdate , tungsten and nickel
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 Cobalt and molybdenum sulfide on

alumina catalysts are in most general
use today because they have proven
to be :
Highly selective
Easy to regenerate
Resistantcatalysts
to poisons
Most economic
for sulfur
removal contain cobalt and
molybdenum sulfides (CoMo) on
alumina supports.
For nitrogen removal, catalysts
composed of nickel-cobalt-molybdenum
or nickel-molybdenum (NiMo)
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 Nitrogen is more difficult to remove

from HC streams than sulfur.
Any treatment that reduces excess
nitrogen concentrations usually will
effectively remove excess sulfur.
Nickel-containing catalysts require
activation(before bringing it up to
reaction temperature) by resulfiding
with:
Carbon sulfide
Mercaptans
Dimethyl sulfide
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 Cobalt-molybdenum catalysts are

selective for sulfur removal.
Nickel-molybdenum catalysts are
selective for nitrogen removal.
Both catalysts will remove both sulfur &
nitrogen.
Nickel-molybdenum catalysts have a
higher hydrogenation activity =>
greater saturation of aromatic rings.
Nickel-tungsten is actually the most
effective for nitrogen removal &
aromatic saturation, but it is much
more expensive & therefore seldom
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Catalyst consumption
Catalyst consumption varies
from 0.001 to 0.007 lb/bbl
(0.003 to 0.02 kg/m3) feed
depending upon:
Severity of operation
Gravity of the feed
Metals content of the feed
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Aromatics Reduction
To control aromatic saturation, the most important
parameter is hydrogen partial pressure.
Depending on the type of feedstock, the required
partial pressure to reduce aromatic content to 10
vol % may vary as 40%.

It has been demonstrated that at specific

conditions (715F, 0.75-2.0 h-1 LHSV, 2450
psig), hydrodearomatizations can be
achieved to levels of less than 10 vol %
using nickel-tungsten on gamma-alumina
catalysts.
Investigators show that at LHSV of 2.0,
aromatics in diesel fuel blending14 stocks may

Dynamics vs. Thermodynamics

Hydrogenation = exothermic equilibrium
yields favored by low temperatures.
But reaction rates increase with temperature.
Hydrogenation of aromatic ring compounds is
a compromise between using low reactor
temperatures (maximum aromatic reduction)
and high temperature (high reaction rates and
minimum amount catalyst per barrel of feed).
Maximum aromatic reduction is achieved
between 705F and 725F because of
interrelation between thermodynamic
equilibrium and dynamic reaction rates.
For a given pressure, the optimum
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temperature is a function of the types
of

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Reactions
Desulfurization is the main
hydrotreating reaction.
However, many others to occur
to a degree proportional to the
severity of the operation.

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Desulfurizati
on
The ease of Desulfurization
depends on the type of
compound, the lower the boiling
point the desulfurization is easy.
The difficulty of desulfurization in
the increasing order is as follow:
Paraffins
Naphthenes
Aromatics
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Denitrogenation
Denitrogenation is more severe
than desulfurization.
Middle distillate fractions that are
from crude oil contain high
concentrations of nitrogen.
This is reduced by using a
catalyst charge of 90% nickelmolybdenum & 10% nickeltungsten.
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Hydrogen consumption:
~ 70 scf/bbl of feed per % Sulfur
~ 320 scf/bbl oil feed per % Nitrogen
~ 180 scf/bbl per % oxygen REMOVED
For olefins & aromatics reduction can be
estimated from the stoichiometric amounts
required.
When an appreciable amount of cracking
occurs due to severe operating conditions,
then the hydrogen consumption increases
rapidly.
Hydrogen make up are from 2-10 times the
stoichiometric hydrogen required. Why ?
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 Because of the solubility loss in

the oil leaving the reactor
effluent separator and the
saturation of olefins produced by
cracking reactions
All reactions are exothermic . The
temperature of the reactor rises
to about 5-20 oF
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Process Variables
Operating Variables:
Temperature
Hydrogen partial pressure
Space velocity

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Temperatu
re
Increasing Temp. Increases
sulfur and nitrogen removal, and
hydrogen consumption
However, excessive increase in
temperature must be avoided,
since this will increase coke
formation.
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Pressure
Hydrogen partial pressure
increase will also increase the
sulfur and nitrogen removal, and
hydrogen consumption.
Increasing pressure Increase
Hydrogen saturation and reduces
coke formation.
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Space
Velocity
Increasing Space Velocity
Reduces conversion Disadvantage
Reduces hydrogen consumption
Advantage
Reduces coke formation
Advantage

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Typical Range of Process Variables

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