Hydrotreating

1) Review of overall refining process

2) Difference between various hydroconversion
processes
3) Objectives of hydrotreating
4) The reasons hydrotreating is carried out
5) The chemistry of hydrotreating process
6) Process flow of 3 types of hydrotreating
processes
7) Operating conditions and process variables in
hydrotreating
Outline of 5th chapter
 Separation Conversion Finishing
Crude oil Gas sweetening,
Gas
Catalytic isomerization blending

Desalting Light naphtha Light distillate

sweetening,
Heavy naphtha Catalytic reforming hydrotreatment or
Atmospheric blending
distillation Kerosene
Alkylation Polymerization
ADR Middle distillate
Gas oil sweetening,
Light vacuum Fluid catalytic hydrotreatment or
Vacuum gas oil cracking blending
distillation Heavy
VDR vacuum gas oil Hydrocracking
Heavy distillate
Dewaxing sweetening,
Visbreaking hydrotreatment or
Solvent blending
deasphalthing Coking
Physical and chemical processes
 Hydroconversion

 Hydroconversion is a term used to describe all different processes in which

hydrocarbon reacts with hydrogen.

Hydrotreating To describe the process of the removal of sulphur,

nitrogen and metal impurities in the feedstock by
hydrogen in the presence of a catalyst.

The process of catalytic cracking of feedstock to

Hydrocracking products with lower boiling points by reacting
them with hydrogen.

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.

4. Produce higher yields of fuel products  breaking

aromatic bonds to lower average MW HCs
 Protection
of environment
reduction in acid rain

 Protection of downstream catalyst

in further downstream processing
 S-compound in diesel fuel give difficulties
in catalytic cleaning of exhaust gases

 Improvement on gasoline properties

 odor, color, stability, corrosion

Why Hydrotreating?
 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).

Role of hydrotreating (HT) in the refinery

1. Meeting finished product specification.
 Kerosene, gas oil and lube oil desulfurization.
 Olefin saturation for stability improvement.
 Nitrogen removal.
 De-aromatization for kerosene to improve octane
number.

Cetane number is the percentage of pure cetane in a

blend of cetane and alpha-methyl-naphthalene.
Represent the ignition quality of kerosene sample.
2. Feed preparation for downstream units:

 Naphtha is hydrotreated for removal of metal and

sulphur.
 Sulphur, metal, polyaromatics from vacuum gas oil
(VGO) to be used as FCC feed.
 Pretreatment of hydrocracking feed to reduce sulphur,
nitrogen and aromatics.
 How hydrotreating being
accomplished?

Treating the feed with hydrogen at elevated

temperature & pressure with the presence of
catalyst.
The operating conditions are a function of type of
feed and desired level of desulfurization in the
treated product
The chemistry of hydrotreating
and hydrogen consumption
Hydrogenation  class of chemical rxn in which net result is the
addition of hydrogen (H)

Reaction schematic:
Hydrogenolisis  process of
cleavage of C-X bond

O
Deoxigenation
S
Desulfurization
N
Denitrogenation
  Sulfur  H2S in the
desulfurization step.
 As hydrogen is added, the
carbon-sulfur bonds are broken
and the remaining hydrocarbon
chains are saturated. This
Sulfur creates some light ends.
Oxygen cmpds
cmpds  Heavier distillates make more
light ends from breaking more
complex sulfur molecules.
Aromatic
Naphta cmpds  The sulfur-containing cmpds are
generally mercaptans, sulfides,
Nitrogen disulfides, polysulfides and
cmpds thiophenes
Chloride
cmpds
 As the feeds become heavier,
more sulfur is in the form of
disulphides and thiopenes.
  Aromatic  cycloparaffin
(naphthenes)
Sulfur
Oxygen cmpds  Hydrogen consumption is a
cmpds strong function of the complexity
Aromatic
of the aromatics.
Naphta cmpds
 Ring saturation arises in heavy
Nitrogen
cmpds distillate (diesel and heating oil)
Chloride hydrotreating and gas oil
cmpds
hydrotreating.
  Organic chlorides are converted
Sulfur to H2Cl
Oxygen cmpds
cmpds  These are usually present in
small amounts and the
Aromatic hydrogen usage per molecule is
Naphta cmpds similar to desulfurization.
Nitrogen
cmpds
Chloride
cmpds
  Nitrogen is converted to NH3 in
the denitrogenation step.

 Examples of nitrogen containing

compounds are pyridines and
Sulfur pyrroles.
Oxygen cmpds
cmpds  Nitrogen removal is minor in
naphtha hydrotreating.
Aromatic
Naphta cmpds  As the feeds become heavier,
Nitrogen denitrogenation becomes more
cmpds significant.
Chloride
cmpds  Nitrogen removal requires about
four times as much hydrogen as
the equivalent sulfur removal.
  Oxygen is converted to water.

 Examples of oxygen containing

compounds are phenols and
Sulfur peroxides.
Oxygen cmpds
cmpds
 Like nitrogen removal, oxygen
Aromatic
removal is minor in naphtha
Naphta cmpds hydrotreating but significant in
heavy distillate hydrotreating.
Nitrogen
cmpds
Chloride  Oxygen requires about two times
cmpds
as much hydrogen as the
equivalent sulfur removal.
 1. The reactants are adsorbed on the
catalyst surface and H2 dissociates.

2. An H atom bonds to one C atom. The

other C atom is still attached to the surface.

3. A second C atom bonds to an H atom.

The molecule leaves the surface.
 What are the catalysts being used?

Two types of catalysts are generally used.

• Cobalt (molybdenum on alumina support) catalysts

are preferred for desulfurization and olefin saturation
since they require less hydrogen consumption for mild
operation.

•Nickel (molybdenum on alumina support) is utilized

for nitrogen removal and aromatic saturation.
 What are the types of
hydrotreating process?

There are 3 types or severities of hydrotreating:-

• Naphtha hydrotreating,
• Distillate (light and heavy) hydrotreating,
• Gas oil hydrotreating.
 Desulfurization of higher molecular weight oil
calls for higher hydrogen consumption & higher
pressures.
 Naphtha Distillate Gas oil
PRIMARY OBJECTIVE
• To remove sulfur
• Upgrade raw kerosene • Saturation of olefinics
contaminant for
distillate to produce HCs to improve storage
downstream
suitable spec kerosene stability of diesel
processes
and jet fuel • Improve H/C ratios
1. Cat reforming  to
• Remove sulfur from increases FCC capacity
improve octane #
diesel for clean fuels and conversion
2. Steam reforming 
to produce H2
FEEDS

• Light and heavy • Liquid distillate

• Atm, vacuum & solvent
naptha from atm streams
deasphalting gas oil
tower
PRODUCTS
H2 rich gas, LPG rich • Kerosene
• Light and heavy
gas, Hydrotreated • Jet fuel
diesel
naphtha • Diesel oil
 Naphtha Distillate Gas oil
hydrotreating hydrotreating hydrotreating
Mercaptans (thiols) Thiophenes Thiophenes
Sulfides Disulfides Disulfides
Minor (significant)
More significant More significant
Pyridines & pyroles
Minor
Significant Significant
Phenol & peroxide
Hydrogen chloride Hydrogen chloride Hydrogen chloride
Small amount Small amount Small amount
Strong function of
Ring saturation Ring saturation
complexity of the
arises arises
aromatics
 Desulfurization

Denitrogenation

Olefin saturation

Deoxygenation
 Air-cooled H2 purged out
the effluent
Vapor: H2S, light
HCs

Mixed
Separation between
and vapor and liquid here
heated
Liquid: preheated
and fed to bottom of
column
Charged
pump Desulfurization
takes place over
catalyst

Rxr effluents:
naphtha, H2S, excess
H2 and light end
 Some of the recycle gas is
also purged
- To prevent the
accumulation of light
hydrocarbons (C1–C4)
- To control hydrogen
partial pressure.

Vapor: H2S, light

HCs Amine unit for
H2S recovery
 Mixed
and
H2-rich gas is
heated
compressed and
recycled to the reactor
Desulfurization &
denitrification take
place over catalyst High flash
naphtha

Air-cooled
the effluent
Kerosene as
The reactor effluent is side stream
flashed in high product
pressure separator
To provide a greater catalyst
volume than in straight
desulfurization service.
Increasing hydrogen partial pressure improves the
removal of sulfur and nitrogen compounds and diminishes
the coke deposits on catalyst.

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.
General Effects of Process Variables
Reactor inlet Temperature & Pressure:

• Increasing temperature will increase hydrogenation but

hastens the deterioration in the number of active
catalyst sites.
• At end of run, temperature control is used to offset the
decline in catalyst activity.
• Increasing pressure increases hydrogen partial pressure
and is used to increase the severity of hydrogenation.
General Effects of Process Variables
Recycle hydrogen:
 Hydrotreaters must have a high concentration of hydrogen
at reactor outlet so the hydrogen amount is much more
than stoichiometric.
 High concentrations are required to prevent coke laydown
on catalyst and poisoning the catalyst. This is particularly
true for the heavier distillates containing traces of resins and
asphaltenes that are subject to coking.
 General Effects of Process Variables

Purge ratio:

Purge ratio= V of H2 in purged gas

V of H2 in make up gas

Purging  to prevent buildup of inert gas & light HCs

 to maintain a high purity of hydrogen as the
light ends formed dilute the hydrogen concentration.