Unit 2

Refining process

Subject: Petroleum Refining Technology

Code: CHCE 3010
Faculty: Dr. Seim Timung
Lecture: 17, 18
 Hydroconversion

• Hydroconversion is a term used to describe all

different processes in which hydrocarbon reacts with
hydrogen.

Hydrotreating Hydrocracking Hydrogenation

Hydrotreating is used to describe the
process of the removal of sulphur,
nitrogen and metal impurities in the
feedstock by hydrogen in the
presence of a catalyst.
Hydrocracking is the process of
catalytic cracking of feedstock to
products with lower boiling
points by reacting them with
hydrogen.
Hydrogenation is used when
aromatics are saturated by
hydrogen to form its
corresponding naphthenes.
Hydrotreating
 Hydrotreating
• Objectives

• Removing impurities, such as sulfur, nitrogen and oxygen for the control
of a final product specification or for the preparation of feed for further
processing (Example: naphtha reformer feed and FCC feed).

• 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 (e.g. atmospheric residue
desulphurization (ARDS) guard reactor).
• Saturation of olefins and their unstable compounds.
Hydrotreating
 Role of Hydrotreating
• 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.

• They are also needed to adjust the final product specification for various
streams, such as light naphtha, kerosene and low sulfur fuel oils (LSFOs).
 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, which 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 from vacuum gas oil (VGO) to be used as
FCC feed.
 Chemistry of hydrotreating
• Desulfurization
a. Mercaptanes

Thiophene
Chemistry of hydrotreating

Pyrrole

Pyridine
Chemistry of hydrotreating

Peroxo group
Chemistry of hydrotreating
 Chemistry of hydrotreating

• Vanadium deposited as vanadium sulfide.

 Reactivity of catalyst
Catalyst Hydro- Hydro- Aromatics
desulfurization denitrogenation hydrogenation
Co-Mo/Alumina Excellent Good Fair
Ni-Mo/Alumina Very Good Very Good Good
Ni-W/Alumina Good Good Excellent

• 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 surface area of (200 – 300 m2/g).

• Co – Mo catalysts are the most popular for desulphurization of straight run

petroleum fractions.
 Reactivity of catalyst

Catalyst Hydro- Hydro- Aromatics

desulfurization denitrogenation hydrogenation
Co-Mo/Alumina Excellent Good Fair
Ni-Mo/Alumina Very Good Very Good Good
Ni-W/Alumina Good Good Excellent

• Ni–Mo catalysts are chosen when higher activity is required for the saturation
of polynuclear aromatic compounds or for the removal of nitrogen and
refractory sulfur compounds.
• While Ni–W catalysts are chosen only when very high activity aromatic
saturation is required
DeNOx catalysts for the removal of nitrogen oxides from
combustion power plant stack gases by selective catalytic reduction
with ammonia; the products are harmless nitrogen and water vapor.
Typical DeNOx catalysts are honeycomb-shaped TiO2WO3V2O5
ceramics.
 Diesel desulfurization

1. Reactor
2. Separator
3. Fractionator
Diesel desulfurization
Hydrocracker
 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 sulfur, nitrogen and metals. Cracking
will break bonds, and the resulting unsaturated products are consequently hydrogenated into
stable compounds.
• Cracking will break bonds, and the resulting unsaturated products are consequently
hydrogenated into stable compounds.
For mechanism of hydrogenation reaction, kindly refer to the link below:
https://www.wou.edu/las/physci/ch334/lecture/lect16.htm
 Role of Hydrocracker
• Hydrocracking plays an important role as one of the main conversion processes in the refinery.
• It is mainly used to produce middle distillates of low sulfur content such as kerosene and
diesel.
• If mild hydrocracking is used, a LSFO can be produced. More recently, it has been used for
aromatic removal by hydrogen saturation.
• More recently, it has been used for aromatic removal by hydrogen saturation.
• This interest in the use of hydrocracking has been caused by several factors, including
 the demand for petroleum products has shifted to high ratios of gasoline and jet fuel
compared with the usages of diesel fuel and home heating oils,
 by-product hydrogen at low cost and in large amounts has become available from
catalytic reforming operations,
 Environmental concerns limiting sulfur and aromatic compound concentrations in
motor fuels have increased.
 Feedstock of hydrocracker
VGO is the main feed for hydrocrakers, however a variety of feeds can be used. The feedstock
type has an important influence on the final products.
Hydrocracking chemistry
 Single stage hydrocracking
• 40 – 80% 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.
 Single stage hydrocracking
• The effluent from the first stage reactor is
sent to a separator and fractionator.
• The fractionator bottoms are sent to the
second reactor.
• In both configurations, the hydrogen is
separated in the high pressure separator and
recycled back to the reactor.
• The hydrocracking catalyst in the first stage
has a high hydrogenation/acidity ratio,
causing sulfur and nitrogen removal.
• In the second reactor, the catalyst used is of
a low hydrogenation/acidity ratio in which
naphtha production is maximized.
• The main reactions taking place in each
reactor.
 Single stage hydrocracking
• However, if middle distillate, kerosene, diesel and jet fuel are to be maximized, a high
hydrogenation/acidity ratio is used.
• A hydrotreatment reactor may be added before the first hydrocracker to help in removing sulfur
and nitrogen compounds from the feed.
• Since H2S and NH3 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.
• This will allow deep hydroconversion.
• The two-stage configuration offers more flexibility than the single stage scheme. It is better
suited for heavy feed stocks (Secherzer and Gruia, 1996).