Process description[edit]

In an industrial hydrodesulfurization unit, such as in a refinery, the hydrodesulfurization reaction

takes place in a fixed-bed reactor at elevated temperatures ranging from 300 to 400 C and
elevated pressures ranging from 30 to 130 atmospheres of absolute pressure, typically in the
presence of a catalyst consisting of an alumina base impregnated with
cobalt and molybdenum (usually called a CoMo catalyst). Occasionally, a combination
of nickel and molybdenum (called NiMo) is used, in addition to the CoMo catalyst, for specific
difficult-to-treat feed stocks, such as those containing a high level of chemically bound nitrogen.
The image below is a schematic depiction of the equipment and the process flow streams in a typical
refinery HDS unit.

Schematic diagram of a typical Hydrodesulfurization (HDS) unit in a petroleum refinery

The liquid feed (at the bottom left in the diagram) is pumped up to the required elevated pressure
and is joined by a stream of hydrogen-rich recycle gas. The resulting liquid-gas mixture is preheated
by flowing through a heat exchanger. The preheated feed then flows through a fired heater where
the feed mixture is totally vaporized and heated to the required elevated temperature before entering
the reactor and flowing through a fixed-bed of catalyst where the hydrodesulfurization reaction takes
place.
The hot reaction products are partially cooled by flowing through the heat exchanger where the
reactor feed was preheated and then flows through a water-cooled heat exchanger before it flows
through the pressure controller (PC) and undergoes a pressure reduction down to about 3 to 5

atmospheres. The resulting mixture of liquid and gas enters the gas separator vessel at about 35 C
and 3 to 5 atmospheres of absolute pressure.
Most of the hydrogen-rich gas from the gas separator vessel is recycle gas, which is routed through
an amine contactor for removal of the reaction product H
2S that it contains. The H
2S-free hydrogen-rich gas is then recycled back for reuse in the reactor section. Any excess gas

from the gas separator vessel joins the sour gas from the stripping of the reaction product liquid.
The liquid from the gas separator vessel is routed through a reboiled stripper distillation tower. The
bottoms product from the stripper is the final desulfurized liquid product from hydrodesulfurization
unit.
The overhead sour gas from the stripper contains hydrogen, methane, ethane, hydrogen
sulfide, propane, and, perhaps, some butane and heavier components. That sour gas is sent to the
refinery's central gas processing plant for removal of the hydrogen sulfide in the refinery's
main amine gas treating unit and through a series of distillation towers for recovery of propane,
butane and pentane or heavier components. The residual hydrogen, methane, ethane, and some
propane is used as refinery fuel gas. The hydrogen sulfide removed and recovered by the amine gas
treating unit is subsequently converted to elemental sulfur in a Claus process unit or to sulfuric acid
in a wet sulfuric acid process or in the conventional Contact Process.
Note that the above description assumes that the HDS unit feed contains no olefins. If the feed does
contain olefins (for example, the feed is a naphtha derived from a refinery fluid catalytic cracker
(FCC) unit), then the overhead gas from the HDS stripper may also contain
some ethene, propene, butenes and pentenes, or heavier components.
It should also be noted that the amine solution to and from the recycle gas contactor comes from
and is returned to the refinery's main amine gas treating unit.

Catalysts and mechanisms[edit]

The main HDS catalysts are based on molybdenum disulfide (MoS2) together with smaller amounts
of other metals.[12] The nature of the sites of catalytic activity remains an active area of investigation,
but it is generally assumed basal planes of the MoS2 structure are not relevant to catalysis, rather
the edges or rims of these sheet.[13] At the edges of the MoS2 crystallites, the molybdenum centre
can stabilize a coordinatively unsaturated site (CUS), also known as an anion vacancy. Substrates,
such as thiophene, bind to this site and undergo a series a reactions that result in both C-S scission
and C=C hydrogenation. Thus, the hydrogen serves multiple rolesgeneration of anion vacancy by
removal of sulfide, hydrogenation, and hydrogenolysis. A simplified diagram for the cycle is shown:

Simplified diagram of a HDS cycle for thiophene

Catalysts[edit]
Most metals catalyse HDS, but it is those at the middle of the transition metal series that are most
active. Ruthenium disulfide appears to be the single most active catalyst, but binary combinations of
cobalt and molybdenum are also highly active.[14] Aside from the basic cobalt-modified MoS2 catalyst,
nickel and tungsten are also used, depending on the nature of the feed. For example, Ni-W catalysts
are more effective for hydrodenitrogenation.

Supports[edit]
Metal sulfides are "supported" on materials with high surface areas. A typical support for HDS
catalyst is -alumina. The support allows the more expensive catalyst to be more widely distributed,
giving rise to a larger fraction of the MoS
2 that is catalytically active. The interaction between the support and the catalyst is an area of

intense interest, since the support is often not fully inert but participates in the catalysis.

Hydrodenitrogenation[edit]
The hydrogenolysis reaction is also used to reduce the nitrogen content of a petroleum stream in a
process referred to as hydrodenitrogenation (HDN). The process flow is the same as that for an HDS
unit.

Using pyridine (C5H5N), a nitrogen compound present in some petroleum fractionation products, as
an example, the hydrodenitrogenation reaction has been postulated as occurring in three steps: [15][16]
Pyridine +
Hydrogen

Piperdine +
Hydrogen

Amylamine +
Hydrogen

Pentane
+ Ammonia

C5H5N + 5H2

C5H11N + 2H2

C5H11NH2 + H2

C5H12 + NH3

and the overall reaction may be simply expressed as:

Pyridine + Hydrogen

Pentane + Ammonia

C5H5N + 5H2

C5H12 + NH3

Many HDS units for desulfurizing naphthas within petroleum refineries are actually
simultaneously denitrogenating to some extent as well

Projects
Chemical Engineering Partners (CEP) licenses state of the art re-refining technology by providing basic
engineering package and optional detailed engineering services to clients world-wide. Some of the project
locations include:

LWART located in Lencois Paulista, Brazil

CEP provided basic engineering and hydrotreating technology for this
150,000 MT/A re-refinery built in Lencois Paulista, Brazil. This plant
design utilized the CEP Process including Wiped Film Evaporation and
Hydrotreating Technology. This is the only plant currently producing API
Group II base oil in South America. LWART successfully started
production in October, 2012.

Universal Lubricants located in Wichita, Kansas, USA

CEP provided basic engineering, hydrotreating technology and detailed
design for this 40,000 MT/A (12 million gallons per year) re-refinery
built in Wichita, Kansas. This plant design utilized the CEP Process
including Wiped Film Evaporation and Hydrotreating Technology.
Modular fabrication was used to reduce capital costs. This plant
successfully started up in October, 2009.

L&T Recoil facility located in Hamina, Finland

CEP provided basic engineering and re-refining technology for this
60,000 MT/A plant. The CEP Process was used including Wiped Film
Evaporator and Hydrotreating for this state of the art plant in Hamina,
Finland. This plant started up in August, 2009.

Heartland Petroleum facility located in Columbus,

Ohio, USA
CEP provided basic engineering and hydrotreating technology for this
plant built in Columbus, Ohio. The Heartland plant is an example how
the CEP hydrotreating process can be integrated into a new or existing
non-hydrotreating process. This plant successfully started in April,
2009.

Evergreen Oil Inc. Line 2 located in Newark,

California, USA
After 24 years of operation of Line 1, Evergreen Oil expanded their
capacity, by adding a second line at the same location. Line 2 was
designed using all the advancements and improvements made to Line
1. Line 2 successfully started operation in 2010.

Olein Recovery Corporation - Puerto Rico Re-Refining Facility

CEP provided basic engineering, hydrotreating technology, material supply and detailed design for this
plant built by Olein in Puerto Rico. This plant started up successfully in 2006.

PAZ facility located in the Middle East

CEP has licensed the Thin Film Evaporation technology and engineering
services to its client to produce an effective and profitable re-refining site in
the Middle East.

Southern Oil facility located in Wagga Wagga,

Australia
CEP has provided its' Thin-Film Evaporation technology to Southern Oil
in Wagga Wagga, NSW, Australia. This plant has been in operation
since 2001.

WGI facility located in Bekasi, Indonesia.

Chemical Engineering Partners has designed and licensed our Thin
Film Evaporation and Hydrotreating technology to WGI in Indonesia
who has been successfully operating since 1995.

Evergreen Oil Inc. Line 1 located in Newark,

California, USA
CEP is the engineering affiliate of Evergreen Oil Inc. Evergreen owns
and operates a state-of-the-art re-refinery in Newark, California,
approximately 30 miles south of San Francisco. This re-refinery has
been in operation since 1986 and utilizes both the CEP Thin Film
Evaporation and Hydrotreating processes. CEP engineers provide
engineering support to this plant and help optimize operation (reliability
and yield improvement).

Technology Overview
The first step in the process is feedstock analysis and selection. Regulatory requirements in the USA
prohibit the processing of used oil with excessively high levels of Polychlorinated Biphenyls or Chlorides.
Process considerations require evaluation of feedstock to ensure that it is suitable for re-refining. Each
load of used oil is tested before being accepted by the re-refinery.
The second step of the process is chemical treatment to reduce fouling in the process equipment. Used
oil is difficult to process. The presence of additives and contaminants makes it very difficult to employ
conventional petroleum processing techniques without accelerated fouling and coking in process vessels
and heat exchangers. We have developed technology to address these problems and we achieve good
run length with our equipment before it must be cleaned due to fouling and coking. As additives packages
and lube oil properties have evolved over the years we have adjusted our processing techniques to
maintain good performance.
The third step in the process is to remove water and light hydrocarbons such as fuel that has been picked
up by the used oil. In some cases it is possible to use the light hydrocarbon by-products as plant fuel. This
is determined by local environmental regulations. If local regulations do not permit the use of these byproducts as plant fuel they can be sold as fuel.

The fourth step of the process is removal of catalyst poisons before the hydrotreating step. Some
additives and contaminants in used oil are detrimental to the hydrotreating catalyst. Rapid deactivation of
the hydrotreating catalyst occurs when these poisons are present. Extensive research and analysis was
conducted by our company to identify the compounds that contribute to catalyst deactivation. Proprietary
technology was then developed to remove the catalyst poisons and extend catalyst life.
The fifth step of the process is to separate the base oil from the additives and high boiling hydrocarbons.
A wiped film evaporator operating under vacuum is used to achieve this separation. The vacuum allows
separation at temperatures below oil cracking temperatures. The lower temperatures and short residence
time in the wiped film evaporator minimize coking that occurs in other types of distillation equipment.
The sixth step is hydrotreating. Three hydrotreating reactors are used in series to reduce sulfur to less
than 300 ppm and increase saturates to over 90%, meeting the key specifications for API Group II base
oil. The use of CEP-HRX catalyst (and if necessary pilot testing) ensures the most successful
hydrotreating process.
The final step is vacuum distillation to separate the hydrotreated base oil into multiple viscosity cuts in the
fractionator.

References:
https://en.wikipedia.org/wiki/Hydrodesulfurization
http://ceptechnology.com/Projects
http://ceptechnology.com/Technology-Overview