A

SEMINAR REPORT

ON

HYDRODESULFURIZATION OF DIESEL

SUBMITTED IN PARTIAL FULFILLMENT FOR THE COURSE OF

BACHELOR OF ENGINEERING

IN

CHEMICAL ENGINEERING

SUBMITTED BY

DEVA MANOHAR SONAR

UNDER THE GUIDANCE OF

Dr. Mrs. K. S. DESHMUKH

DEPARTMENT OF CHEMICAL ENGINEERING

DATTA MEGHE COLLEGE OF ENGINEERING

AIROLI, NAVI MUMBAI- 400708.

(2017-2018)

1
 UNIVERSITY OF MUMBAI
DATTA MEGHE COLLEGE OF ENGINEERING
PLOTNO-98, SEC-3, AIROLI, NAVI MUMBAI-400 708

DEPARTMENT OF CHEMICAL ENGINEERING

CERTIFICATE

This is to certify that:

Mr. DEVA MANOHAR SONAR

Has successfully presented a seminar on

HYDRODESULFURIZATION OF DIESEL

in semester VII and submitted the report in partial fulfilment for the award of Bachelor of
Engineering in Chemical Engineering of University of Mumbai during academic year 2017-
2018.

Dr. Mrs. K. S. DESHMUKH INTERNAL EXAMINER

(Project/Seminar Guide)

Dr. Mrs.K.S. DESHMUKH Dr. S. D. SAWARKAR

(Head of Department-Chemical) (PRINCIPAL)

2
 ACKNOWLEDGEMENT

I am gratified to the Chemical Engineering Department, Datta Meghe College of Engineering

for giving me the opportunity for presenting a seminar on out
HYDRODESULFURIZATION OF DIESELin the final year as per the curriculum of
degree course of chemical engineering.

I am thankful to Dr. Mrs. K. S. DESHMUKH, my project/seminar guide for mentoring me

throughout the course and for sharing her valuable knowledge and time. She has been a
constant source of motivation, never expecting anything less than the best efforts. Without her
concern, advice and motivation it would have been difficult to complete the seminar.

I would like to further extend my gratitude to all the staff members of Chemical Engineering
Department. I would also like to thank all our faculty members and librarians for their kind
co-operation and support.

Last but not the least I would like to thank all our friends and family for their unconditional
support and help.

3
 TABLE OF CONTENTS

SR. NO. TOPIC PAGE

NO.
1 INTRODUCTION 5

2 PURPOSE OF DESULFURIZATION 8

3 TYPES OF DESULFURIZATION 13

4 CONCLUSION 30

5 REFERENCES 31

4
 CHAPTER 1

INTRODUCTION

The quality of life on earth is linked directly to the overall quality of the environment. The
natural ecosystem encompasses all living and non-living things existing on earth naturally. It
is the environment that interacts with all living species. Petroleum hydrocarbons belong to the
most widespread contaminants of soil, air and water. The largest and most widely used energy
source in the world is crude oil. However, it contains sulphur usually in the form of organic
sulphur compounds. Sulphur compounds exist in various forms and can be classified into four
main groups: mercaptans, sulphides, disulphides and thiophenes. It is an undesirable
component because it forms sulphur dioxide (SO2) during fuel oil combustion. The

combustion of sulphur compounds are not only causing corrosion but also contributing
considerably to acid rains and air pollution, deforestation, smog, and global warming, as well
as several human health concerns such as cardiovascular disease, cancer, creation of asthmatic
symptoms and other respiratory diseases. The simplest way to decrease the amount of SO2

emitted into the air is to reduce the amount of sulphur in fuel. Hence, desulphurization of
diesel oil is essential to overcome these challenges.

At present, oil desulphurization technology is broadly divided into two categories, which are
hydrodesulphurization (HDS) and non-hydrogenation hydrodesulphurization (NHDS). HDS
is used to remove sulphur from hydrocarbons in petroleum refineries that requires either
increasing reactor residence time, or carrying out reactions under high temperature and
pressure. The catalysts used in HDS are not active in removing refractory sulphur compounds
like thiophenes and its derivatives. These compounds require high hydrogen and energy

5
consumption in the HDS process. Non-HDS technology is a reverse case as it does not require
hydrogen and energy consumption. Adsorption is the most common HDS alternative method
currently used to achieve ultra-clean fuels. It is often employed to remove trace impurities,
such as the removal of trace amounts of aromatics from aliphatics, and metal oxides are the
adsorbents utilized in petroleum processing industries for the desulphurization of diesel oil.
HDS is however an expensive process in terms of utilizing expensive operating conditions i.e.
high temperature, high pressure of hydrogen gas and expensive catalyst, as well as it is
inefficient to eliminate the sterically hindered sulfur compounds and thereby cannot achieve
ultralow levels of sulfur in the product fuels . An alternative to HDS process the
desulfurization through adsorption, wherein sulfur compounds are selectively removed
through adsorption on the solid adsorbent leaving behind sulfur free fuel. However the process
is in the juvenile stage and in order to be recognized as a commercially acceptable process
researchers are striving to increase its efficiency. New Federal regulations require the removal
of sulphur in both gasoline and diesel to very low levels, forcing existing technologies to be
pushed into inefficient operating regimes.

6
 HISTORY

Although some reactions involving catalytic hydrogenation of organic substances were

already known, the property of finely divided nickel to catalyze the fixation of hydrogen on
hydrocarbon (ethylene, benzene) double bonds was discovered by the French chemist Paul
Sabatier in 1897.Through this work, he found that unsaturated hydrocarbons in the vapor
phase could be converted into saturated hydrocarbons by using hydrogen and a catalytic
metal, laying the foundation of the modern catalytic hydrogenation process.

Soon after Sabatier's work, a German chemist, Wilhelm Norman, found that catalytic
hydrogenation could be used to convert unsaturated fatty acids or glycerides in the liquid
phase into saturated ones. He was awarded a patent in Germany in 1902 and in Britain in
1903, which was the beginning of what is now a worldwide industry.

In the mid-1950s, the first noble metal catalytic reforming process (the Platformer process)
was commercialized. At the same time, the catalytic hydrodesulfurization of the naphtha
feed to such reformers was also commercialized. In the decades that followed, various
proprietary catalytic hydrodesulfurization processes, such as the one depicted in the flow
diagram below, have been commercialized. Currently, virtually all of the petroleum
refineries worldwide have one or more HDS units.

By 2006, miniature microfluidic HDS units had been implemented for treating JP-8 jet fuel
to produce clean feed stock for a fuel cell hydrogen reformer. By 2007, this had been
integrated into an operating 5 kW fuel cell generation system.

7
 PURPOSE OF DESULFURIZATION

Diesel fuel is a multi-purpose petroleum fuel used in trucks, trains, boats, buses, planes,
heavy machinery and off-road vehicles. It also remains one of the largest sources of fine
particle air pollution, which has serious health impacts. Besides fine particles or soot, Diesel
fueled engines also emit nitrogen oxides that can form ground level ozone. Beginning in
2001, the U.S. Environmental Protection Agency (EPA) passed rules requiring use of ultra-
low sulfur diesel (ULSD) fuel in diesel engines like trucks and buses, construction
equipment, and more recently, stationary sources.

Ultra-low sulfur diesel (ULSD) has only 15 parts per million (ppm) of sulfur. Low sulfur
fuel has 500 ppm sulfur and uncontrolled sulfur diesel may have levels much higher [34-37].
The use of ULSD fuel in conjunction with re-designed advanced emission-control devices
lowers the levels of released hydrocarbons, sulfur and nitrogen compounds, along with
harmful particulate matter, to almost zero. Nitrogen oxides chemically react to form a lower-
atmosphere ozone layer and contribute to acid rain. Burning ULSD fuel greatly cuts the
amount of sulfur dioxide, a major contributor to acid rain. The oxides rise high into the
atmosphere, lowering the pH of rain drops.

Forms Sulphur dioxide (SO2) during fuel oil combustion (greenhouse gas).

Contributing considerably to acid rains and air pollution, deforestation, smog, and global
warming.

Several human health concerns such as cardiovascular disease, cancer, creation of asthmatic
symptoms and other respiratory diseases.

Sulphur compounds also deactivate some catalysts used in diesel oil processing.

8
 EFFECTS OF SULFUR DIOXIDE

The SO2 is hygroscopic, when it is in the atmosphere it reacts with humidity and forms
sulphuric and sulphurous aerosol acid that is later part of the so-called acid rain. The intensity
in the formation of aerosols and the permanence of them in the atmosphere depend on the
meteorological conditions and the quantity of catalytic impurities (substances that accelerate
the processes) present in the air. But in general, the average time of permanence in the
atmosphere is around 3-5 days, so it can be transported to greater distances.

The air pollution by SO2 has the following effects on human beings:

9
 Corneal haze
Breathing difficulty
Airways inflammation
Eye irritation
Psychic alterations.
Pulmonary oedema.
Heart failure.
Circulatory collapse.

Sulphur dioxide is also associated with asthma, chronic bronchitis, morbidity and mortality
increase in old people and infants.

Sulphur is a highly noxious venom for people's health, although we can be more resistant than
other creatures that live with us. For example, the level of 0.3 g per cubic metre of air implies
a potential risk for human health, but for trees, 0.2 g is extremely dangerous. Because of that,
sulphur oxides (SOx) and sulphuric acid (HSO4) are related with the damage and destruction
of vegetation, soil deterioration, construction material and watercourses.

The recommended air quality standards for sulphur dioxide are:

0.20 parts per million (ppm) for a 1-hour exposure period

0.08ppm for a 24-hour exposure period
0.02ppm for an annual exposure period.

These standards are designed to protect sensitive individuals, such as children and
asthmatics.

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Images giving us more hazardous effects of Sulphur Dioxide: -

11
12
 CHAPTER 2

TYPES OF DESULPHURIZATION

ABSORPTIVE DESULPHURIZATION

EXTRACTIVE DESULPHURIZATION

BIO-DESULPHURIZATION

HYDRODESULPHURIZATION

13
 ABSORPTIVE DESULPHURIZATION

Adsorption can be used for desulfurization of petroleum fractions based on the ability of
solid adsorbent material to selectively adsorb organic sulfur compounds. There are two types
of adsorptive desulfurization: adsorptive desulfurization during which physical and/or
chemical adsorption of organic sulfur compounds takes place on the surface of the adsorbent,
and reactive adsorption desulfurization during which organic sulfur compounds react with
chemical species on the surface of the adsorbent and the sulfur is chemically bound, usually
in the form of sulfide, while the newly formed hydrocarbon compound is released into the
stream.
Adsorption is one of the methods which can be used to achieve ultra-low sulfur content in
diesel fuel. It is considered the most effective method for the removal of the trace amounts of
residual sulfur in fuels after HDS treatment. . The idea behind this approach is to selectively
separate less than 1 wt% of fuel mass using selective adsorption for removing sulphuric
compounds and leave the 99 wt.% of nonsulfur-containing fuel mass untouched. In this work
desulfurization of diesel fuel was carried out in a batch adsorber system.

14
 The above diagram shows the schematic representation of the ADU.

Absorptive desulphurization using a low-cost absorbent-

Raw materials:

Diesel was bought locally from one petrol station in Nasik, (Bharat Petroleum) and
Neem leaves were collected from nearby trees.

Adsorbent:

Neem leaves were collected from local source. They were washed with tap water,
distilled water to be free from dirt and allows drying in an oven at 75C for 24 hours,
grinded and sieved. Fractions of maximum size of 106 micrometer were collected
and kept in close jar.

Batch Adsorption Study:

All the adsorption experiments were carried out at 283, 288 and 293K with different
initial concentrations. An equal amount (2g) of Neem leaves powder was introduced
into 100mL bottles and10mL of Diesel was added to each bottle and shaken for 3.5h.

15
 Immediately after this, the sample was filtered and the clear solution (filtrate) was
analyzed using a spectrophotometer.

The following conclusions were deduced from these graphs below-

A graph of Sulphur content vs time measured in hours-

A graph of amount of Sulphur removal in percentage vs time-

16
 Effect of temperature vs Sulphur removal in percentage-

17
 CONCLUSIONS AND RESULT

The desulphurization of diesel oil by adsorption process using neem leaves powder
shows a reduction in the amount of Sulphur by more than half of the original amount
of Sulphur. The optimal conditions were recognized as contact time of 3.5hrs and
dose of neem leaves powder of 2gm in 10ml of diesel at temperature of 20 OC was
obtained.

The effect of different temperatures on adsorption process has been observed which
shows that temperature favors the percentage removal of Sulphur in Diesel which
represents the nature of process as an endothermic process, since with the increase in
time and temperature, concentration of Sulphur removal also increases & maximum
removal of Sulphur is 65% at 20-degree C.

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 EXTRACTIVE DESULPHURIZATION

EDS is a liquid-liquid extraction process and is the most widely studied alternative
desulfurization technology. Liquid-liquid extraction process.
The driving force for this process is solubility, the components to be removed
preferentially 16 migrates to the liquid where they have the greatest solubility.
In an EDS process sulfur compounds are removed from fuels by contacting the fuel
with a suitable solvent.

Extraction can be used for desulfurization because of higher solubility of organic Sulphur
com- pounds in appropriate solvent than other hydrocarbons present in a petroleum fraction.
The organic Sulfur compounds are removed from the feed into the solvent, after which the
mixture of sulfur rich solvent and feed is separated. [1] CHU Xuemei et.al have studied
Desulfurization of Diesel Fuel by Extraction with [BF4]based Ionic Liquids. Authors have
systematically investigated the extractive removal of sulfur compounds from Dongying and
Liaohe diesel fuels with [BF4] based ionic liquids. T. Adamiet.al.reported the Extractive
desulfurization of FCC gasoline with two solvents (sulfonate and furfural). Authors carried
out different experiments for determination of suitable.

solvent regarding the process parameters including temperature, batch time, solvent / FCC
gasoline ratio and extraction times. They investigate that maximum desulfurization
efficiency isobtained at high levels of temperature and sulfolane / FCC gasoline ratio; time
in researched range of values had small impact and minimum sulfur content in raffinate of
196 mg kg-1 was obtained at higher levels of temperature, time and sulfolane / FCC
gasoline ratio. Authors also developed mathematical model for predicting sulfur content in
raffinate after extractive batch process with sulfolane and proven with analysis of variance.
Wang Haojie et.al. Deep Extractive Desulfurization of Gasoline with Ionic Liquids Based on
Metal Halide Ionic liquid. Different desulfurization activity of ionic liquid is tested by
authors. Investigators also reported that FCC gasoline could be obtained after three
extraction runs at an ionic liquid/oil volume ratio of 0.1, with the yield of FCC gasoline
reaching 94.3%. And the ionic liquid could be recycled 5 times with merely a slight
decrease in activity. Desulfurization of Liquid Fuels by Selective Extraction Method studied
by K. Abinaya. Author investigates various new approaches for desulfurization of ultra
clean gasoline, diesel and other liquid fuels by extraction with ionic liquids. And
investigator also investigates extraction method deep sulphur reduction by using various
ionic liquid.

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 ADVANTAGES OF EDS

EDS has a number of advantages over the conventional HDS technology.

Firstly this process does not require severe operating conditions;
it operates at ambient pressure and temperature.
Secondly there is no H2 consumption and a need of expensive
catalysts, thus the process is economical.

20
 Extraction can be used for desulfurization because of higher solubility of organic
sulfur compounds in appropriate solvent than other hydrocarbons present in a petroleum
fraction. The organic sulfur compounds are removed from the feed into the solvent, after
which the mixture of sulfur rich solvent and feed is separated.
Ionic liquids (IL) have been recognized as novel designable solvents (i.e., their properties
can be tuned by altering their ionic structures to meet specific demands), which are liquids
over a wide temperature range including room temperature. One of the most important
advantages is that ionic liquids can be tuned/controlled by tailoring their cationic and
anionic structures to optimize their physicochemical properties. As a kind of extraction
solvent, IL does not remain in the organic phase, which can be greatly convenient for
separation [8], and therefore, the desulfurization using ionic liquids has received growing
attention. [BF4] -based ionic liquids are promising extractants in future industrial
applications because of their low viscosities and wide liquid ranges.

21
 BIODESULPHURIZATION

Biodesulfurization also often referred to as microbial desulfurization is an

environmentally friendly, biological process that can be used to remove sulfur from
fuels
This technology appears as a viable complementary process to HDS.
It requires mild operating conditions (i.e. ambient temperature and pressure), thus
saving energy costs. Further energy cost cuts are due to the fact that the bio
desulfurization process reduces the need for hydrogen.

Biodesulfurization is a process that removes organic sulfur compounds from fossil

fuels using enzyme-catalyzed reactions. Biocatalytic sulfur removal from fuels has
applicability for producing low sulfur gasoline and diesel fuels. Microbial desulfurization or
biodesulfurization is described as the process by which the use of a catalyst of biological
nature enables the removal of sulfur content in oil fractions at moderate pressure and
temperature conditions. Given its specificity, it is presented as a promising alternative for
the removal of organic-sulfured molecules resistant to conventional technologies, such as
dibenzothiophenes and their substituted forms (Monticello, 1998). Development of a
biodesulfurization process includes the isolation and production of the biocatalyst
(microorganism or enzyme), the desulfurization reaction (non-aqueous bio catalysis), and
finally, the separation of products and quality controls. Most recent papers in this area
describe significant efforts intended to isolate new desulfurizing microorganisms as well as
the genetic improvement of such microorganisms.

22
 In the same way, significant advances are observed worldwide in terms of bio
catalysis in the organic or anhydrous phase and in the field of bioengineering as a whole,
where concepts of metabolic engineering (biocatalyst design), construction of new
bioreactors and development of sophisticated separation systems are combined These
microorganisms transform Dibenzothiophene (DBT) into 2-hydroxybiphenyl (2-HBP),
which remains in the organic phase while the sulfur is eliminated in the form of inorganic
sulfate in the aqueous phase of the system.

Advantages of BDS
UNIT-

BDS process is that it is highly selective due to the involvement of

biological catalysts i.e. enzymes and also does not produce any
undesirable products.
The biodesulfurization technology has also been found to generate
only a fraction of the greenhouse gas emissions generated by HDS.
This technology can only be applied as a complementary process.
Not yet shown viable for commercial production.

23
 OXIDATIVE DESULPHURISATION

Oxidative desulfurization is a process during which organic sulfur compounds are oxidized
and subsequently removed from the feed by a separation method. The methods used for
separating oxidized sulfur compounds from treated fuel feeds include extraction, adsorption,
distillation, and thermal decomposition.

ODS offers several advantages compared with HDS. For example, the refractory-substituted
dibenzothiophenes (DBTs) are easily oxidized under low temperature and pressure
conditions so expensive hydrogen is not required and, therefore, the capital requirement for

24
an ODS unit is significantly less than that for a deep HDS unit. As the use of expensive
hydrogen is avoided, these processes are more suitable for small and medium size refineries;
especially those that are isolated and not located close to a hydrogen pipeline. The properties
of sulfur and carbon are similar in some ways, e.g., the electronegativity of sulfur is very
similar to that of carbon. Therefore, the sulfur-carbon bond is relatively non-polar and
sulfur-containing compounds exhibit properties quite similar to their corresponding organic
compounds. This is the reason why the solubilities of sulfur-containing compounds and
hydrocarbons in polar and non polar solvents are nearly identical. However, if these sulfur-
containing compounds that are present in fuels could be oxidized to their corresponding
sulfoxides or sulfones their solubility in polar solvents would increase with an increase in
their polarity. The electronic d-orbitals of sulfur are available for the oxidation of sulfur-
containing compounds that will react with oxidants relatively easily. The dipole moment of
the oxidized sulfur-containing compounds increases and they are more soluble in polar
solvents.

Generally, desulfurization by selective oxidation involves two main steps: First, the sulfur-
containing compounds present in diesel are oxidized to the corresponding sulfoxides and
sulfones by an oxidant, and then these sulfoxides and sulfones are removed from diesel by
extraction, adsorption, or distillation. The major organic acids used in ODS are acetic acid
and formic acid.

Due to increasingly strict environmental protection regulations, producers of motor fuels

have been forced to improve existing processes and investigate new alternative methods of
removing sulphur from motor fuels. By lowering the sulphur content with the process of
oxidative desulphurization, apart from directly decreasing the negative impact on the
environment, an improvement in product quality and significant cost effectiveness has been
achieved. The level of sulphur content in the fuel specifications has been dramatically
decreased from 2000 mg kg1 to 10 mg kg1 in the last twenty years13. The oxidative
desulphurization process, as one method of producing diesel fuel with very low sulphur
content, includes the formation of oxidized sulphur compounds (sulphoxides and sulphones)
in contrast to the hydrodesulphurization where the sulphur compounds are reduced with the
formation of hydrogen sulphide.

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 The oxidative desulphurization process (ODS) includes two steps: the oxidation of sulphur
compounds present in diesel fuel, such as dibenzothiophene, into corresponding sulphoxides
and sulphones, and easy removal of the formed sulphones by extraction (or adsorption) due
to their high polarity46. In the ODS process, dibenzothiophene can be easily oxidized
under mild reaction conditions (low reaction temperature, low pressure) and without the use
of hydrogen, which renders the process financially feasible. Since the use of expensive
hydrogen is avoided, the process is applicable to small and medium-sized refineries,
especially refineries located far from the source of hydrogen6,7. Recently, several oxidation
systems8 have been studied, and hydrogen peroxide has been considered a powerful oxidant
of sulphur compounds911. In this study, the oxidative desulphurization of real diesel fuel
was investigated in the catalyst/oxidant system (acetic acid / hydrogen peroxide) in a 70 mL
batch reactor. Based on previous experiments with model diesel fuel, the influential
parameters were investigated on real diesel samples enriched with dibenzotiophene.
Furthermore, sulphur removal was investigated at different parameters in the oxidation
process (sulphur concentration in feedstock, temperature, reaction time) and at optimal
values of extraction parameters.

HYDRODESULPHURIZATION

Hydrodesulphurization (HDS) is the most widely used chemical process for the
removal of sulfur compounds from diesel fuels.
HDS consists of catalytic hydro treating with Cobalt Molybdenum (Co-Mo/Al2O3).
During this catalytic process the organic sulfur compounds (S-compounds) are
converted to hydrogen sulfide (H2S) and the corresponding hydrocarbons.

Hydrodesulfurization (HDS), a mild form of hydro cracking, is a refining process used for
removing organic sulfur compounds from petroleum fractions. Hydrodesulfurization (HDS)
is a catalytic chemical process by which sulfur (S) is removed from natural gas and from
refined petroleum products like petrol, jet fuel, kerosene, diesel fuel and fuel oils in the form

26
of hydrogen sulfide or sulfur dioxide. This process is used to upgrade the octane rating of the
naphtha streams.Fuels obtained through hydrodesulfurization reduce sulfur dioxide emissions
in automotive vehicles, aircraft, trains, ships, gas or oil burning power plants, residential and
industrial furnaces and other forms of fuel combustion.Sulfur converted to oxides causes
major corrosion problems. The original organosulfur compounds in petroleum can also cause
corrosion of engines.

The industrial hydrodesulfurization processes include facilities for the capture and removal of
the resulting hydrogen sulfide gas. In petroleum refineries, the hydrogen sulfide gas is then
subsequently converted into byproduct elemental sulfur or sulfuric acid.

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 cobalt and molybdenum (usually called a CoMo catalyst) catalyst.
Occasionally, a combination of nickel and molybdenum (called NiMo) is used, in addition to
the Co,Mo catalyst, for specific difficult-to-treat feed stocks, such as those containing a high
level of chemically bound nitrogen.

Schematic diagram for hydrodesulphurization unit-

27
Process description: -

TEMP AND PRESSURE: - 350C AND 30 to 100 bars.

The H2S formed during the catalytic reaction is separated from the
desulfurized fuels and then converted into elemental sulfur (S)
usually by the Claus process.
The hydrodesulphurization process is unsuitable for ultra-deep
desulfurization
High opt. conditions lead to high operating costs.
High temperatures also increase coke formation in the refining process
and also lead to an increase in the deactivation rate of the catalyst.
High pressures on the other hand cause increased side reactions i.e.
saturation of olefins.

28
Process chemistry: -

Hydrogenation is a class of chemical reactions in which the net result is the addition of
hydrogen (H). Hydrogenolysis is a type of hydrogenation and results in the cleavage of the
C-X chemical bond, where C is a carbon atom and X is a sulfur (S), nitrogen (N) or oxygen
(O) atom. The net result of a hydrogenolysis reaction is the formation of C-H and H-X
chemical bonds. Thus, hydrodesulfurization is a hydrogenolysis reaction. Using ethanethiol
(C
2H
5SH), a sulfur compound present in some petroleum products, as an example, the
hydrodesulfurization reaction can be simply expressed as

For the mechanistic aspects of, and the catalysts used in this reaction see the section
catalysts and mechanisms.

Process description: -

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.

29
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.

30
 CHAPTER 3

CONCLUSION

1. We compared different desulfurization methods.

2. Drawbacks of the conventional HDS can be avoided by using
alternative processes according to necessary process
parameters.
3. The process of sulphur removal can be optimized to great
extent.
4. Different crude sources have different sulfur contents and
therefore different treatment methods should be employed.
5. Ultimately low sulfur content results to cleaner and
better environment.

31
 REFERENCES

Hydrodesulfurization and hydrodenitrogenation: chemistry and engineering by,

Toshiaki Kabe, Weihua Qian, Atsushi Ishihara.

https://en.wikipedia.org/wiki/Hydrodesulfurization

Desulphurization Techniques for Liquid Fuel a Review- http://www.ijetmas.com/

Modern desulfurization methods used in waste incineration equipment,

Martyna NIESLER1, Katarzyna VORBRODT-STRZAKA2-

http://awmep.org/?journal=ago

Modern petroleum refining processes by B.K. Bhaskara Rao Fourth edition.

Recent Advances in the Science and Technology of Desulfurization of Diesel Fuel Using
Ionic Liquids by Elaheh Kowsari.

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33