INTRODUCTION

1.INTRODUCTION
1.1 GENERAL

As the petroleum resources are depleting and the crudes being

refined are becoming higher in density and have higher content of hetero
atoms (S,O,N etc) the need and demand for high-quality middle distillates
has grown significantly over the past decade and continues to grow in the
international market.
Stringent environment legislation regarding fuel specifications has
been imposed worldwide over the last decade in order to improve the
quality of diesel fuels with a view to reduce oxides of sulphur(SO X), oxides
of nitrogen(NOX) and particulate matter (PM) in the diesel engine exhaust
emissions which are major contributors to environmental pollution. In
order to meet the increased demand for

on-road diesel, the refiners use

heavy distillates as blending components into the diesel pool. For the above
reasons, the refining industry today faces on the one hand tighter
specifications and on the other hand higher production demands for diesel.
As a result, refiners worldwide have started revamping or optimising the
existing middle-distillate hydrotreaters to achieve deep desulphurisation.
The tightening of diesel fuel specifications began in 1993 when the
USA lowered sulphur to 500ppmw maximum. The California Air
Resources Board (CARB) went one step further by mandating a maximum
aromatic level as well as a minimum cetane level. Similar specifications
2

are being considered by the European Commission (EC), which requires

a maximum of 50ppmw sulphur as well as maximum cetane and
minimum polyaromatic levels. Germany is also considering tax incentives
to encourage refiners to produce and market diesel fuel with 10ppmw
sulphur.
In December 2000, the US Environmental Protection Agency (EPA)
introduced a new mandate to further reduce the level of sulphur in on-road
diesel by 97 percent (to 15ppmw maximum) starting in mid-2006.
In a typical refinery, diesel fuel is produced from one or more
blending components derived from crude distillation and conversion units.
The main blending components are heavy naphtha, straight run diesel,
hydrocracker diesel, Light Cycle Oil (LCO) from fluid catalytic cracker
(FCC), Coker diesel etc.
The desirability of these streams (for example LCO) would require
much more severe treating then others eg: Straight Run Light Gas Oil
(SRLGO).
The technologies for removing sulphur are not necessarily the same
as the technologies required to upgrade other diesel fuel qualities. In the
opinion of many refiners and process vendors, the technologies for
removing sulphur from diesel fuel are probably the least expensive and
easiest to implement compared to those required to upgrade other diesel
fuel qualities.
At present, the most common diesel sulphur specifications
worldwide are around 500ppmw. However, the sulphur specifications are
being revised in many of the countries conforming to Euro-III/Euro-IV
specifications. In India, BUREAU OF INDIAN STANDARDS (BIS) has
3

laid down specification for auto fuels. Inline with global specification,
India has also reduced diesel fuel sulphur level from 1.0 wt%
(10000ppmw) down to 350ppmw (Euro-III or Bharat-III equivalent norms)
over the last decade and is likely to be reduced further to 50ppmw (EuroIV or Bharat-III equivalent norms) by April 1, 2010.
Initially, the diesel hydrodesulphurisation units in India were
designed to produce 500ppmw sulphur that consists of two reactors
operating in series. The typical operating conditions of the industrial units
are as follows: reactor temperature of 340oC,Reactor pressure of 40kg/cm2,
LHSV of 2.0h-1 and hydrogen-to-oil ratio of 200L/L
Current diesel specifications in India and proposed changers are
compared with Euro-III and Euro-IV specifications in table 1.1.

Table 1.1 Existing and future specifications of diesel

Characteristics
Density @ 15o C , kg/cm3
Kinematic viscosity @ 40o
C,cSt
Flash point, o C
Pour point , oC, max.,
Winter
Summer
Cetane Number, min
Cetane Index , min
RCR on 10 % Residue
max.
Total Sulphur, wt.% max.
Polycyclic Aromatic
Hydrocarbon (PAH), wt.%
, max.
Distillation , 95 vol.%
Recovery@ oC, max.

Bharat-III
(current)
820-845
2.0-4.5

BharatIV
820-845
2.0-4.5

Euro- III

Euro- IV

820-845
2.0-4.5

820-845
2.0-4.5

35
3
15

35
-

35
-

51
46
0.3

51
-

51
46
0.3

51
48
0.3

0.035
11

0.005
11

0.035
11

0.005
11

370

360

360

360

1.2. CRUDE ASSAY

Crude oil is defined as the mixture of naturally occurring
hydrocarbons that is refined in to diesel, gasoline, heating oil, jet
fuels, kerosene and literally

thousands of

other products

called

petrochemicals. Crude oil are named according to their contents and

5

origins, and classified according to their per unit

weight (specific

gravity). Heavier crudes yield more heat upon burning, but have
lower API gravity and market price in comparison to light (or sweet)
crudes.
1.2.1 COMPOSITION OF CRUDE OIL

The composition of crude oil varies according to where it was

obtained. This largely has to do with the type of ground in which
the oil was formed, and what contaminants were present and in what
relative concentrations. In addition to colour variations, there are also
various contaminant levels and various flowing properties. Variations
aside, crude oil, on average, has the composition shown below.
Carbon (C)

84-89

Hydrogen (H) 11-14

Sulfur (S)

0.1-4.5

Nitrogen (N) 0.01-0.8

Metals

0.0-0.01

Crude oil is comprised of:

1.

Paraffins

2.

Oleffins

3.

Naphthenes
6

4.

Aromatics

1.2.2 TYPES OF CRUDE

The different Types of Crude oil have variations in viscosity
and appearance from one oil field to another. The variations range in
odour, color and in the basic properties and qualities. While all Types of
crude oil are basically hydrocarbons, there are differences in their
properties, especially in the variations in the molecular structure. The many
variations may also influence the suitability of the different types of crude
oil for particular products and the resulting quality of the products.
The different Types of crude oil are classified based on the
American Petroleum Gravity (API) gravity and viscosity. The properties
may vary in terms of proportion of hydrocarbon elements, sulfur content
etc as it is extracted from different geographical locations all over the
world. If the API gravity of the crude oil is of 20 degrees or less, it is
graded as 'heavy', those with an API gravity of 40.1 degrees or greater than
that is known as 'light' and if the oil ranges between 20 and 40.1 degrees, it
is graded as 'intermediate'. Classifications are made based on the sulfur
content as well. Crude oil with low content of sulfur means 'sweet' and the
presence of high content sulfur is known as 'sour'. The purity of crude oil
increases or decreases based on the sulfur content as sulfur is an acidic
material.

1.2.3.DISTILLATION COLUMN

Figure 1.2.3. distillation column

1.2.4.DESCRIPTION OF DISTILLATION PROCESS

8

The diagram above is a schematic flow diagram of a typical oil

refinery that depicts the various unit processes and the flow of intermediate
product streams that occurs between the inlet crude oil feedstock and the
final end products. The diagram depicts only one of the literally hundreds
of different oil refinery configurations. The diagram also does not include
any of the usual refinery facilities providing utilities such as steam, cooling
water, and electric power as well as storage tanks for crude oil feedstock
and for intermediate products and end products.
The atmosphric distillation unit

is the first processing unit in

virtually all petroleum refineries. It distills the incoming crude oil into
various fractions of different boiling ranges, each of which are then
processed further in the other refinery processing units.
The incoming crude oil is preheated by exchanging heat with some
of the hot, distilled fractions and other streams. It is then desalted to
remove inorganic salts (primarily sodium chloride).
Following the desalter, the crude oil is further heated by exchanging
heat with some of the hot, distilled fractions and other streams. It is then
heated in a fuel-fired furnace (fired heater) to a temperature of about
398 C and routed into the bottom of the distillation unit.
The cooling and condensing of the distillation tower overhead is
provided partially by exchanging heat with the incoming crude oil and
partially by either an air-cooled or water-cooled condenser. Additional heat
is removed from the distillation column by a pump around system as shown
in the diagram below.
9

As shown in the flow diagram, the overhead distillate fraction from

the distillation column is naphtha. The fractions removed from the side of
the distillation column at various points between the column top and
bottom are called sidecuts. Each of the sidecuts (i.e., the kerosene, light
gas oil and heavy gas oil) is cooled by exchanging heat with the incoming
crude oil. All of the fractions (i.e., the overhead naphtha, the sidecuts and
the bottom residue) are sent to intermediate storage tanks before being
processed further.
The reduced crude is sent to vacuum distillation , to obtain products
such as asphalt , wax, tar etc, The products obtained from distillation
column are processed in respective units.

1.2.5.MAJOR PRODUCTS
Petroleum products are usually grouped into three categories: light
distillates (LPG, gasoline, naphtha), middle distillates (kerosene, diesel),
heavy distillates and residuum (heavy fuel oil, lubricating oils, wax,
asphalt). This classification is based on the way crude oil is distilled and
separated into fractions (called distillates and residuum) as in the above
drawing.
Liquified

petroleum gas (LPG)

Gasoline (also known as petrol)

Naphtha

Kerosene and related jet aircraft fuels

10

Diesel fuel

Fuel oils

Lubricating oils

Paraffin wax

Asphalt and tar

Petroleum coke

11

LITERATURE REVIEW

12

2.LITERATURE REVIEW

2.1.GENERAL
Babich

and

Moulijin (2003)

reported

that

organosulfur

compounds are usually present in almost all fractions of crude oil

distillation. Higher boiling point fractions contain relatively more sulfur
and the sulfur compounds are

of higher molecular weight. The

reactivity of organosulfur compounds varies widely depending on their

structure and local sulphur atom environment. The low boiling crude oil
fraction

contains

mercaptans,

mainly the

aliphatic

organosulfur

compounds:

sulfides , and disulfides. They are very reactive in

conventional hydro treating processes and they can easily be completely

removed from the fuel. Other processes like merox can be applied to
extract mercaptans and disulfides from gasoline and light refinery
streams.
For higher boiling crude oil fractions such as heavy straight
run naphtha, straight run diesel and light FCC naphtha, the organosulfur
compounds

predominantly

contain
13

thiophennic

rings. These

compounds

include

thiophenes

and benzothiophenes and

their

alkylated derivatives. These thiophene containing compounds are more

difficult than mercaptans and sulphides to convert via hydrotreating. The
heaviest fractions blended to the gasoline and diesel pools are bottom
FCC naphtha , coke naphtha , FCC and coker diesel, contains mainly
alkylated

benzthiophenes,

alkylbenzthiophenes,

as

dibenzothiophenes

well

as

(DBT)

polynuclear

organic

and
sulphur

compounds,i.e. the least sulphur compounds in the HDS rection.

The reactivity of sulphur compounds in the HDS follows this order
(from

most

rective

thiophene>BT>alkylated

to

least

BT>DBT

reactive);
and

thiophene>alkylated

alkylated

DBT

without

substituents at the 4 and 6 positions>alkylated DBT with one substituent at

either the 4 or 6 position>alkylated DBT with alkyl substituents at the 4 or
6 position. Deep desulfurisation of the fuel implies that more and more of
the least reactive sulphur compounds must be converted.

2.1.LIETERATURE REVIEW ON HYDRODESULPHURISATION

PROCESS
The conventional HDS process is usually conducted over sulfided
Co-MO/Al2O3 and Ni-Mo/Al2O3cataylsts. Their performance in terms of
14

desulfurisation level, activity and selectivity depends on the properties of

the specific catalyst used , the reaction conditions, nature and
concentrations of sulphur compounds present in the feed stream, and
reactor and process design.
Chunsang song (2003) reported that the key

to ultra-deep

desulfurisation is the removal of refractory sulphur compounds from diesel

fuels.

These

compounds

are

higher

molecular

weight

dibenzothiophenes(DBTs) that contain substituents in positions adjacent

to the sulphur atom. In addition to straight-run gas oil , the light cycle oil
from fluid catalytic cracking of heavy oils is a major blend stock for diesel
fuels which tends to have the highest contents of refractory sulphur
compounds especially 4,6-dimethyldibenzothiophene (4,6- DMDBT), 4,6diehtylbenzothiophene(4,6-DEDBT),

4-methyldibenzothiophene

(4-

MDBT) and dibenzothiophene(DBT).

Knudsen et al.(1999) reported that about four times more active
catalysts are required to reduce the diesel fuel sulfur content from 500 to
50ppmw compared to a typical Co-Mo catalyst at constant LHSV and the
corresponding temperature increament is about 38C.
Knudsen et al. (1999) reported that the effect of process variables
such as LHSV, temperature, hydrogen partial pressure, hydrogen sulfide
15

partial pressure and hydrogen to oil ratio on catalyst activity applied to

deep desulfurisation could be predicted by a suitable kinetic expression.
They found that the equation 2.1 could be used to describe the kinetics of
Co-Mo and Ni-Mo catalysts for very deep desulfurisation of diesel. In the
expression for the rate of desulfurisation,the first term represents the direct
extraction route,which is enhanced by an increase of the hydrogen partial
pressure and inhibited by the presence of H2S. The second term represents
the hydrogenation route, which is also enhanced by an increase of
hydrogen partial
compounds,

pressure and inhibited

by the presence of aromatic

and in particular heterocyclic compounds (denoted by F in

the equation)

2.2.LITERATURE REVIEW ON CATALYST

For Co-Mo catalysts, the second term can to a good approximation
be neglected, and the rate constant k, can be determined by integration of
the expression. The partial pressure of hydrogen sulfide, P H 2S

can be

expressed in terms of the sulfur concentration C S , which means that an

explicit expression can be obtained for k. The rate constant of catalyst
type, temperature and feedstock

16

For Ni-Mo catalyst both terms are important, and the removal of
the inhibitors has to be solves simultaneously in the rate equation.
Lappas et al.(1999) carried out hydrodesulfurisation of LCO and
SRGO blend in a continuous flow, trickle bed hydrotreating pilot plant unit
using a commercial Co-Mo catalyst and investigated the effect of operating
parameters

(temperature,

pressure, weight hourly space velocity,

hydrogen-to oil-ratio) on sulfur removal and aromatics saturation and

reported that by decreasing the space velocity and by increasing the
temperature, the pressure and the hydrogen-to -oil-ratio , the product
density and the aromatics and sulfur content of diesel decreased.
Selakovic and Jovanovic (2001) carried out hydrodesulfurisation of
middle distillates with various blends of LGO-LCO and LGO-LVGO using
Co-Mo catalyst of different producers with product sulfur specifications
and determined the required severity in achieving low sulfur levels.
Lamourelle and Nelson (2001) discussed various means to produce
ultralow sulfur diesel products using new generation Ni-Mo and Co-Mo
catalyst combinations. They studied various revamp options for making
ultralow

sulphur diesel

from existing hydro treating units, hydrogen

strategy , reaction pathways , catalyst options.

17

Bhaskar et al. (2004) developed a three phase non-isothermal

heterogeneous model to simulate the performance of pilot plant and
industrial trickle bed reactors applied to the hydrodesulfurisation of diesel
fractions. The developed model was found to simulate the performance of
the industrial reactor adequately. The model was also applied to study the
influence of operating conditions on product quality.
Bhaskar et al. (2004) developed a three phase non- isothermal
heterogeneous model to stimulate the performance of pilot plant and
industrial trickle-bed reactors applied to the hydrodesulphurisation of diesel
fractions. The developed model was found to stimulate the performance of
the industrial reactor adequately. The model was applied to study the
influence of operating conditions on product quality.
The reactive reaction rates of various sulphur species are shown in
table 2.1. The more difficult sulphur species i.e. the substituted
dibenzothiophenes, have the highest boiling points and are more prevalent
in streams with high end points.

18

Table 2.1. Relative reaction rates and boiling points of various sulphur
species
Sulphur species

Relative Reaction

Boiling Point, oF

Rate
Thiophene
100
185
Benzothiophene
30
430
Dibenzothiophene
30
590
Methyl Dibenzothiophene
5
600-620
Dimethyl Dibenzothiophene
1
630-650
Trimethyl Dibenzothiophene
1
660-680
The basic reactions that take place during hydrodesulfurisaton are
as follows,
RH +H2S

Mercaptans

RSH + H2

Sulfides

R2SH + 2H2 2RH +H2S

Disulfides

RSSR + 3H2 2RH +2H2S

Aromatics

ArS +2H2 Aromatic + H2S ( excluding ring saturation)

Aromatic ring saturation is a reversible reaction that is controlled by

equilibrium.

19

Salvatore and Michael (2004) reported that desulphurisation

reactions can follow a number of paths, but two routes are generally
favoured under typical hydro treating conditions. The most common route
for removing sulfur is the direct extraction, or hydrogenolysis, reaction
(carbon-sulfur bond breakage). This mechanism is predominant when the
sulfur requirement is above 350ppm. At this level most of the sulfur in the
more

reactive

compounds

(up

to and

including non-substituted

dibenzothiophene) has been removed. Typically, conventional Cobaltmolybdenum (Co-Mo) catalysts and low-to-moderate reactor pressure are
applied to favour this reaction mechanism.
Salvatore and Michael (2004) reported that removing sulfur from
most difficult compounds such as 4,6-dimethyldibenzothiophene, generally
follows the hydrogenation route. It is easier to break the sterically hindered
carbon-sulfur bond if one of the aromatic rings is first saturated. Saturating
the ring changes the molecules spatial configuration and makes the sulfur
atom more accessible to react with the catalysts active sites. After the
aromatic ring is hydrogenated, the sulfur atom can be removed via
hydrogenolysis. Nickel-molybdenum (Ni-Mo) catalysts and higher pressure
help promote the hydrogenation reaction mechanism.

20

Bhaskar et al. (2004) reported that the hydrogenation route was

found to be slower than direct extraction for most of alkyl-substituted DBT
molecules but is much faster for sterically hindered DBTS.
Knudsen et al. (1999) reported that Co-Mo catalysts desulfurise
primarily via the direct extraction route. Ni-Mo catalysts, exhibit a higher
hydrogenation activity,

have a relatively

higher

selectivity for

desulfurisation via the hydrogenation route.

As compared with the Ni-Mo catalysts, the Co-Mo catalyst is not
as good for the removal of 4,6-DMDBT, but better than Ni-Mo catalyst for
removal of DBT and 4-MDBT.
Juarez et al. (1999) carried out hydrotreating of SRGO-LCO blends
to evaluate the effect of LCO on product quality at varied operating
conditions over a commercial Co-Mo catalyst and determined apparent
reaction orders and activation energies.
Bhaskar et al. (2000) reported that the revised specification of
diesel fuel can met by increasing the hydro treating capacity, operating the
existing units at high severity levels and using a modified higher activity
hydro desulphurisation catalysts .

21

FEED USED

22

3.DIESEL
Diesel is produced from the fractional distillation of crude oil
between 200 C and 380 C at atmospheric pressure , resulting in a
mixture of carbon chains that typically contain between 8 and 21 carbon
atoms per molecule.

The

best diesel fuels are straight-run

Stocks,

derived from simple distillation of crude oil.

3.1.COMPOSITION
Diesel is composed of about
(i) 75%

saturated hydrocarbons (primarily paraffins including n, iso,

and cycloparaffins),
(ii) 25%

aromatic

hydrocarbons

(including

naphthalenes

and alkylbenzenes).
The average chemical formula for common diesel fuel is C12H23, ranging
approximately from C10H20 to C15H28.

3.2TYPES OF DIESEL FUEL

In India we have two types of diesel fuels:
1. High speed diesel (HSD) used in automotive applications and
2. Light diesel oil (LDO) used in stationary applications
23

3.3.DIESEL PROPERTIES
Sulphur content
Affects wear, depsits, and particulate emmissions. Diesel fuels
contain varying amounts of various sulphur compounds which increase oil
acidity. Legislation has reduced sulphur content of highway fuels to 05%
by weight. Off road fuel has an average of 0.29% sulphur by weight.
Cetane number
A measure of the starting and warm-up characteristics of a fuel. In
cold weather or in service with prolonged low loads, a higher cetane
number is desirable. Legislation dictates the Cetane Index shoud be 40 or
above.
Aromatic content
By definition, aromatic content is characterised by the presence of
the benzene family in hydrocarbon compounds that occur naturally in the
refining of diesel fuel. In the chemical

make up of fuel, the heavier

aromatic compounds of toluene, xylene, and naphthalene are also present.

Limiting these aromatic compounds has the effect of reducing burning
temperature and thus NOX formation.

24

Cloud & pour point

Affect low-temperature operation. The cloud point of the fuel is the
temperature at which crystals of paraffin wax first appear. Crystals can be
detected by a cloudiness of the fuel. These crystals cause filters to plug.

API gravity
Related to heat content, affecting power and economy. Gravity is an
indication of the energy content of the fuel. A fuel with a high density (low
API gravity) contains more BTU's per gallon than a fuel with a low density
(higher API gravity).

API gravity

141.5
specific gravity at 60 o F

131.5
60o F

Ash
Measures inorganic residues - The small amount of noncombustable metallic material found in almost all petroleum products is
commonly called ash. Ash content should not exceed 0.02 mass percent.

25

Water sediment
Affect the life of fuel filters and injectors. The amount of water and
solid debris in the fuel is generally classified as water and sediment. It is
good practice to filter fuel while it is being put into the fuel tank. More
water vapor condenses in partially filled tanks due to tank breathing caused
by temperature changes. Filter elements, fuel screens in the fill pump, and
fuel inlet connections on injectors must be cleaned or replaced when they
become dirty. These screens and filters, in performing intended function,
will become clogged when using a poor or dirty fuel and will need to be
changed more often. Water and sediments should not exceed 0.1 volume
percent.

Viscosity
Affects injector lubrication and atomization. The injector system
works most effectively when the fuel has the proper "body" or viscosity.
Fuels that meet the requirements of 1-D or 2-D diesel fuels are satisfactory
with Cummins fuel systems.

26

Carbon residue
Measures residue in fuel - can influence combustion. The
tendency of a diesel fuel to form carbon deposits in an engine can be
estimated by various tests to determine the carbon residue after 90% of
the fuel has been evaporated .

3.4.INFERENCE
It is found that
1.

Specific gravity, flash point, viscosity, sulfur content, and

carbon residue increase with increase in service severity.

2.
The cetane number (which measures the fuels ignition
quality) decreases with increase in service severity. There is also a
decrease in volatility with increase in service severity.
3.
Properties are, however, inter-related and it is difficult to
isolate the effect of any single variable
4.
It is found that the self-ignition temperature of the normal
paraffins decreases as the length of the chain increases.
5.
Since the cetane rating of the fuel is a measure of the
ignition characteristics of the fuel, it can be concluded that the
heavier members of the paraffin family have higher cetane ratings.
6.
In fact, cetane, C16H34 (hexadecane) is the primary
reference fuel in the cetane scale with an arbitrary cetane rating of
100 while other normal paraffins have cetane ratings that vary
27

almost linearly with the length of the chain.

3.5.Characteristics of Hydrocarbons as Diesel Fuel
S.N

GENERAL

HYDROCARBON

CHARACTERISTICS

O
1.

FORMULA
n-paraffins

CnH2n+2

Low specific gravity & high

Iso-paraffins

(Straight chain)
cetane number
CnH2n+2
(Branch Same sp.gr as 1 but lower

Cycloparaffins

chain)
CnH2n

cetane no. & B.P.

Higher sp. Gr. Than 1 but

CnH2n-6

lower cetane number

Higher sp.gr & B.P but lower

CnH2n-12

cetane number than 1-3

Highest sp. Gr & B.P. &

2.
3.
4.
5.

Benzenes
Naphthalenes

lowest cetane no.

Important characteristics of diesel fuel
Knock characteristics-requires high cetane number
1.

Starting characteristics-requires high volatility but will give lower

power
2.

Smoking and Odor-high volatility will give better mixing and lower

smoke but also lower power

3.

Corrosion and Wear-due to presence of sulfur and ash

4.

Ease of Handling-should have low pour point and viscosity for ease

of handling but high flash and fire point for safety and fire hazard.
5.

Density, heat of combustion and cleanliness.

28

3.6.DIESEL FUEL SPECIFICATIONS

GENERAL
FUEL ASTM TEST GRADE LOW GRADE HIGH
CLASSIFICATION
METHOD
SULPHUR
SULPHUR NO.
NO. 1-D
2-D
Flash point0C Mm
D 93
Water and sediment, D 2709
vol, max.
Distillation
D 86
0
temperature,
C
recorded
Min
Max
Viscosity,
kinematic
0
mm2/S at 40 C
Max
D 86

38
0.05

52
0.05

288

282
338

288
1.3-2.4

338
1.9-4.1

Ash, Max
Sulphur wt, max

0.01
0.05

0.01
0.05

D 445
D 2622

29

HYDROTREATING

4.1HYDROTREATING

Hydrotreating (HDT) is a catalytic process , which effectively

removes sulphur and other impurities like nitrogen, oxygen and metals
from crude oil and petroleum distillates.
A refining process

for

treating

petroleum

atmospheric or vacuum distillation units (e.g.,

fractions

naphthas,

from
middle

distillates, reformer feeds, residual fuel oil, and heavy gas oil) and other
petroleum (e.g., cat cracked naphtha, coker naphtha, gas oil, etc.) in the
30

presence of catalysts and substantial quantities of hydrogen. Hydrotreating

includes desulfurization, removal of substances (e.g., nitrogen compounds)
that deactivate catalysts, conversion of olefins to paraffins to reduce gum
formation in gasoline, and other processes to upgrade the quality of the
fractions.
Hydrotreating applications include Hydrodesulfurisation (HDS) of
kerosene, Hydrodesulfurisation (HDS) of naphtha, Hydrodesulfurisation
(HDS )of diesel, hydrofinishing of lube oil base stocks, hydrofinishing of
wax etc.

4.2HYDROTREATING REACTIONS
The chemical reactions that are of primary interest in hydrotreating
include
1.
2.
3.
4.
5.
6.

Hydrodesulfurisation (HDS)
Hydrodenitrogenation (HDN)
Hydrodeoxygenation (HDO)
Hydrogenation of aromatic compounds
Saturation of olefins
Hydrodemetallation (HDM)

4.2.1.HYDRODESULPHURISATION
Hydrodesulfurization (HDS) is a catalytic chemical process widely
used to remove sulfur (S)

from refined petroleum products such as

gasoline or petrol, jet fuel, kerosene, diesel fuel. The purpose of removing
the sulfur is to reduce the sulfur dioxide (SO2) emissions that result from
using those fuels in automotive vehicles, aircraft, railroad locomotives,
31

ships, gas or oil burning power plants, residential and industrial furnaces,
and other forms of fuel combustion.
R-S-R + 2H2 RH + RH +H2S

4.2.2.HYDRODENITROGENATION
The hydrogenolysis reaction is also used to reduce the nitrogen
content of a petroleum stream and removes as ammonia in a process
referred to as hydrodenitrogenation (HDN). The rate of HDN reaction
was little lower than the rate of HDS reaction.
R=N-R+ 3H2 RH + RH

4.2.3.HYDRODEOXYGENATION
During hydrotreating, oxygen compounds in the form of naphthenic
acids, phenols, alcohols, aldehydes etc were also removed as water vapour
from the feed.
R-O-R + 2 H2 RH + RH +H2O

4.2.4.HYDRODEMETALLATION
Metals like nickel, vanadium, iron, copper, sodium etc present in
traces get adsorbed over the catalyst
32

R-M + H2 + A RH + M-A

4.2.5.HYDROGENATION OF AROMATIC COMPOUNDS

Aromatics combined with hydrogen and get converted in to
napthenes.
C10 H8 + 2 H2 C10 H12

4.2.6.SATURATION OF OLEFINS
Olefins combines with hydrogen and get saturated
R=R + H2 HR-RH

4.3.UNDESIRABLE REACTIONS
The undesirable reactions that occur in hydrotreating are
1.
2.

Hydrocracking
Coking

These undesirable reactions reduce the yield of the product. At high

temperature and pressure of HDS reaction, Hydrocracking occurs as a side
reaction. Hydrocracking reaction has to be minimised, because it consumes
hydrogen, reduces the product yield and the hydrogen purity of the recycle
gas. It is limited by the selection of catalyst with low hydrocracking
capacity and working at low temperature. During HDS reaction the heavy
33

molecules are adsorbed on the acidic site of the catalyst and reduce the
catalytic activity

4.4.HYDROTREATING OPERATING VARIABLES

The principle operating variables affecting the performance of
hydrotreating reactions are as follows:
1.
2.
3.
4.

Reaction temperature
Hydrogen partial pressure
Liquid hourly space velocity and
Hydrogen-to-oil ratio

Reaction temperature :
Reactor temperature has strong influence on hydrotreating
reactions. Increasing reactor temperature increases conversion of sulphur,
nitrogen and oxygen compounds. But increasing the reactor temperature
also increases the side reactions namely, hydrocracking and coking.
Hydrogen partial pressure
Hydrogen partial pressure can be increased by increasing the
hydrogen recycle rate or hydrogen purity at a given feed rate. Increasing
hydrogen partial pressure reduces coke formation by suppressing
polymerization and condensation reactions. Adequate hydrogen-to-oil ratio
is to be maintained to have desirable cycle length.
34

Liquid hourly space velocity

Increasing Liquid Hourly Space Velocity(LHSV) increases feed rate
processed per unit volume of catalyst and hence reduces the severity of
hydrotreating reactions. However, lower LHSV will produce product with
low sulphur, nitrogen and oxygen. LHSV is fixed based on the design feed
rate of the unit.
Hydrogen-to-oil ratio
Hydrogen-to-oil ratio can be increased by increasing the hydrogen
recycle rate or hydrogen purity at a given feed rate and should be kept as
high as possible to decrease the rate of undesirable gases and to improve
the catalyst efficiency by avoiding coke formation.

35

CATALYST USED

5.1. HYDRO TREATING CATALYST

There are two types of catalyst available for hydrotreating purposes.
They are Cobalt-Molybdenum and Nickel- Molybdenum on alumina
support. Cobalt and Nickel are responsible for catalytic action whereas
Molybdenum acts as a promoter. Nickel- Molybdenum catalyst exhibits a
higher hydrogenation activity than Cobalt- Molybdenum catalyst and is
more suitable for treating cracked stocks. Very often the support material
also has catalytic action related to its chemical nature.

5.2.CATALYST OPTIONS FOR PRODUCING ULTRA LOW

SULPHUR DIESELS
36

Proper choice of catalyst is of paramount importance in the

production of Ultra Low Sulphur Diesel (ULSD). Recent advances in
hydrotreating catalyst technologies have significantly improved the sulphur
removal capability. The use of the most advanced hydrotreating catalyst or
catalyst system can significantly increase the desulphurisation capability of
the existing hydrotreaters.
New and improved HDS catalyst for ULSD production have been
developed and marketed by Akzo Nobel(KF 757, KF 848), Criterion
(Century and Centinel), Haldor-Topsoe(TK 573, TK 574), IFP, united
catalyst/Sud-Chemie, Advanced Refining, Exxon Mobil. Nippon Ketjen in
Japan and RIPP in China.
Improved level of desulphurisation can be obtained by using a more
active catalyst. Ther are both Co-Mo and Ni-Mo type of catalyst available
for the production of ULSD. But typically to reach ultra low sulphur levels
in the diesel product, a low space velocity and a high hydrogen partial
pressure will be needed if acceptable operating catalyst cycle is desired. NiMo catalyst will be a better choice for the production of ultra low sulphur
diesel at low space velocity and high hydrogen partial pressures. But for
existing units constrained by pressure and throughput, Co-Mo catalyst is a
better choice since it is better at high space velocities compared to Ni-Mo
catalyst.
In general, for low to moderate pressure and high-temperature
desulphurisation of distillate fuels, Co-Mo catalyst may be better than NiMo catalyst. For high-pressure and low-temperature conditions, Ni-Mo
catalyst performs better than Co-Mo catalyst.

37

The new generation catalyst exhibit 30-40% higher HDS activity

compared to previous generation catalyst (either Co-Mo or Ni-Mo). Use of
such high activity new generation catalyst will help in achieving ultra low
sulphur levels in existing units without shortening catalyst life.
About 15% more catalyst can be loaded using dense loading in
place of sock loading. This result in a 3-4oC reduction in start-of-run (SOR)
temperature for the same desulphurisation activity. Dense loading result in
a higher pressure-drop, which combined with a more uniform packing
normally obtained with dense loading will improve liquid distribution
within the catalyst bed.

38

PROCESS FLOWSHEET

39

FIGURE 5. HYDROTREATING PROCESS FLOW SHEET

40

PROCESS DESCRIPTION

41

6.PROCESS DESCRIPTION
The experiments have been carried out in a pilot plant that
was designed and assembled to perform hydrotreating operation . The
reactor of this pilot plant is a 500 cm 3
pressure of 90Kg/cm2 . the flow chart

vessel which can operate at

(demonstrates the schematic

process flow diagram (PFD) of this pilot plant . As it is shown in this

figure, the feed and hydrogen are mixed with a certain ratio before flowing
into the reactor. The mixed feed enters to the reactor with definite pressure
to achieve a predetermined temperature for performing the HDS reactions.
There are four thermocouples along the reactor for determining
the skin and the inside reactor temperature. The reactor product stream is
fed to a flash drum to separate gas and liquid products. The liquid product
is accumulated in a drum and the gas product is transferred for online
analysis to determine the H2S and H2 content of stream.
In addition to feed preparation, the catalyst should be presulfided
before using it with actual feed. Presulfiding of

catalyst is done by

dimethyl disulfide (DMDS), which is added to the Isomax gas oil, and
circulated through the reactor bed.
This is performed to strengthen the activity and selectivity of
catalyst. To execute the procedure, an inert gas followed by a pure H 2
stream is fed to the reactor. Then the reactor temperature is raised to a
certain value.

42

Presulfiding procedure was followed by a set of experiments which

was carried out to investigate the reproducibility of pilot plant setup and to
find out a suitable procedure for carrying out the main set of experiments.
The liquid samples were analyzed by Raney nickel method to
determine the total sulfur content. The results elucidated that for
improvement of reproducibility of experimental results, twelve hours
should pass to attain steady state of pilot plant system. By passing each six
hours the liquid sample is collected to analyze. The average total sulfur
content for each experiment is calculated by averaging the set of results
which are attained during the experiment. By passing one day the operating
condition can be changed to carry out another
experiment.

6.1.PROCESS OPTION FOR ULSD PRODUCTION

The main process option or types of improvements that may be
required to produce ULSD are listed and discussed below. Some of these
options can be readily implemented and may not have serious cost
implications while some other options require additional capital
investments. All these process options can improve product sulphur and
combination of them can be used to reduce sulphur significantly, but no
single option is adequate in producing ULSD.

43

Raising reactor temperature

This is obvious option to increase the desulphurisation activity. The
maximum reactor temperature is limited by design furnace outlet
temperature of the unit. Higher reactor temperature will also result in
shorter catalyst run lengths and severely restrict its usefulness.

Reducing throughputs
Reducing feed rates can decrease liquid hourly space velocities in
the reactor and thus increase the rates of hydrodesulphurisation and result
in lower product sulphur. The required throughput reduction is estimated to
be 8 times lower for the production of ULSD from a current level of 350
ppmw product sulphur making this option impractical.

Increasing hydrogen partial pressure

Increasing the hydrogen partial pressure in the reactor can reduce
the reactor SOR temperature and also reduces the rate of catalyst
deactivation. Hydrogen partial pressure can be increased by increasing the
purity of makeup hydrogen or purging the recycle gas and increasing its
purity.
Increasing the hydrogen purity by 10% of the recycle gas corresponds to
about 3oC decrease in average SOR temperature, and a 20-30% increase
cycle length. The effect of increasing hydrogen partial pressure by
increasing total pressure is less than by increasing hydrogen purity: a 10%
increase in hydrogen partial pressure corresponds to about 1oC decrease in
44

average reactor temperature. The reason for lower response is that H 2S

partial pressure is also increased and total pressure is increased.

Increasing hydrogen sulphide partial pressure

Hydrogen sulphide strongly inhibits HDS reactions and its partial
pressure has great impact on hydrogen partial pressure. SOR temperature
should be raised to achieve the same HDS level when the recycle gas
contained large amount of hydrogen sulphide. This effect is lager at higher
total reactor pressure and more pronounced for Co-Mo catalysts than NiMo catalysts. Scrubbing the recycle gas to remove hydrogen sulphide will
decreased H2S partial pressure and increase hydrogen partial pressure. The
increased partial pressure of hydrogen can increase the catalyst life by
reducing coke formation.

Increasing hydrogen-to-oil ratio

Increasing hydrogen-to-oil ratio will reduce the inhibition effect of
H2S and ammonia and thereby increase the desulphurisation activity of
catalyst. This effect is rather small compared to the needs of achieving
ULSD. Increasing hydrogen-to-oil ratio by 50% may only gain 4-8% in
catalyst activity. Increasing the recycle gas-to-oil ratio also decreases the
reactor average hydrogen sulphide partial pressure and thus in turn
increases the apparent catalyst activity.

45

Adding reactor volumes

The catalyst volume can be increased either by adding new reactors
to existing units or by installing new dehydrosulphurisation units.
Generally doubling the catalyst volume results, in a 20oC decrease in
average temperature, if all other operating conditions are unchanged.
Increased catalyst volume decreases the deactivation rate of the
catalyst by reducing the start of run temperature in addition to the
availability of more deactivation temperature span. In addition, low LHSV
by itself reduces deactivation rate eve at the same SOR average reactor
temperature. Though this option requires new capital investment, it is the
best option in terms of good flexibility of feed stock and product quality.

Reactor internals
Reactor internals play a key role in improving the contact of the
reactant with the catalyst. Improper distribution of the reactants over the
catalyst will contribute to channelling through the catalyst bed, resulting in
an inefficient utilisation of the catalyst, development of hot spots and
premature catalyst deactivation due to coke formation. It was reported that
around one percent of bypassing of feed over catalyst an contribute 50 to
150 ppmw sulphur in the diesel product. Properly designed reactor internals
with good distribution of reactants over catalyst surface is necessary while
producing ultra low level of sulphur.

46

EXPERIMENTAL
DETAILS

47

7.EXPERIMENTAL DETAILS
Pilot plant studies were carried out to evaluate the performance of
DHDT catalyst.
The objective of the present work is to evaluate the DHDT catalyst
to study the effect of temperature on the performance of Diesel
hydrotreating catalyst.
The catalyst evaluation studies were carried out in a high pressure
catatest unit Procured from Vinci Technologies, France. The hydrotreating
reactions were carried out in co-current down flow mode of operation
without hydrogen recycle.

Feedstock Details
A straight run diesel sample collected from crude distillation
column was used in the pilot plant study. The characteristics of the straight
run

diesel

feed

are

presented

in

table

1.

Catalyst evaluated:
The DHDT catalyst is from procatalyse is NiO-MoO 3/Al2O3 type.
The characteristics of this catalyst are tabulated in table-2.

48

Table7.1.Characteristics of procatalyse hydrotreating catalyst.

Properties

Surface area , m2/gm

206

Pore volume ,ml/gm

0.55

Bulk density ,kg/L

0.737

Loss on ignition at 550o ,wt %

2.1

Single Grain Crushing Strength , DaN/mm

Average of 10 pellets

12.7

Max

18.0

Min

6.9

Bulk Crushing strength MPa

1.01

Ni O content ,wt %

4.2

Co O content ,wt %

Mo O3 content ,wt %

18.0

Table 7.2.Properties of Diesel Products Hydrotreated in Pilot Plant

Reactor
Reactor pressure - 77.7 kg/cm2, Hydrogen / Oil Ratio 150 lit/lit.
49

Properties
Reactor Temp,o C
LHSV , hr
Density @15o C

Operating conditions
310
320
330
0.7
0.7
0.7
0.8410 0.8392 0.8365

g/ml
API Gravity
36.8
o
Viscosity @ 40 C 4.47
,cSt
Cetane Index
52.9
Sulfur , ppmw
254
o
Aniline Point, C 76
ASTM D-86 Dist, Vol % ,o C
IBP
245
5
258
10
263
20
271
30
279
50
298
60
310
70
325
80
344
90
369

340
0.7
0.8345

350
0.7
0.8318

360
0.7
0.8289

37.1
4.34

37.7
4.32

38.1
4.21

38.7
4.19

39.3
4.13

53.4
137
76.5

54.4
88
78

55.7
67
79

56.7
55
81.5

57.7
42
83

241
256
261
269
277
297
309
324
342
368

238
253
259
268
276
295
308
322
344
366

235
255
261
269
277
296
307
323
341
365

233
254
259
267
276
295
307
322
340
364

232
249
256
265
273
293
305
320
339
362

The experimental data obtained as a effect of temperature and

pressure, on the sulfur content of products hydrotreated over different
temperature is presented in the table.
The sulfur and nitrogen content of the hydrotreated products were
decreased due to the conversion of sulfur and nitrogen in the feed to
hydrogen sulfide and ammonia respectively. The aromatic content of the
products was found to decrease owing to the hydrogenation of aromatics to
naphthenes

results in the decrease of density and specific gravity of

hydrotreated products. The decrease in density results in a higher API

gravity product. Saturation of olefins also increases the percentage of
saturates in the hydrotreated product. The increase in aniline point of the
50

hydrotreated products indicates that the product is highly paraffinic(more

saturated or less aromatic) than the feed. The decrease in aromatics reduces
the amount of carbonaceous residue in the product. The increase in aniline
point and API gravity results in a higher cetane number product , which in
turn indicates a lower ignition delay. The viscosity of the hydrotreated
products was also decreased which in turn relates to ease of starting of
diesel engine.

7.1.EFFECT OF TEMPERATURE
The
between

effect of reactor temperature on product quality was studied

310o C and 360oc at

0.7 liquid hourly space velocity and

77.7 Kg/cm2.
The tables show the effect of reactor temperature on product
sulfur hydrotreated over catalyst NiO-MoO 3/Al2O3

at a hydrogen-to-oil

ratio of 150L/L.
With catalyst and 77.7kg/cm2 reactor pressure, the product with a
sulfur content of

254ppmw to 42 ppmw was obtained at a reactor

temperature of 360oC and a LHSV of 0.7h-1 indicating a conversion of

about 98.7 %. As expected ,highest conversion of sulfur compounds was
achieved at the severe most operating conditions employed.
From the table , it is shown that increase in temperature has
decreased the level of sulphur content in the feed. At a temperature of
310oC the sulfur content was 254 ppmw. As the temperature increases to
360oC sulphur content decreases to 42 ppmw.
It was found that the sulfur content of the product decreases with
increasing reactor temperature at constant LHSV. The effect of reactor
51

temperature on product sulfur was more pronounced at higher liquid hourly

space velocities and the sulfur conversion decrease at higher reactor
temperature.

7.2.EFFECT OF PRESSURE
The data show that the increase in the reactor pressure improved
product quality. The API gravity and cetane number of the hydrotreated
products increased and the sulfur and aromatic contents decreased with
increased reactor pressure. The rate of hydrodesulfurisation reaction is
faster at higher pressure. The reason for this effect of pressure is considered
to be that the higher the pressure better is the contact between hydrogen,
and hydrocarbons and the catalyst. In general, the effect is considerably
weaker at higher pressures i.e., sulfur conversion decreases with increasing
pressure. However, very high pressures reduce the activity of the catalyst,
owing to the adhesion of carbon to its surface.
At higher operating pressures, the effect of pressure on sulfur
conversion

becomes

insignificant.

The

partial

pressure

and

the

concentration of hydrogen sulfide in the gas phase goes up as the

conversion of sulfur compounds increases. Beyond a certain operating
pressure, the concentration of hydrogen sulfide in the gas phase decreases
because of the increase in solubility of hydrogen sulfide in liquid phase.
In general, the hydrotreated products showed a decrease in density,
viscosity, sulfur, nitrogen and aromatic contents, and increase in API
gravity, aniline point, cetane number and saturates content when the
temperature is increased.

52

The polyaromatics content of the hydrotreated products was well

below 11wt% meeting Euro-III as well as Euro-IV specifications.

7.3.EFFECT OF ANILINE POINT

This is an approximate measure of the aromatic content of a
hydrocarbon fuel. It is defined as the lowest temperature at which a fuel oil
is completely miscible with an equal volume of aniline. Aniline is an
aromatic compound and aromatics are more miscible in aniline than are
paraffins. Hence, the lower the aniline point, the higher the aromatics
content in the fuel oil. The higher the aromatics content, the lower the
cetane number of the fuel. The aniline point can thus be used to indicate the
probable ignition behavior of a diesel fuel. aniline point increases from 76
to 83.

7.4.EFFECT OF IBP
According to American Society for Testing and Materials
petroleum- analysis distillation procedures, the recorded temperature when
the first drop of distilled vapor is liquefied and falls from the end of the
condenser.
The initial boiling point in the feed is actually higher than that of
the product. So when the initial boiling point is taken for 5 vol % it has a
certain higher temperature and finally if the temperature is noted for 90
vol % certainly it will have a temperature less than the 5 vol %.
53

7.5.OVERALL HDS KINETICS

The kinetics for sulfur removal from real feedstocks are complex
and depend on the distribution of sulfur compounds and the degree of
conversion. For industrial feedstocks, the structural differences between the
sulfur containing molecules make it impractical to produce a complex rate
equation to describe the HDS kinetics. Hence, in the present work the
following conventional power law kinetic expression was used (Juarez et
al.1999):

1 1

1
k(n 1)
n 1 n 1

Sp Sf
LHSV

where S is the sulfur content in the feedstock (wt%), S the sulfur content in
the product (w%). n the apparent reaction order and k is the kinetic
constant.
The data at various space velocities, temperatures and product
sulfur contents were used for kinetic data analysis and to determine the
following apparent reaction orders and activation energies.

Diesel indx
The Diesel Index indicates the ignition quality of the fuel. It is
found to correlate, approximately, to the cetane number of commercial
fuels. It is obtained by the following equation

54

Diesel Index

aniline po int

F x Degrees API gravity 60 F

o

100

Diesel Index and cetane number are usually about 50. Lower values will
result in smoky exhaust

Cetane improvement
Cetane number or CN is a measurement of the combustion quality
of diesel fuel during compression ignition. It is a significant expression of
the quality of a diesel fuel. Cetane has improved significantly . as the
temperature is increased the cetane number is increased 52.9 to 57.7.

Cetane improvers
These are compounds that readily decompose to give free radicals
and thus enhance the rate of chain initiation in diesel combustion. They
promote fast oxidation of fuels and thus improve their ignition
characteristics. Chemical compounds such as alkyl nitrates, ether nitrates,
dinitrates of polyethylene glycols and certain peroxides are well known
cetane improvers. In general, however, in view of their low cost and ease
of handling, most commercial significance has been attached to different
primary alkyl nitrates.

Cetane index

55

Cetane index is used as a substitute for the cetane number of diesel

fuel. The cetane index is calculated based on the fuel's density and
distillation range (ASTM D86). There are two methods used, ASTM D976
and D4737.

56

DESIGN OF FEED
VESSEL & SEPERATOR
OF A PILOT PLANT

8.1. DESIGN OF FEED VESSEL :

Design of feed vessel of hydro treater in a pilot plant
57

The feed vessel is a unfired pressure vessel . Pressure vessels used

in industry are leak-tight pressure containers, usually cylindrical or
spherical in shape, with different head configurations. They are usually
made from carbon or stainless steel and assembled by welding. Early
operation of pressure vessels and boilers resulted in numerous explosions,
causing loss of life and considerable property damage. In 1925 the
committee issued a set of rules for the design and construction of unfired
pressure vessels.

8.2.DESIGN CRITERIA
The Code design criteria consist of basic rules specifying the design
method, design load, allowable stress, acceptable material, and fabrication,
inspection certification requirements for vessel construction.The design
method known as "design by rule" uses design pressure, allowable stress,
and a design formula compatible with the geometry of the part to calculate
the minimum required thickness of the part. This procedure minimizes the
amount of analysis required to ensure that the vessel will not rupture or
undergo excessive distortion. In conjunction with specifying the vessel
thickness, the Code contains many construction details that must be
followed. Where vessels are subjected to complex loadings such as
cyclic, thermal, or localized loads, and where significant discontinuities
exist, the Code requires a more rigorous analysis to be performed. This
method is known as the "design by analysis" method.

8.3.SPECIFICATIONS
58

1.
2.

Here the operation is considered to be running for 12 hours .

Maximum liquid flow rate : 600 ml/hr.
(pumping capacity)
3. For a day, the flow rate is : 7.2 lt /day
4. Consider 30% excess for the N2 inert atmosphere.

5. So Z, we have to design the capacity of the vessel

approximately to be 10 litres.
6. Let the feed vessel considered to be cylindrical.
7. Volume
8.

= (/4) d2 L

Length of the cylindrical vessel = 320 mm

9. Diameter of the cylindrical vessel = 200m.

10. so, the volume = 10 litres
11. L/D ratio = 320/200 =1.6

MATERIAL OF CONSTRUCTION:
1.
2.

The material used here is SS316 .

It is stainless steel and the maximum allowable stress is

18100.
3.
It can withstand temp of about 500 o C & pressure of about
150 Kg/cm2 .

59

TABLE8.4.Thickness calculation
DIMENSIONS
Design pressure
Design temperature
Inside radius
Maximum allowable stress
Joint efficiency (from table uw12)
Circulated thickness (circular stress)
Circulated thickness (longitudinal stress)
Internal corrosion allowance
External corrosion allowance
Total thickness
Desired thickness

UNIT
Kg/cm2
o
C
Mm
PSI
%
Mm
Mm
Mm
Mm
Mm
Mm

VALUES
3
150
100
18100
0.7
3.42
1.71
0
1.25
4.67
12

TABLE 8.5. Max Allowable stress in PSI

UPTO

UPTO

SS 316

SS 316L

SS 304

MS

100OF
200
300
400

37.7OC
93.33
148.89
204.44

18800
18400
18100

14100
12700
11700

15700
14100
12900

11500
11500
11500

60

500
600
650
700
750
800
850
900
950

260.00
315.56
343.33
371.11
398.89
426.67
454.44
482.22
510.00

18000
17000
16700
16300
16100
15900
15700
15600
15400

10900
10400
10200
10000
9800
9600
9400

12100
11400
11200
11100
10800
10600
10400
10200
10000

11500
11500
11500
11500

8.6.CALCULATION OF CIRCULAR THICKNESS:

(i) (Circular stress)
((D.P *14.5) * (I.R/25.4) /

((M.A.S*J.E) - 0.6*D.P*14.5)) *25.4

((1 * 14.5) * (100/25.4) / ((18100*0.7) - 0.6*1*14.5))*

25.4 =

3.42

(ii) (Longitudinal stress):

((D.P*14.5)*(I.R/25.
4) /((2*M.A.S*J.E) + (0.4*D.P*14.5))* 25.4
((1*14.5) * (100/25.4) / ((2*18100*0.7) +(0.4*1*14.5))*25.4 = 1.71

Total thickness :
(C.T.C+I.C.A+E.C.A)
(3.42+ 0 + 1.25 ) = 4.67
61

External pressure : 0

8.7.DESIGN OF GAS LIQUID SEPERATOR

62

Figure8.7. GAS LIQUID SEPERATOR

A vaporliquid separator is a device used in several
industrial applications to separate a vaporliquid mixture. For the common
variety, gravity is utilized in a vertical vessel to cause the liquid to settle to
the

bottom

of

the

vessel,

where

it

is

withdrawn.

In low

gravity environments such as a space station, a common liquid separator

will not function because gravity is not usable as a separation mechanism.
In this case, centrifugal force needs to be utilized in a spinning centrifugal
separator to drive liquid towards the outer edge of the chamber for removal.
Gaseous components migrate towards the center. The gas outlet may itself
be surrounding by a spinning mesh screen or grating, so that any liquid that
does approach the outlet strikes the grating, is accelerated, and thrown
away from the outlet.

63

SPECIFICATIONS
1.

Operation : Continous
2.
gas.
3.
4.
5.
6.
7.

Consider the seperator is occupied with 60% liquid & 40%

Volume
L/D ratio
Length
M.O.C

: 1 lt
: 165/90 = 1.8
: 165 mm
Diameter : 90 mm
: SS316.

8.8.Thickness calculation
DIMENSIONS
Design pressure
Design temperature
Inside radius
Maximum allowable stress
Joint efficiency (from table uw12)
Circulated thickness (circular stress)
Circulated thickness (longitudinal stress)
Internal corrosion allowance
External corrosion allowance
Total thickness
Desired thickness

8.9.Calculation of circular thickness:

(i) (Circular stress)
64

UNIT
Kg/cm2
o
C
Mm
PSI
%
Mm
Mm
Mm
Mm
Mm
Mm

VALUES
77.7
400
45
18100
0.7
1.6
1.6
0
1.25
2.85
12

((D.P *14.5) * (I.R/25.4) /

((M.A.S*J.E) 0.6*D.P*14.5))*25.4
(

(77.7 * 14.5) * (45/25.4) / ((18100*0.7) - 0.6*77.7*14.5))*25.4 = 1.6

(ii) (Longitudinal stress):

((D.P*14.5)*(I.R/25.4)/((2*M.A.S*J.E) + (0.4*D.P*14.5))*25.4
((77.7*14.5) * (45/25.4) / ((2*18100*0.7) +(0.4*77.7*14.5))*25.4 = 1.6

Total thickness :
(C.T.C+I.C.A+E.C.A)
(1.6+ 0 + 1.25 ) = 2.85

External pressure : 0

FIGURE 8.10 CETANE RESPONSE FOR VARIOUS CETANE

IMPROVERS

65

Scope of the project work

The scope of the project work includes the following:
1.

To evaluate the performance of various activity new

generation hydrotreating catalyst in a pilot plant trickle-bed reactor

66

to determine the required severity level and different combination of

catalyst for the production of ultra low sulphur diesel.
2.
To study the effect of reactor temperature and liquid hourly
space velocity on product quality at constant reactor pressure and
hydrogen-to-oil ratio using different hydrotreating catalysts.

Applications
1.

Useful in the production of Ultra Low Sulfur Diesel

(ULSD) as per fuel quality regulations assigned by government.

2.
We are able to minimize pollution in the environment by
reducing mainly sulfur & also other impurities present in the diesel
by hydro treating process.

67

RESULTS &
DISCUSSIONS

9.RESULTS & DISCUSSIONS

The hydrotreated products from pilot plant were characterized in
detail to study the extent Hydrodesulphurisation and cetane improvement.

68

1.

Increase in temperature has increased the HDS activity as

evidenced by reduction in sulphur content progressively of 254

ppmw to 42ppmw.
2.
Increase in temperature has beneficially increased the
important property namely Cetane Index also. The Cetane Index
increase observed was 4.5 to 10.5 units

CONCLUSIONS
The pilot plant studies help in concluding the demand less than
50ppm product sulphur can be achieved from high sulphur Raw Diesel
Sample. The Cetane improvement is remarkable from Diesel feed which
has high aromatic content.

APPENDIX

1) Determination of Density (ASTM D-4052)

The density, specific gravity and API volume (approximately 0.7ml)
of diesel was introduced into an oscillating sample tube. The change in
69

oscillating frequency caused by the change in mass of the tube was

measured. Using the calibration data the density, specific gravity and API
gravity were determined.

2)

Determination of Kinematic Viscosity (ASTM D-445)

Kinematic viscosity is the resistance to flow of fluid under gravity.

Kinematic Viscosity was determined at 40o C using Ubbelohdes

Viscometer. Time was measured for a fixed volume of liquid to flow under
gravity through the capillary of a calibrated viscometer under a
reproducible driving head and at a closely controlled and known
temperature. The kinematic viscosity is the product of the measured flow
time and the calibration constant of the viscometer.

3)

Determination of Pour Point (ASTM D-97)

The Pour Point is the lowest temperature, expressed as a multiple of

3o C at which the oil is observed to flow when cooled and examined under
prescribed conditions.
The Pour Point was determined using Pour Point apparatus. The
Pour Point is an index of the lowest temperature of its utility for certain
applications.
After preliminary heating, the sample was cooled at a specified rate
and examined at intervals of 3o C for its flow characteristics. The lowest
temperature at which movement of the sample occurred was observed and
recorded as the pour point.

70

4)

Determination of Aniline Point (ASTM D-611)

Aniline Point is the minimum equilibrium solution temperature, in

degree Celsius, of a mixture of equal volumes of aniline and the sample

under test. The aniline point is used to estimate the aromatic content of
mixture.
Specified equal volumes of aniline and sample were placed in a
tube and mixed mechanically. The mixture was heated at a controlled rate
and the temperature at which two phases become miscible was noted. The
mixture was then cooled at a controlled rate and the temperature at which
two phases separate was recorded as the aniline point.

5)

Determination of Flash Point (ASTM D-93)

Flash Pont is the minimum temperature at which the vapors from

test sample will give a momentary flash on application of a standard flame

under specific test conditions. The flash point is determined using PenskyMartens closed cup apparatus.
A brass test cup of specified dimensions, filled to the mark with test
sample and fitted with a cover of specified dimensions, was heated and the
sample stirred at specified rates. An ignition source was directed into the
test cup at regular intervals with simultaneous interruption of the stirring,
until a flash detected. The temperature at which flash was detected is
reported as flash point.

6)

Determination of Ramsbottom Carbon Residue (ASTM D-524)

71

It is the amount of carbonaceous residue formed by evaporation and

thermal degradation (phyrolysis) of the sample.
The sample was weighed into a special glass bulb having a capillary
opening and placed in a metal furnace maintained at approximately 550 o C.
The sample was quickly heated to the point at which all volatile matter is
evaporated out of the bulb with or without decomposition while the heavier
residue remaining in the bulb undergoes cracking and reactions. In the
latter portion of the heating period, the cole or carbon residue was
subjected to further decomposition or slight oxidation due to the possibility
of breathing air in to the bulb. After a specified heating period, the bulb
was removed from the bath, cooled in a dessicator, and the residue
remaining was again weighed and expressed as a percentage of the original
sample and reported as Ramsbottom Carbon Residue.
Provision

is

made

for

determining

the

proper

operating

characteristics of the furnace with a controlled bulb containing a

thermocouple, which must give a specified time-temperature relationship.

7)

Determination of Total Sulfur (ASTM D-2622)

The total sulfur content of diesel is determined by Energy

Dispersive S-ray Fluorescence spectrometry.

The diesel sample is placed in a beam emitted from the X-ray
source. The resultant excited characteristics X-radiation is measured and
the accumulated count is compared with counts from previously prepared
calibration samples to obtain the sulfur concentration in mass%.

8)

Determination of Total Aromatics and Total Saturates (IP-391)

72

Diesel sample contains monoaromatic, diaromatic and polyaromatic

hydrocarbons.
A known mass of diesel sample was diluted in the mobile phase (nheptane) and a fixed volume

20L

of the solution was injected into a High

Performance Liquid Chromatography (HPLC) fitted with a polar column.

This column has little affinity for the non-aromatic hydrocarbons whilst
exhibiting a pronounced selectivity for aromatic hydrocarbons. As a result
of this selectivity the aromatic hydrocarbons are separated from the nonaromatic hydrocarbons into distinct bands according to their ring structure
i.e., MAH, DAH, PAH compounds. At a pre-determined time, after the
elution of DAHs the column was back flused to elute the PHAs as a single
Sharp band.
The column was connected to a refractive index detector that
detects the components as they elute from the column. The electronic
signal from the detector was continually monitored by a data processor. The
amplitudes of the signal from the sample aromatics were compared with
those obtained from previously run calibration standards in order to
calculate % mass of MAHs, DAHs, PAHs in the diesel. The sum of MAHs,
DAHs and PAHs is reported as the total content of the aromatic contents in
the sample.
The Saturates content of the sample is obtained by subtracting the total
aromatics content from 100 percent.

9)

Determination of Nitrogen (ASTM D-4629)

73

ANTEK

N2

analyzer as per ASTM D-4629 method determines the

Nitrogen content of the sample.

10)

Determination of ASTM Distillation Characteristics (ASTM D-

86)
The distillation characteristics of the sample were determined using
ASTM D-86 Distillation apparatus.
A 100 mL specimen of the sample was distilled under prescribed
conditions. The distillation was performed in a laboratory batch distillation
unit at ambient pressure under conditions that were designed to provide
approximately one theoretical plate fraction. Systematic observations of
temperature readings and volumes of condensate were made. The volume
of the residue and the losses were also recorded.
At the conclusion of the distillation the observed vapor
temperatures can be corrected for barometric pressure and the data were
examined for conformance to procedural requirements, such as distillation
rates. The test was repeated if any specified conditions have not been met.
Test results are commonly expressed as percentage recovered and
corresponding temperature in a table.

74

REFERENCES

References

75

1. Babich I.V. and Moulijn J.A. (2002), science and technology of novel
processes for deep sulfurisation of oil refinery streams : a review, fuel,
vol.82,pp.607-631.
2. Bhaskar M.,

Valavarasu G., and Balaraman K.S (2000), deep

desulfurization of a diesel blend in a pilot plant trickle bed reactor ,

Petroleum Science and Technology, vol.18, No.7 & 8, pp.851-869.
3. Bhaskar M.,

Valavarasu G., Selvavathi V. and Sairam B.(2004),

Production of ultra Low Sulfur Diesel-Catalyst and process options, XII

Refinery Technology Meet, Goa, India, September23-25,2004;pp.474-486.
4. Bhaskar M., Valavarasu G., Sairam B., Balaraman K.S and Balu K.(2004),
Three Phase Reactor Model to Simulate the performance of pilot-plant
Trickle Bed

Reactors Sustaining Hydrotreating Reactions, Ind.

Eng.Chem
Res., Vol.43,pp.6654-6669.
5. Chunshan Song (2003), An overview of

new approaches to deep

desulfurization for ultra-clean gasoline, diesel fuel and jet fuel, Catalysis
today , Vol.86,pp.211-263.
6. Lamourelle A.P and Nelson D.E.(2001), Ultra low aromatic diesel,
Petroleum Technology Quarterly , june 2001.
7.

Perrys chemical engineers handbook. 7th ed. /

prepared by a staff of specialists under the editorial

direction of late editor Robert H.
Perry : editor, Don W. Green : associate editor, James
OHara Maloney.

76

8.

Salvatore T.JR. and Gunter P.M (2004), Fundamentals of ULSD

Production, Petroleum Technology Quarterly Summer 2004,pp.29-35.

77