INTERNSHIP REPORT

On

Diesel Hydro Desulphurization Unit (DHDS)

Undertaken at Indian Oil Corporation Limited,
Mathura Refinery.

(Duration: 15th May, 2024 to 14th June, 2024)

Under the supervision of

Mr. Pradeep Kumar Pal (CPNM)

Submitted By :- Abhinesh Tyagi

Student Of

National Institute of Technology, Raipur, Chhattisgarh (492010)

 CERTIFICATE
Date: 14th June, 2024

This is to certify that this report has been prepared by Mr. Abhinesh Tyagi, a B.Tech student
in Chemical Engineering at NIT Raipur, Chhattisgarh. During his internship at IOCL’s
Mathura Refinery, Mathura (from 15th May 2024 to 14th June 2024), his diligent work has
been duly approved by his supervisor as his official internship report.

Approved by
Mr. Pradeep Kumar Pal Mr. Ram Raj
CPNM Senior Manager, L&D
 ACKNOWLEDGEMENTS
There are many individuals who assisted me during my internship, both directly and
indirectly. I would like to express my sincere gratitude to IOCL’s Mathura Refinery
for providing me with the opportunity to undergo training from 15th May 2024 to
14th June 2024.

I am especially thankful to Mr. Ram Raj and Mr. Madan Mohan for their invaluable
guidance throughout my internship. Their efforts in managing our training and
providing insightful discussions and support were crucial to my learning experience.
Additionally, I extend my thanks to the Training Department and the Fire and Safety
Department for their continuous help and direction.

I am also deeply grateful to Mr. Pradeep Kumar Pal (CPNM), Mr. R.R Singh
(SPNM), Mr. S.K. Rajoria (PNM), and several others who patiently explained the
operations of the plant and provided the essential conceptual understanding for my
project. The numerous discussions with them have significantly enhanced my
practical knowledge of the plant and the industry.

I would like to extend my appreciation to all the employees of the refinery, including
officers and staff, for taking the time to assist me during my internship. Their
explanations of the processes, equipment, and various aspects of production and
refinery operations were invaluable. They guided me during field visits, ensured my
personal safety, and were consistently kind and supportive, making extra efforts to
help me understand and clarify my doubts.

Regards,

Abhinesh Tyagi
NIT Raipur, Chhattisgarh
 TABLE OF CONTENTS

OVERVIEW OF MATHURA REFINERY

ABOUT FIRE AND SAFETY
PROJECT TITLE
OBJECTIVE OF STUDY
METHODOLOGY OF STUDY
STATEMENT OF PROBLEM
INTRODUCTION
PROCESS DESCRIPTION
UTILITIES
PROCESS CHEMISTRY
CATALYST DESCRIPTION
FEED AND PRODUCT
MATERIAL BALANCE CALCULATION
FURNACE EEFICIENCY
TYPICAL PROCESS PARAMETERS
TROUBLESHOOTING
SAFETY CONDIDERATIONS
FINAL RESULT AND CONCLUSION
SCOPE OF FUTURE STUDY
ABOUT MATHURA REFINERY:

Mathura refinery products various products: LPG, Motor Spirit, Mineral Turpentine Oil (MTO),
Superior Kerosene (SK), Aviation Turbine Fuel (ATF), High Speed Diesel (HSD), Furnace Oil
(FO), Naphtha, and Lube Oil Products. Other products include bitumen, propyleneand sulphur. It
consists of the following units:

Atmospheric and Vacuum Distillation Unit (AVU):

This unit consists of four sections which are Crude oil desalting section (made up of two parallel
sections of two stage desalters in series), Prefractionator column and naphtha stabilization,
Atmospheric distillation of crude oil and Vacuum distillation ofReduced crude oil. Crude oil is
preheated by the bottoms feed exchanger, further preheated and partially vaporized in the feed
furnace and then passed into the atmospheric tower. The Atmospheric distillation column separates
most of the lighter end products such as gas, gasoline, naphtha, kerosene and gas oil from crude
oil. The bottom product of this column is Reduced Crude oil, which is sent to Vacuum distillation
Unit.

Fluid Catalytic Cracking Unit (FCCU):

The feed to this unit is Heavy Vacuum Gas Oil from the Vacuum Distillation Unit. It is catalytically
cracked to produce lighter products and middle distillates. The products are LPG, Gasoline, Cycle
oil and Clarified Oil. It consists of three sections: catalytic section, fractionation section and gas
concentration section. The catalytic process has fluidized catalytic cracking in which the catalyst
helps the reactions to take place at high pressures and temperatures. Cracking reaction is takes
place inside the riser. In this unit there is a system in which catalyst continuously regenerated in
regenerator. Reactor is established at the top of riser where majorly separation work is going on.

Vis-Breaker Unit (VBU):

The Visbreaker Unit is designed for processing a mixture of Atmospheric and Vacuum Residue.
The Visbreaker is essentially a Thermal cracking unit designed to operate at mild conditions and
to retain all the cracked light oils in the bottom product. This results in reduction of viscosity of
bottom product.

Continuous Catalytic Reforming Unit (CCRU):

This unit produces high octane reformate, which is the main product, from straight run naphtha
through the process of catalytic reforming. The by-products of this unit are hydrogen and LPG. It
consists of three sub-units: Naphtha Splitting Unit, Naphtha Hydro-treater Unit, Catalytic
Reforming and Catalytic Regeneration Unit.

A catalytic reforming process converts a feed stream containing paraffin’s, Olefins and naphthene
to aromatics. The octane no. of the gasoline coming from the AVU is around 66, whereas the
required value of the octane no. is 87, 88 and 93.

Once Through Hydrocracker Unit (OHCU):

This unit processes Heavy vacuum gas oil (HVGO) from VDU to produce high value middle
distillates. The products from this unit are gas oil, LPG, Light and Heavy Naphtha, ATF/Kerosene,
Diesel and UCO. UCO is then sent to FCC ass feed. This unit majorly consists of four sections
which are: Reaction section, Hydrogen compression section, Fractionation section and Light End
Recovery section. The feed is sent to the reactor section consisting of two reactors in series, from
where the cracked feed is sent to the fractionator for producing different product cuts. The gases
are recovered in the Light End Recovery section. Major product of this unit is diesel with cetane
number 61.

Diesel Hydro De-Sulphurisation Unit (DHDS):

DHDS unit is provided to produce low Sulphur content diesel by catalytically converting
to hydrogen sulphide in presence of hydrogen at high temperature and medium pressure.
Used to match BS6 standards for diesel. The Sulphur content in product of this unit is
about 8ppm only.

Diesel Hydro-Treating Unit (DHDT):

DHDT unit is provided to produce low Sulphur content and boost upcetane number of
diesel by catalytically converting to hydrogen sulphide in presence of hydrogen and
olefins and aromatics are converted to paraffin’s, in presence of high temperature and
pressure.

Hydrogen Generation Units (HGU-I & HGU-II):

HGU I & HGU II processes Naphtha and Natural Gas catalytically to produce 99.99
%(mol) purity hydrogen gas, which is used in various hydro treating processes. These
units have mainly 3 sections first is hydro desulphurization, second is steam reforming
section and third is purification section.

FCC Gasoline De-Sulphurisation Unit (PRIME-G):

Prime-G processes FCC gasoline to produce BS6 grade gasoline by hydro

desulphurization process.

Bitumen Blowing UNIT (BBU):

This unit processes Short Residue (SR) from VDU to produce three grades of Bitumen
which is marketed as final products. It has alreadybeen revamped with Biturox technology
to increase throughput with energy optimization.

Propylene Recovery Unit (PRU):

PRU to recover petrochemical feed stock propylene from FCCU cracked LPG.

Sulphur Recovery Unit (SRU):

There are four SRUs, which are equipped with three Claus reactors and1 Super Claus
each. It produces elemental Sulphur from the acid gas and sour gas streams coming from
Amine regeneration and Sour water stripping unit.

Tail Gas Treating Unit (TGTU):

TGTU having capacity of 180 TPD is designed, in accordance with the RAR process
(Reduction Absorption Recycle) to treat the tail gas coming from Sulphur Recovery Unit.

Effluent Treatment Plant (ETP)

Effluent treatment plant in Mathura refinery works to maintain water quality which is
going outside the refinery to meet the norms set by indian government. This plant works
to remove oil and grease, total suspended solids, acids and bases, bacteria’s and other
impurities like Sulphur, nitrogen etc.

ABOUT FIRE AND SAFETY

Safety is the first thing comes to mind when we talk about working in a chemical industry.in Mathura
refinery as we know that we are working in a lot of flammable fuel so the main threat in Mathura refinery
is with fire.in Mathura refinery for the safety of lives in case of fire they have a team of fire fighters with
a proper set of equipments. In each unit of Mathura refinery there are cylinders of dry chemical powder
placed everywhere.

Manual call points (mcp) are established so that fire information can be transferred easily. there are
assembly points in each section of refinery where a yellow light is always blinking to indicate that. There
are 4 types of siren codes to indicate the situation in case of any threat

1st is wailing siren for continuously 2 minutes for major fire.

2nd is wailing siren of 2-2 minutes for 3 times with a gap of 1 minute in case of disaster.

3rd is all clear siren

4th is testing siren

All types of sirens are checked time to time so that at the time of nessecity they can we used.

Safety shoes are compulsory in battery area and safety helmet is compulsory when visiting in a plant.

There are a lot of other safety accessories like fire resistant suite, ear buds and ear mufs etc.

1 - TITLE OF THE PROJECT:

Quality up gradation of HSD in Diesel Hydro Desulphurization Unit to produce Euro-VI HSD
(used in transportation and automobile).

2 - OBJECTIVES OF THE STUDY:

The objective is to control and optimize various parameters affecting the process and quality to
get of high quality HSD as per EURO-VI standards, this will help in controlling Sox & Nox emission
to reduce environmental air pollution.

3 - METHODOLOGY OF THE STUDY:

Study is carried out by preparing the available Process Flow Diagrams, Study operation and
maintenance of the Plant. Study is carried out on collecting Data such as Feed Quality, Product
Specifications, Catalyst characteristics, Equipment Details and Resources available etc.

4 - STATEMENT OF PROBLEM:
Interlocks are provided to prevent losses and failures in case malfunctioning of safety valves,
electric motors, and power & utilities failures.

5- INTRODUCTION:
Indian Oil Corporation Limited (IOCL) is the largest commercial undertaking in India, which
operates the largest number of refineries in the country. Currently IOCL, refineries produce
Gasoline & Diesel conforming to BS-6 specifications. IOCL MATHURA REFINERY had
already achieved Auto Fuel Policy 2025 in various categories.

CAPACITY OF THE PLANT

The existing unit has a capacity of 1.25 MMTPA to produce 8ppm Sulphur content diesel.
Diesel Hydro Desulphurization Unit is capable of producing diesel with <10ppm shulphur from a
feed having 1.437% sulphur content.The unit treats the following gas-oils fractions.
Straight Run Gas oil
Vacuum Diesel
Total Cycle Oil (TCO) from FCCU

Hydrodesulphurization Section
The purpose of the section is to reduce Sulfur in diesel to desired level using hydrogen from
Catalytic Reformer or Hydrogen Generation Units. In addition to the deep desulfurization, the
Diolefin and olefins will be saturated and a denitrification will also occur. The choice of catalysts
and operating conditions is made in order to avoid hydrogenation of the aromatics.
Feedstocks are blended from various sources, straight run or cracked products Sulfur and
nitrogen contents are depending upon the crude. Cracked products are characterized by the
presence of unsaturated hydrocarbons (olefins, diolefins and aromatics), mercaptans, Pyridine,
Quinoline, Thiophen.
Nowadays, more and more stringent specifications are imposed upon sulfur content of diesel
delivered by refineries. Denitrification improves the product stability. The required level of
desulfurization and denitrification is achieved by catalytic hydro treating process. Removal of “S”
 & “N2” from aromatic/cyclic (sulphur & nitrogen compounds) an additional bed installed in
upstream of the desulfurization bed. The unit is able to produce treated Diesel Oil with
maximum sulfur content of 100 ppm by providing an additional second Reactor in series.

Amine Treatment Section

The Amine Treatment Section is designed to remove Hydrogen Sulfide (H2S) from gaseous
hydrocarbons effluents using a 25% wt. Di-Ethanol Amine (DEA).
.
6 - DETAILED PROCESS DESCRIPTION
Make LEAN AMINE
up H2 FUEL GAS
Compression WASHAmine
WATER
section
section
RICH Amine
AMINE section
Treat Wash water
gas section

feed Separation Stripping

Feed Reaction
section section section section
PROD
UCT
SOUR WATER
A) Feed section

The feed for Diesel hydrodesulphurization unit is mixture of Diesel having boiling range in between
226 – 400 deg C and max sulphur content allowed up to 1.437 % (wt).

The Diesel feed is supplied from different sources to feed tank to have required blend of
Feeds as per Feed specification in the feed tank. Through a pump feed send to the Feed Surge
Drum of DHDS unit. Three banks of filters are provided in the inlet of feed surge drum. The feed
filter is of semiautomatic, self cleaning, internal backwashing type capable of removing solid
particles of 25 microns or larger. The pressure in feed surge drum is maintained by split range
pressure control using fuel gas especially during filter backwash to ensure required pressure of
2
3.0 Kg/cm g at the backwash inlet. Temperature of feed is 740 C. The backwash fluid is
collected in a backwash tank and Backwash transfer pumps are provided to pump the
backwash fluid to the slop header.
Feed Diesel is pumped to reactor system by the feed charge pump. It is a multistage centrifugal
pump.
 B) Reactor system

The feed pump takes suction from the feed surge drum and pump the feed to the reactor section.
The feed from feed pump is split into two parallel trains in ratio 60:40. The 60% split goes to the
new reactor with three beds and 40% split goes to the two existing reactor in series. The parallel
trains are designed to produce diesel product with less than 8 ppm sulphur.
All three HDS reactors are loaded with Topsoe‟s hydrotreating catalyst. These catalysts are highly
active and ensures that the required sulfur and aromatic specifications are met. In addition to bulk
catalyst, the top bed of 1st HDS reactor and 3rd HDS reactor is loaded with different layers of
grading catalysts, which are designed to prevent pressure drop build-up. Quench gas is added
between the beds of 3rd HDS reactor to control the reaction temperature. Similarly, quench gas
is added between the beds of 1st HDS reactor and at inlet of 2nd HDS reactor to control the
reaction temperature. The quench gas flow is set to obtain equal bed outlet temperature for 3rd
HDS reactor and 1st / 2nd HDS reactors. This mode of operation normally results in low catalyst
deactivation rate. For case 2 EOR, no quench flow is maintained for all reactors to provide
sufficient heat for preheating old reactor feed
Diesel feed from charge pump is combined with a hydrogen rich gas stream from the recycle
compressor. The combined feed enters the shell side of the combined feed exchangers where
feed is heated by the reactor effluent. Combined feed is heated in combined feed exchanger to a
temperature of 268-300oC and at pressure 33.8 kg/cm2. The combined feed leaving the
exchanger is all vapour, and flows to fuel gas fired Heater where it is heated to the required reactor
temperature. Combined feed is heated in fuel gas fired heater to a temperature of 340-341oC. In
the reactor catalyst reacts with the feed to remove sulfur, nitrogen, oxygen and halides and metals
from the feed and olefins & di-olefins saturation. The effluent from the reactor is cooled on the
tube-side of the combined feed exchanger at temperature 125 0 C and 54 kg/cm2g pressure and
the product condenser at temperature 50 0C and 51.2 kg/cm2g pressure. To control rise of
temperature due to exothermic reaction H2 Quench inject between the beds and temperature rise
allow 4 - 60C maximum.

C) Wash water section

A Water Wash Injection point is provided in the Reactor effluent piping upstream of the Combined
feed exchanger and Products Condenser so that any Ammonium salt buildup in the reactor
effluent exchangers, process lines or condenser may be washed out. Wash water from Water
Break Tank is injected by Wash Water Injection Pump. Its injection rate should be 4.5% of Feed
rate.
 D) Separator section

The hot separator performs a two-phase separation where the liquid phase flows to stripper after
mixing with HC liquid from cold separator and the vapor phase which contains hydrogen,
hydrogen sulfide, ammonia, light ends and some naphtha flows to the effluent air cooler followed
by an effluent trim cooler.

Wash water is added at the upstream of the reactor effluent air cooler through a continuous wash
water spray nozzle to avoid precipitation of ammonium salts, thereby providing protection to the
associated equipment from getting fouled and corroded.

The three-phase stream from effluent trim cooler namely the HC gas, HC liquid and sour water is
separated in the cold separator. The sour water from the cold separator is routed to sour water
flash drum. The HC liquid stream separated in the cold separator is mixed with hot liquid from hot
separator. The mixed liquid is preheated in stripper feed/bottom exchanger; stripper feed/effluent
exchanger and stripper preheat exchanger before it flows to the product stripper. Stripper feed
temperature is controlled by adjusting HDS reactors effluent flow through stripper preheat
exchanger.
The sour gas from cold separator is sent to HP amine absorber K.O. drum to remove any
carryover of liquid. The H2S in sour gas from HP amine absorber K.O. drum is absorbed in the
amine absorber using aqueous amine solution. The vapor from the amine absorber flows to the
recycle gas K.O. drum, to remove any liquid entrained with the vapor. Hereafter, the vapor is
compressed by the recycle gas compressor. At the amine absorber vapor outlet, a part of vapor

E) Compression section

the recycle gas compressor circulates hydrogen rich gas through the reactor section. Make up
gas is added to compensate for the consumption of hydrogen in the reactor loop. It is
compressed by a single stage reciprocating compressor and then mixed with recycle gas at
recycle gas compressor section.

F) Stripper section

The liquid hydrocarbon in the Separator is passes through the Stripper Feed-Bottoms Exchanger,
allowing heated material to enter near the top of the Stripper. Stripper consists of 36 nos. of valve
trays. Feed from the feed/bottom exchanger is fed on tray no. 9. The column operates at top
pressure of 5.2 kg/cm2g and top temperature of 150-160oC. The bottom temperature is maintained
at 260-265oC. M.P. Steam is fed into the bottom of column to strip off lighter hydrocarbons and
H2S from the feed. Generated vapor strips hydrogen sulfide, water, light hydrocarbons and
dissolved hydrogen from the feed, which then passes overhead to the Stripper Condenser and
Stripper Receiver. Normally, no net overhead liquid product is produced, and all of the liquid in
the Stripper Receiver is pumped back to the Stripper as reflux by Stripper Reflux Pumps. The
Stripper bottoms material is pumped by Stripper Bottom Pumps through the Stripper Feed-
bottoms Exchanger and is then routed directly to the Diesel product tank.

G) Amine absorption section

H.P. Amine Absorption System

Cold separator top gas having unconverted Hydrogen and H 2S fed (through the knock out drum)
in H.P. amine absorber, consists of 20 nos. of valve trays the gas is washed by Lean Amine fed
at the top. H2S is absorbed in the Lean amine. The nearly H 2S free Hydrogen gas is recycled
back to the Reactor section with the help of recycle gas compressor. Column operate at
temperature 500 C and 33 kg/cm2g pressure. The rich amine from the bottom of the H.P. amine
absorber is fed in L.P. amine absorber.

L.P. Amine Absorption System

The hydrocarbon sour gas from stripper/stabilizer reflux drum is fed into L.P. sour gas knock out
drum to remove HC liquid from the gas. The HC. sour gas is then fed into the L.P. amine
absorption column consists of 20 nos. of valve trays. Column operate at temperature 67 0 C and
5 kg/cm2g pressure. The gas is washed by amine (from the bottom of the H.P. amine absorber)
fed from the top. H2S from gas gets absorbed in lean amine. The sweet gas from the top of the
column is routed to the fuel gas header and rich amine is taken out from the bottom of the column
and sent to the Amine Regeneration unit

8- UTILITIES
 UNIT MINIMUM NORMAL MAXIMUM MECH. DGN
1. INSTRUMENT AIR
Pressure Kg/cm2(a) 7.0 8.0 9.0 11.0
Dew Pt. Deg C - 15
Temperature Deg C 40 65
2. NITROGEN
Pressure Kg/cm2(a) 7.0 8.0 10.5
Temperature Deg C Ambient 65
3. STEAM
(a) Medium Pressure Steam
Pressure Kg/cm2(a) 5.0 6.0 7.0 9.0
Temperature Deg C 190 210 235 260
(b) High Pressure Steam
Pressure Kg/cm2(a) 38.0 40.0 42.0 46.0
Temperature Deg C 380 390 400 420
4. Cooling Water
Pressure (S) Kg/cm2(a) 4.8 8.0
Temperature (S) Deg C 33 65
Pressure (R) Kg/cm2(a) 3.2
Temperature (R) Deg C 45 65
5. DM Water
Pressure Kg/cm2(a) 6.5
Temperature Deg C Ambient
6. Fuel Gas
Pressure Kg/cm2(a) 3.5 4.0 4.5 7.0
Temperature Deg C 40
7. FLARE
Flare header is of 36” at the B/L. It is provided with a spectacle blind also. The unit flare header
joins main refinery flare header after unit’s flare KOD. Inside the B/L it is given the slope of 1:500
towards flare KOD. All the PSV’s of hydrocarbon vessels and all the pressurized vessels are
connected to this line for the safe disposal of hydrocarbons.
9) - PROCESS CHEMISTRY
Hydro treating is carried out at high temp. & high pressure in a hydrogen atmosphere in the
presence of a catalyst. Pressures generally range from 33-35 kgf/cm2 (g) & temperature from 355-
4250C.
A) Hydro treating Chemistry

Diesel feed stocks typically contain Sulfur, Nitrogen, and metals etc. which are removed in the
hydro treating reactor. Hydrotreating reactions are catalyzed by the metal sites on the catalyst.

The primary hydrotreating reactions are sulphur and nitrogen removal as well as olefin
saturation. The products of these reactions are the corresponding contaminant-free
hydrocarbon, along with H2S and NH3. Other treating reactions include oxygen, hydrogen
is consumed and heat is liberated.

A) Chemical Reactions

The chemical reactions involved in the hydrodesulphurization process are of two types.

The desirable reactions: i.e. the reactions, which concur to the purpose of the process:
 Elimination of sulfur
 Elimination of nitrogen and oxygen
 Elimination of metals
 Saturation of olefins and diolefins
The undesirable reactions: these are the reactions, which result in a loss of valuable
components of the feed or a decrease of catalyst activity
Desirable Reactions
A) Desulphurization Reactions
 Mercaptans, sulfides and disulfides react easily leading to the corresponding
saturated or aromatic compounds.
 Sulfur combined into cycles of aromatic structure, like thiophene, is more difficult
to eliminate.
 These reactions are exothermic; they produce hydrogen sulfide and consume
hydrogen.
1. (Mercaptans) C-C-C-C-SH +H2 C-C-C-C+ H2S

2. (Sulfide)
C-C-S-C-C+2H2 2 C-C+H2S
 3. (Disulfide)
C-C-S-S-C-C-+3 H2 2 C-C+ 2H2S
4. (Cyclic Sulfide)

C C C-C-C-C + H2S
+ H2 C
C C
S C-C-C + H2S
5. (Thiophenic)

C-C-C-C + H2S
C -------- C
+ 4 H2
C C C

S C-C-C
B) Denitrification Reactions
 The rate is lower than that of the desulfurization reactions. These reactions lead
to ammonia formation with hydrogen consumption.
 These reactions are also exothermic.
 (PYRIDINE)
C C-C-C-C-C + NH3
C C
+5H2 C
C C
N C-C-C-C +NH3

 (QUINOLINE)
C C C
C C C C C-C-C-C
+ 4H2 +NH3
C C C C C
C N C
 (PYRROLE)
C C C-C-C-C +NH3
+4H2
C C
N C

H C-C-C + NH3
C) Hydrogenation of oxygenated compounds
 Hydrogenation of bond C - O
  Alcohols and phenols
R - OH + H2  R - H + H2 O
Aldehydes

R - C = O + 2H2  R - CH3 + H2O

H
 Acids
O

R - C = O + H2  R - C + H2O

OH H
- Hydrogenation of bond C = O

(PHENOLS)

C C
C C-OH C C
+ H2 +H2O
C C C C
C C

D) Hydrogenation of Olefinic Compounds

These reactions are highly exothermic. Olefins and diolefins are converted to saturated
compounds. The rate of hydrogenation of olefins and diolefins is faster than that of
hydrodesulphurization rate.
a. (Linear Olefins)

C-C=C-C-C-C + H2 C-C-C-C-C-C (and isomers)

b. (Cyclic Olefins)

C C
C C C C
+ H2
C C C C
C C
E) Hydrogenation of Aromatic Compounds
The hydrogenation of aromatics has thermodynamic limitations. These reactions are
exothermic and the number of molecules decreases. So they are favored at low temperature
and high pressure.
For a given pressure, when the temperature increases the hydrogenation rate increases first, to
reach a maximum, and then decreases as the temperature continues to increase. For a given
temperature, the hydrogenation rate increases rapidly with the pressure.
 Benzene

+ 3 H2 C6H12
 Naphthalene

+2 H2 + 3 H2

Naphthalene Tetraline Dicyclohexane

F) Demetalization
Metals are retained on the catalyst by a combination of adsorption and chemical reaction. The
catalyst has a certain maximum tolerance for retaining metals. Removal of metals from the feed
normally occurs in plug flow fashion with respect to the catalyst bed. Typical organic metals native
to most crude oils are nickel and vanadium. Iron can be found concentrated at the top of catalyst
beds as iron sulfides, which are corrosion products. Sodium, calcium and magnesium are due to
contact of the feed with salt water or additives.
G) Halides Removal
Organic halides, such as chlorides and bromides, are decomposed in the reactor. The inorganic
ammonium halide salts which are produced when the reactants are cooled are then dissolved by
injecting water into the reactor effluent
All of the reactions discussed above are exothermic and result in a temperature rise across the
reactor.
Undesirable Reactions
The maximum product yield is achieved by limiting the undesirable reactions.

A) Hydro-cracking
It is an undesirable reaction and must be minimized, because it consumes hydrogen, reduces
the product yield and the hydrogen purity of the recycle gas. It is limited by the selection of
catalysts with low hydro-cracking capacity and operating at low temperature. Hydro cracking
increases with the increase in temperature (for kinetic reasons)
  R - CH2 - CH2 - R’ + H2 R - CH3 + R’ - CH3

B) Coking

 Under the design operating conditions, heavy molecules are adsorbed on the
acidic sites of the catalyst, may be condensed and progressively polymerize on
the catalyst and form coke. The coke deposit is the main cause of catalyst activity
reduction.

Thermodynamics and Kinetics

The sulfur compounds (Mercaptans, sulfides, disulfides) are easily hydrogenated to
corresponding saturated or aromatic hydrocarbons, with production of H2S. The reactions are
exothermic:
Mercaptans:
R - SH + H2  R–H + H2S : 17 Kcal/mole
Disulfides

’ ’
R-S-S-R + 3 H2  R-H + R -H + 2 H2S
Sulfides

R-S-R + 2 H2  2 R-H + H2S : 28 Kcal/mole

The nitrogen compounds are hydrogenated to saturated or aromatic corresponding
hydrocarbons, with production of NH3. The reactions require higher H2 partial pressure and are
exothermic.
The hydrogenation of unsaturated hydrocarbons is characterized by an important heat release
(exothermic reaction) and a reduction of volume. Consequently, from a thermodynamic view,
these reactions are favored at low temperature and high pressure. The typical heats of reaction
(per mole of reactant) are as follows:
Diolefins to olefins : 26 Kcal/mole
Olefins to paraffin’s : 30 Kcal/mole
Alkenyl aromatics to alkyl aromatics : 47 Kcal/mole
 Aromatics to naphthenic : 50 Kcal/mole
The thermodynamics indicates also that, in opposition to aromatics, the hydrogenation of
diolefins is almost complete at 300oC with a low hydrogen partial pressure.
The operating conditions result from a compromise between the thermodynamic considerations
and the minimum temperature required by the kinetics of the reactions.

Amine Section

The chemistry involved in H2S removal with Diethanol Amine is below Hydrogen Sulfide, H2S or
HSH, is a weak acid, and ionizes in water to form hydrogen ion and sulfide ion.

H2S + H2O H3O+ + HS-- ……………….(1)

Since it is a fairly weak acid, only a fraction of the H2S will ionize.

Diethanolamine is a weak base and ionizes in water to form amine ion and hydroxyl ion:

(HOCH2CH2)2NH + H2O (HOCH2CH2)2NH2+ + OH- …………………..(2)

When H2S dissolves into the solution containing the amine ion, it reacts to form a weakly
bonded salt of the acid and the base:

(HOCH2CH2)2NH2+ + HS- (HOCH2CH2)2NH3SH ……………..……(3)

The sulfide ion is thus absorbed by the amine solution

This salt formation reaction does not proceed to completion. As the arrows indicate, an
equilibrium level of hydrogen sulfide remains in the hydrocarbon stream. The overall reaction
can be summarized by the following equation:

(HOCH2CH2)2NH + H2S (HOCH2CH2)2NH3SH …………………(4)

Operating variables are selected to favor the forward reaction of equation (4) in the absorption
step of the process and, conversely, selected to favor the reverse reaction in the amine
regeneration step of the process. It is the reversibility of this reaction that permits solution
regeneration and continuous removal of H2S by amine treating.
10) – CATALYST DISCRIPTION

Hydro Treating Catalysts:

Hydro treating catalysts are high surface area materials consisting of an active component and a
promoter, which are uniformly dispersed on a support. Co-Mo and
Ni-Mo catalyst generally used for Hydrotreating process
Co-Mo catalysts have been designed primarily for desulfurization, but some denitrogenation and
demetalization is also achieved. , Co-Mo catalysts have the highest desulfurization performance
at the lower operating pressures. These catalysts also have the lowest denitrogenation
performance due to low hydrogenation activity.
Ni-Mo catalysts have been designed for desulfurization, but particularly for hydrogenation and
denitrogenation. Metal removal can also be achieved. These catalysts can treat feedstock of
widely varying properties. Ni-Mo catalysts have higher denitrogenation activities than Co-Mo and
are therefore used for cracked stocks or other applications where denitrogenation and/or
saturation is as important as desulfurization. Ni-Mo catalysts show a greater response in
denitrogenation and desulfurization performance to changes in H 2 partial pressure than Co-Mo.
CATALYST POISONS
(A) Temporary Poisons
CO, CO2, NH3 & Coke Deactivates Catalyst temporarily and can be regenerated
by regenerations techniques as burning with air.
(B) Permanent Poisons
1. Metal Deposition
2. Catalyst Deactivation as life
3. Coke Formation
11) – FEED AND PRODUCT
A) - Feed Stock
A blend of 65% wt SRGO ,15% wt SRVD and 25% wt Total Cyclic Oil
C) - Feed quality
 D)

1. Desulphurized Diesel:-
B) - Make Up Hydrogen Quality
H2 (vol %) : 98.5 min.
CO + CO2 (ppm) : 20 max.
N2 (vol %) : 0.02 max.
Methane (mol %) : 0.1 max.

C) - Injection Water Quality

Total dissolved solids : 3 wt. ppm (Max)
H2S + NH3 : 20 wt. ppm (Max)
Filtered to : 40 microns (Max

12) - MATERIAL BALANCE

Basis –

FEED PRODUCT

Diesel – 156250 Kg/hr Hydrotreated Diesel - ?

Sulphur – 1.437 % Sulphur – 08 PPM

Nitrogen – 347PPM Nitrogen – 70 PPM

Feed Diesel = 156250 Kg/Hr

Density of diesel = 854Kg/m3

Hydrogen

Hydrogen = 1218 Kg/Hr

Density of hydrogen = 0.0818 Kg/m3

Sulphur in feed

Sulphur in feed = 1.437 % of feed

Therefore Mass of Sulphur = Mass of feed diesel *Sulphur in feed

= 156250Kg/Hr * 1.437/100= 2245.3125 kg/Hr.

Reactor
Feed Diesel = 156250 kg/hr. hydrotreated diesel =?

Hydrogen = 1218 kg/hr. Sulphur = 8 PPM

Sulphur = 1.437% = 2245.3125 kg/hr. H2S =?

Nitrogen = 347 PPM = 54.22 Kg/hr. NH3 =?

Unreacted H2 =?

Nitrogen in feed

Nitrogen in feed = 347 PPM = 347 /1000000 = 0.000347 %

Therefore Mass of Nitrogen = Mass of feed diesel * % Nitrogen in feed

= 156250 Kg/Hr * 0.000347

= 54.22 kg/Hr.

Therefore for sulphur balance

% of Sulphur in product = sulphur in product / sulphur in feed * 100

% of Sulphur in product = 8 / 1437000 * 100 = 0.000556715 %

Therefore % sulphur converted = 100 – 0.000556715 = 99.9994432 %

Therefore sulphur reacted in reactor = 2245.3125 * 0.999994432 = 2245.299998 kg/hr

Unreacted sulphur that goes with product = 2245.3125 – 2245.299998 = 1.25019 kg/hr

Sulphur in diesel compounds such as marcaptans and benzothiophenes get dethatched by

various combination and recombination of reactions and final reaction for H2S formation is as
below.
Reaction

S + H2 = H2S

32 2 34

As per stoichiometry 32 kg of S reacts with 2 kg of H2 to give 34 kg of H2S.

Therefore 224529.9998 kg of S produces H2S = 2245.299998 * 34 / 32 = 2385.631247 kg/hr.

Hydrogen reacted for desulphurization reaction = 2245.299998 * 2 /32 = 140.3312498 kg/hr

Therefore for nitrogen balance

% of nitrogen in product = nitrogen in product / nitrogen in feed * 100

% of nitrogen in product = 70 / 347 * 100 = 20.17291 %

Therefore % nitrogen converted = 100 – 20.17291 = 79.83 %

Therefore, nitrogen reacted in reactor = 54.22 * 0.7983 = 43.28 kg/hr

Unreacted nitrogen that goes with product = 54.22 – 43.28 = 10.94 kg/hr

Nitrogen in diesel compounds such as pyridine and pyrroles get dethatched by various
combination and recombination of reactions and final reaction for NH3 formation is as below.

Reaction

N2 + 3 H2 = 2 NH3

28 6 34

As per stoichiometry 28 kg of N2 reacts with 2 kg of H2 to give 17 kg of NH3.

Therefore 43.28 kg of N2 produces NH3 = 43.28 * 34/ 28 = 52.55 kg/hr.

Hydrogen reacted for denitrification reaction = 43.28 * 6 /28 = 9.27 kg/hr.

Total hydrogen reacted in rector = H2 for desulphurization + H2 for denitrification

Total hydrogen reacted in rector = 140.33125 kg/hr. + 9.27 kg/hr

Total hydrogen reacted in rector = 149.6 kg/hr.

Total hydrogen unreacted = hydrogen in feed – reacted hydrogen

Total hydrogen unreacted = 1218 kg/hr. –149.6 kg/hr.

Total hydrogen unreacted = 1068.4 kg/hr.

Overall Material balance =

Feed diesel + H2 = Product diesel + H2S + NH3 + Unreacted H2

156250 + 1218 = Product diesel + 2385.63 + 52.55 + 1068.4

Therefore, product diesel = 153961.42 kg/hr.

13) FURNACE EFFICIENCY CALCULATION

Diesel mass flow rate = 156250 kg/hr.

Hydrogen volumetric flow rate = 4500.0 m3/hr.

fuel gas mass flow rate = 1100 kg/hr.

density of hydrogen gas = 0.08375kg/m3

FURNACE
T1=280 deg C T2=348 deg C

Fuel gas = m

Fuel Gas= m (calorific value = 50240 KJ/Kg)

Mass flow rate of hydrogen = volumetric flow rate * density

Mass flow rate of hydrogen = 45000*0.08375

Mass flow rate of hydrogen = 3768.75 kg/hr.

Heat taken by feed = (M Diesel * CP1 * (348-280)) +( M hydrogen * CP2 * (348-280))

Heat taken by feed = (156250 * 1.75 * 68) + (3768.75 * 14.8 * 68)

Heat taken by feed = 22386620 KJ/hr.

Heat given by Fuel gas = mass of fuel gas (kg/hr) * calorific value (KJ/kg)

Heat given by Fuel gas = 1100* 50240

Heat given by fuel gas = 55264000 KJ/hr.

Efficiency of furnace = (Heat taken by feed/ heat given by fuel gas) *100

Efficiency of furnace = (22386620/55264000) *100

Efficiency of furnace = 40.5%

14) - TYPICAL PROCESS PARAMETERS AND CONSEQUENCES OF DEVIATION

1. Reactor Inlet Temperature - RIT (Max. 3560C -EOR):

At high RIT high catalyst activity will result in very high reactions and coke
deposition on catalyst leading to its deactivation. Extremely high temperatures
 (>4000C) will result in physical and permanent damage to the catalyst.

Separator Pressure (Hydrogen Partial Pressure):

Licensor has specified a minimum hydrogen partial pressure of 35 kg/cm 2 at

reactor outlet, corresponding to 44 kg/cm2 at the Cold Separator with CRU
Hydrogen. Pressures lower than this will result in low hydrogen availability at the
reaction sites and lead to early catalyst deactivation. High pressure will result in
high temperature/pressure in MUG discharge and may result in MUG tripping.

2. Hydrogen/Hydrocarbon Ratio:

Recommended minimum is 150. Lower ratios will result in higher residence time for the
feed and cause early catalyst deactivation. Very high ratios (>250 at high throughput)
result in high loading and high discharge temperature in RGC.
3. Stripping Steam/Stripper Feed Ratio:

Initially a ratio of 20-22 was recommended. However, after optimization we are

currently operating at 18-20. Low stripping steam will result in slippage of H 2S
and lighter hydrocarbons with the product. In such cases product may fail in flash
and/or Cu corrosion. High stripping steam (>25) will cause flooding in the Stripper
overhead section, high naphtha yields with high endpoint and loss in product
yield

5. Pressurization Rate

HP section pressurization rate is 15.0Kg/Cm2 per hour. High rate of

pressurization may disturb catalyst bed. MPT (Minimum Pressurization
Temperature) is 80OC

6. Rate of Increase of Temperature

Recommended rate of increase of catalyst bed temperature is 20-25OC per

hour upto 220OC. Then heating rate is 30OC per hour. High rate of heating will damage
catalyst and loose its physical properties.

7. Very High Del T in bed

A typical range for the del T in the first catalyst bed is 20-25OC, the del T of
2 bed is same as 1st bed
nd

15) - TROUBLE SHOOTING

1) Feed Composition
a) ASTM Initial Boiling Point – Light Fraction Content
An abnormally high content of light components causes an excess vaporization, a
reduction of catalyst washing and a drop in the PPH2 resulting in an increase in
the reactor pressure drop and shortening of the catalyst life.

b) ASTM End Boiling Point- High Fraction Content

The direct effect is high because the heavy fraction is richer in contaminants. A
 high end point, associates however with the right fractionation is not a problem in
itself, as far as the other specifications (contaminants and gums are satisfied.)

c) Diolefins and alkenyl aromatics, Origin of the Feed

Diolefins and olefins are present in cracked feed stocks. A diolefins and alkenyl
aromatics content higher than design means an increased exothermicity. If this
increased exothermicity is not balanced by an increased quench., it induces a
higher delta T across the catalyst. The end result is a shorter cycle duration due to
a higher build-up of polymers.
If the content of reactants in cracked feeds increases , the straight run dilution flow
at the reactor inlet and the quench flow must be increased in order that
%reactants at bed inlet = constant.
A diolefins and/or alkenyl aromatics content higher than the design basis requires
proportionally a higher hydrogen amount. If it cannot be met by the normal action
of the pressure control on the make-up hydrogen flow rate, then the consequence
will be the same as for a too low hydrogen excess i.e.

- A reduced H2 content of the recycle gas

- A closure of the make-up compressor spill back valve
- A decrease of reaction section pressure.
Usually it will be necessary to decrease the feed flow rate.

d) Existing Gum Content

All measures must be taken into limit the content of existing gums because it
decreases the catalyst cycle.
The means available to limit the gums content must be applied.
- Add anti-polymerization agent (or anti oxidant) at the bottom of the proper
columns, and also in-line before the reactor inlet and before the heat
exchangers

- Avoid floating roof storage, use storage under inert gas pressure
- Avoid direct feed from storage, send the storage feed for redistillation
- improve the operation of the distillation
e) Over-Reactive Feed
This is characterized by an increase in delta T of the first catalyst bed.
This situation could occur in normal operation, owing to an unexpected high
content of reactive products (olefins)
Dilution (Less olefin content feed i.e. mainly SRGO) and inter-bed quench are then
used to lower the temperatures of the inlet temperature of reactor
The WABT of the first bed has to be maintained by decreasing the inlet
temperature of the reactor

2) Hydrogen Gas Purity(CO content)

The most common incident is an increase of the carbon monoxide content of the
hydrogen make-up gas (upset of the hydrogen purification unit)
Since CO tends to inhibit the activity, its presence is balanced by rising the temperature
in the reactor. Beyond certain contaminant limits, however (see table of contaminants),
the temperature increase may exceed the limits set for the catalyst. It is clear that these
limits must never be exceeded, at the risk of having a product out of specification.
This increase in temperature also favors polymer deposits on the catalyst. It is therefore
 important for the CO content to return to normal rapidly.
Upon return to normal, the previous activity of the catalyst will be recovered. The
temperature in the reactor can then be lowered to its former value.
Any positive difference between the reactor temperature after return to normal CO
content and the temperature before the increased CO content is an indication of deposits
that may have been formed on the catalyst.
3) Decrease in Hydrogen Make-Up Gas Flow rate
The decrease in flow rate of make-up gas must be accompanied by a proportional
reduction of the feed rate in order to keep a constant H 2/HC ratio at the reactor inlet.
The total reactor feed must always be kept above 60% of the design total reactor feed.
Below these values the unit must be shut down (see emergency procedures: lack of make-
up gas)
4) Loss of Catalyst activity
Any accelerated deterioration of the catalyst activity must be accompanied by a search of
this cause.
A number of parameters can be checked rapidly
- Operating conditions (verification of instruments, if any)
- CO content of the hydrogen make-up gas
- Characteristics of feed to be tested
 ASTM distillation
 Existing gum content
 Diene value and bromine number
 Water and sulfur content
If this search fails to provide any information, a more thorough investigation is necessary,
covering the following potential source of troubles
- Upstream use of chemicals (anti-foam, anti-acing, anti-oxidants,
additives, extraction solvent)
- Unusual feeds from the cracking unit
- Washing operation(amine, caustic)
Any suspected deviation must be followed by analysis to confirm the contaminate on the
catalyst
If nothing wrong is detected, perform systematic analysis covering all the potential
contaminants (refer to the section on contaminates)
Operation should be undertaken to remedy any abnormal situation that is identified.

16) - SAFETY CONSIDERATION

A chemical plant contains a large variety of hazards. Chemical hazards include fire and
explosion hazards, reactivity hazards and toxic hazards. A successful safety programme
can mitigate this type of problems. Mechanical hazards cause worker injuries from
tripping, falling or moving equipment.
Hydrocracker being a high-pressure system/unit, this hazard increases the risk. The risks
involved with the system are as follows:

A) - Hydrogen Sulfide Poisoning

Hydrogen sulfide is both an irritant and an extremely poisonous gas. Breathing even low
concentrations of hydrogen sulfide (H2S) gas can cause poisoning. Many natural and refinery
gases contain more than 0.10 mol-percent H2S. The current OSHA permissible exposure limits
are 20 mol-ppm ceiling concentration and 50 mol-ppm peak concentration for a maximum 10-
minute exposure.

E) - Nickel Carbonyl Formation

Nickel carbonyl Ni (CO), is known to be an extremely toxic gas. Its primary effect is to
cause lung damage with a lesser effect on the liver. The maximum average exposure to
nickel carbonyl recommended by NIOSH is 0.001 wt-ppm (1 wt-ppb), and a maximum
spot exposure of 0.04 wt-ppm (40 wt-ppb). Nickel carbonyl can form over nickel catalyst
in an oxidizing atmosphere, like that present in regeneration

17) - FINAL RESULT AND CONCLUSION

Study provides ample knowledge and great opportunity to understand and learn the process of

Diesel hydrodesulphurization. At the same time it provides knowledge about the safe and efficient

operation of Diesel hydrodesulphurization unit. The knowledge of this study gives new confidence

and approach towards the job which will be beneficial for future growth.

By close and steady monitoring in a efficient manner, we can get improve quality of
HSD fuel (used in transportation and automobile) to EURO-VI standards. This will help
in controlling Sox emission to reduce environmental pollution. To meet product spect
fixed by government. It is important to maintain consistently safe and optimum operation
in the unit.

18) - SCOPE OF FUTURE STUDY

There is vast scope of further study in the unit in future. Some of the points are given

below.

1. Hydrogen sulfide gas produced in the DHDS unit can be utilized for the production of
sulfur.

2. For energy conservation, we can recover heat of the flue gases by installing an air
preheater system in the furnace stack. Combustion air will gain heat from flue gases of the
furnace. This would improve the efficiency of furnace and also save the environment from the
global warming.

3. The properties of diesel are affected by nuclear radiation or not. It is the matter of future
research.