DHDT

INTRODUCTION TO
DIESEL HYDROTREATING
August 1, 2019
Copyright © HPCL-Mittal Energy Ltd.
TOPICS
 WHAT IS HYDROTREATING?  PROCESS DESCRIPTION
 HOW TO HYDROTREAT?  FEEDS & PRODUCTS OF DHDT
 WHY HYDROTREATING?  SALIENT FEATURES
 STARTUP & SHUTDOWN

 DESIGN BASIS

HYDROTREATING
• A Process in which Hydrocarbon Feed is treated with hydrogen

in presence of catalyst at high temperature & pressure.
• HDT Feeds have high degree of contaminants like sulfur,

nitrogen which can cause corrosion and contribute to increase
in pollution. Hydro treating reduces sulfur & nitrogen content.
• Feed may have high olefin/aromatics content and product

requires less aromatics. Hydro Treating saturates
olefins/reduces aromatic contents.
HYDROTREATING
What It Does:
Sulfur Removal
Nitrogen Removal
Aromatic Saturation
Olefin Saturation
Consumes Hydrogen
HYDROTREATING REACTIONS
Desirable reactions: i.e. the reactions, which concur in the purpose

of the process:
 Elimination of sulfur.
 Elimination of nitrogen and oxygen.
 Elimination of metals.
 Saturation of olefins and diolefins
Undesirable reactions
The maximum product yield is achieved by limiting the undesirable
reactions
• Hydro cracking
• Coking
– Sulfur Removal
• 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.
MERCAPTAN DESULFURIZATION
SULFIDE DESULFURIZATION
THIOPHENE DESULFURIZATION
– Nitrogen Removal
• The rate is lower than for the desulfurization reactions.
• These reactions lead to ammonia formation.
• These reactions are also exothermic.
PYRIDINE HYDRODENITROGINATION
PYRIDINE
PHENYLAMINE
– Hydrogenation of oxygenated compounds
Alcohols and phenols R - OH + H2 ® R - H + H2O
Hydrogenation of bond C=O

Aldehydes
R - C = O + 2H2  R - CH3 + H2O
H
– Aromatic Saturation (Hydrogenation)

• Reactions of hydrogenation of aromatics are exothermic and the
numbers of molecules decrease. So they are favored by 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.
TOLUENE METHYLCYCLOHEXANE (C7H14)

– Olefin Saturation (Hydrogenation)

• These reactions are highly exothermic. Olefins and diolefins are
converted to saturated compounds.
• The hydrogenation rate of olefins and diolefins is faster than the
hydrodesulphurization rate.
Examples
R - CH = CH2 + H2  R - CH2 - CH3
– Demetallization
• The organo-metallic compounds (containing As, Pb, Cu, Ni, Va...)
are cracked and the metals are trapped on the catalyst.
– Hydrocracking
Hydrocracking is undesirable in Hydrotreater Units because:
• consumes hydrogen
• reduces the product yield and the hydrogen purity of the recycle gas.
CH - R
2
+H + R - CH
2 3
• Hydrocracking reactions has a tendency to increase with increase in temperatures and can
be limited by catalyst selection (by choosing a catalyst with low Hydrocracking capacity
and working at low temperature.
– Coking
Heavy molecules which when adsorbed on the acidic sites of the
catalyst, may be condensed and progressively polymerize on the
catalyst to form coke. The coke deposit is the main cause of catalyst
activity reduction
HOW TO HYDROTREAT?

DESIGN BASIS – DHDT – CRUDE CASE
Design Case Crude Processed Blend Percentage Capacity, TPA

Case 1 Arab Medium 100% 4 135 000
Case 2 Arab Heavy + 90 wt% Arab Heavy + 10 wt% 4 089 104
Doba Doba
Case 3 Check Arab Heavy + 70% AH + 30% Maya 3 269 210
Case Maya
Run Length : Minimum 29 Months before first regeneration.
Turndown : 50% turndown
Feedstock : The feed stock of this unit is a mixture of LGO, HGO, Vacuum Diesel
LKO & HKO, Heavy Naphtha from CDU/VDU, Coker Naphtha, LCGO from
DCU, LCO from FCC Unit and DSO rich stream from the LPG treating Unit.
Processing : The process objective is to minimize the production of naphtha
Objective and maximize production of diesel to meet the Euro IV
specifications
DESIGN BASIS – DHDT – COLD FEED CASE
Crude Basis Achievable Capacity

Design Case
Case 1: Arab maximum capacity achievable with 60% of design capacity of the unit. No
Medium 100% of cold feed steam generation in 507-E-018 (Diesel
Product LP Steam Generator)
maximum cold feed content in order 60% of cold feed in the blend. No
to keep design capacity of the unit steam generation in 507-E-018 (Diesel
Case 2: Arab maximum capacity achievable with 95% of design capacity of the unit. No
Heavy + Doba 100% of cold feed steam generation in 507-E-018 (Diesel
maximum cold feed content in order 90% of cold feed in the blend. No
to keep design capacity of the unit steam generation in 507-E-018 (Diesel
DESIGN BASIS Feed Properties Case 1
FEED CHARACTERISTICS DEISGN CASE 1: ARAB MEDIUM
TEST Unit Method LCO LKO HKO LGO HGO VAC Diesel Coker LCGO DSO Rich
Naphtha Naphtha
Specific gravity, D4052 0.945 0.792 0.822 0.86 0.891 0.888 0.7139 0.8581 0.745
D60/60
TBP cut range °C 140-370 200-250 250-300 300-350 350-370 370-475 C5-140 140-370 -
IBP 173 136.9 139.8 159.4 199.5 251.8 45 153 20
5% 156.5 178.9 217.4 267.8 285.6 - - 56
10% 181 162.7 193.8 236.8 289.9 299.3 56 187 79
30% 199 173.3 221.2 272.6 328.2 322.2 71 237 115
50% 223 184.2 236.4 293.2 345.3 335.5 87 272 132
70% 254 197.5 249.8 311.1 359.7 346.5 102 302 144
90% 311 221.3 271.2 336.9 379 361.5 118 331 156
95% - 232.4 281.2 348.4 388.9 368.2 - - 161
FBP 352 253.6 300 369 411 382.8 135 373 176
Sulfur wt % D2622 0.0377 0.192 0.612 1.454 2.132 2.088 0.73 3.09 2
Mercaptan Sulfur ppmw D2120 200 150 - - - 1230 - -
Total nitrogen wt pm D4629 93 20 47 50 295 439 275 1000 3
Bromine number g/100g D1159 0 0.2 0.5 0.7 0.7 88 19 0
Total aromatics FIA vol % D1319 26 25 - - - 14 35.1 -
Smoke point mm D1322 24.4 21.5 14.5 - - - - -

Aniline point °C D611 52.9 51.4
Pour point °C D97 - - -7 15.3 15 - -
Cetane index (calcul D4737 44.3 49.5 49.2 48.2 50.1 35.2 43.2
(calculated) axens)
Cetane index (data D4737 43.6 48.8 48.5 47.4 49.3 21.5 40
(calculated) HPCL)
Conradson carbon wt % D189 <0.001 <0.001 <0.001 <0. 1 <0.1 - 0.2
Ni + V ( FX) or ppm wt IFP 9422 <1 <1 <1 <1 <1 <1 <1 <1 <1
DESIGN BASIS Feed Properties Case 2
FEED CHARACTERISTICS DEISGN CASE 2: ARAB HEAVY + DOBA
TEST Unit Method LCO LKO HKO LGO HGO VAC Diesel Coker LCGO DSO Rich
Naphtha Naphtha
Specific gravity, D4052 0.944 0.783 0.817 0.855 0.889 0.878 0.7143 0.8581 0.745
D60/60
TBP cut range °C 140-370 200-250 250-300 300-350 350-370 370-475 C5-140 140-370 -
IBP 172 137 153.3 161.7 202.2 250.8 45 154 19.9
5% 155.8 191.4 226.1 277 284.2 - - 56.5
10% 180 160.9 203.7 247.1 298.7 296.5 57 186 79.7
30% 205 170.7 224.4 280.2 335.8 318.3 72 234 115.2
50% 236 180.5 236.8 296.8 352.3 330.8 87 270 132.4
70% 273 193 248.2 313.9 364.7 341.4 102 300 144.1
90% 316 215.2 265 340.2 381.2 354.9 118 330 155.7
95% 226.3 273.8 351.9 390.4 361.7 - - 161
FBP 352 247.2 291.4 370.9 410.6 375.2 135 373 176.4
Sulfur wt % D2622 0.0398 0.188 0.618 1.435 2.036 1.854 0.7 2.85 2
Total nitrogen wt pm D4629 96 2.3 15 90 100 120 175 1404 2
Bromine number g/100g D1159 0 0.2 0.5 0.7 0.7 90 32 0
Total aromatics FIA vol % D1319 15 20 10.1 32.5 -
Smoke point mm D1322 - 23.5 19.6 19 - - - -
Aniline point °C D611 51.3 49.8
Pour point °C D97 - - - -26 -23 -18
Cetane index (calcul D4737 46.8 52.4 53.1 50.7 53.5 34.9 42.8
(calculated) axens)
Cetane index (data D4737 46.1 51.6 52.3 50 52.7 21.5 40
(calculated) HPCL)
Conradson carbon wt % D189 <0.01 <0.01 <0.01 <0. 1 <0.1 0.2
Ni + V ( FX) or ppm wt IFP 9422 <1 <1 <1 <1 <1 <1 <1 <1 <1
DESIGN BASIS – DHDT – Feed Properties
Properties of Diesel from VGO-HDT Unit FEED BLEND PROPERTIES
Property UOM Case 1 Case 2 PROPERTY UOM Case 1 Case 2
Specific Gravity 0.8798 0.8755 Flowrate kg/h 516875 511138
Sulfur, wt% 0.01 0.01
Specific Gravity, d60°F/60°F 0.8501 0.8484
Nitrogen, wtppm 100 100 ASTM D86 °C
Aromatics %wt 42 IP 45 45
Distillation TBP
5% 149 134
IBP 120 120
5% 188 178 10% 173 165
10% 216 201 30% 235 237
30% 277 263 50% 273 277
50% 316 308 70% 307 308
70% 345 339 90% 340 339
90% 370 371
95% 362 361
95% 378 378
EBP 390 395 EP 411 410
HYDROGEN MAKE-UP CHARACTERISTICS

Type All Cases
Source HGU
Composition %vol
Nitrogen 50ppmvol
H2 99.5
Impurities ppm vol
CO + CO2 20
Chlorine et Chloride <1
O2 50
Water 50
PRODUCT PROPERTIES
HYDROTREATED DIESEL
Property Unit Value
3
Specific gravity /Density @15°C, kg.M (MIN-MAX) 0.82 - 0.845
Total Sulphur, max ppmw <30
Cetane Index 46.5 min
Cetane number 51.5 min
95% recovery, max C 360
Flash point (Abel), min C 60
PAH (max) mass% 11
Water content.max. ppmw 100
3
Oxidation stability.max Gm/m 25
Aviation Turbine Fuel
3
Specific gravity /Density @15°C, kg.M (MIN-MAX) 0.7775 - 0.84
Total Sulphur, max Wt% 0.25
Mercaptan S max ppm 20
Aromatics max Vol% 20 max
Olefins max Vol% 5
o
Flash Point, Abel min C 38
Smoke Point min mm 21
Kinematic Viscosity at -20 °C cSt 8
10% recovery, max 205
o
FBP C max 300
Stabilized Naphtha
Specific Gravity, d60°F/60°F 0.7372 - 0.744
Sulphur, max. Wppm 10
2
RVP kg/cm abs <0.5
Nitrogen, max ppmw <1
Chlorides max ppmw <1
Mercaptan Sulphur, max ppmw <1
DESIGN BASIS – HDT – Process Variables
Liquid Hourly Space Velocity:
The space velocity is the amount of liquid feed, expressed in volume that is
processed in one hour, divided by the amount of catalyst, expressed in volume.
Volume of feed at 15°C (per hour)

Liquid Hourly Space Velocity : LHSV = --------------------------------------------------
Volume of catalyst
Both High and Lower LHSVs are undesirable, as:
Higher LHSV will lead to higher WABTs, faster coking which in turn will lead to
reduced cycle length.
Lower LHSV will lead to lower pressure drops which will lead to liquid mal-
distribution.
LHSV Design Case 1 1.25
LHSV Design Case 2 1.24

Reactors Temperatures
For a given catalyst, a given feed composition and a given LHSV a minimum temperature exists, suitable
for obtaining the expected results. This temperature is the one to be adjusted at the inlet to the
reactor beds. In case of a new or regenerated catalyst this temperature is called “Start Of Run”. With
the other parameters constant, it will be necessary to progressively increase the inlet temperature
during a run to balance the catalyst deactivation.
The weighted average bed temperature applies to each catalyst and is defined as follows:
For a reactor with three catalytic beds: catalyst weight WABT

bed 1 M1 WABT1
WABT1
An increase of temperature (i.e. WABT) has the
bed 2 M2 WABT2
following effects, assuming the space velocity
(i.e. the feed rate) and feed characteristics stay
unchanged: bed 3 M3 WABT3
Increase catalyst activity (M1 x WABT1 + M2 x WABT2 + M3 x WABT3)

 Decrease the recycle gas purity. WABT =
Reactor M1 +M2+M3
 Increase the coke deposit

DESIGN BASIS – DHDT – Operating Conditions
Case 1; Case 1; Case 2: Case 2:
SOR EOR SOR EOR
507-R-001 bed 1 inlet temperature, °C 334.0 375.6 332.2 374.6
507-R-001 bed 1 outlet temperature, °C 358.0 389.7 358.9 390.2
507-R-001 bed 2 inlet temperature, °C 335.2 373.4 334.0 372.6
507-R-001 bed 3 outlet temperature, °C 357.4 390.8 358.0 391.2
507-R-001 inlet pressure, kg/cm2 g 69.8 72.4 69.8 72.4
507-R-001 outlet pressure, kg/cm2 g 66.0 66.0 66.0 66.0
H2 chemical consumption 0.8476 0.7442 0.9680 0.8400
H2 dissolution 0.1041 0.1013 0.1033 0.1010
H2 mechanical losses (estimated) 0.0470 0.0470 0.0470 0.0470

Hydrogen partial Pressure
An increase in hydrogen partial pressure (ppH2) favors the hydrogenation reactions and reduces
polymerization reactions and coke deposit.
The ppH2 mainly results from four operating parameters:
The hydrogen make-up flow rate / the purge flow rate
The hydrogen recycle gas purity. Minimum required hydrogen 50 kg/cm² abs
The hydrogen recycle flow rate. partial pressure (pph2) at the
Operating pressure. outlet of the reactor
Minimum Hydrogen Recycle 150 Sm3/m3
Ratio
Hydrogen Recycle ratio
The H2/HC ratio, at reactor inlet, is the ratio of pure hydrogen in the recycle gas (make-up and quench
excluded) in Sm3/h to the fresh feed flowrate (m3/h at 15°C).
H2 Pure hydrogen ( Sm 3 / hour ) in recycle gas


HC Fresh feed flowrate ( m 3 / hour ) at 15C
Maintaining proper hydrogen recycle gas purity and recycle gas to feed ratio is essential for suppressing
the formation of heavy condensed hydrocarbons which would subsequently deposit as coke on the
catalyst.

DESIGN BASIS – DHDT – Process Variables
Action of Process Variables on Reaction
VARIABLE HYDROGEN PARTIAL OPERATING LIQUID HOURLY SPACE
PRESSURE TEMPERATURE VELOCITY
DESULFURIZATION
HYDROGENATION OF
AROMATICS
HYDROGENATION OF
OLEFINS
CRACKING
COKING
DENITRIFICATION

DIESEL-HYDROTREATER UNIT 507
H2 Gas
SR feeds
Cracked
Feeds Recycle Gas Compressor
Feed from
70 kg/cm2g
Storage 360 oC Amine
CHPS
Heater HHPS Off Gases to
VGO HDT
Reactor CLPS
HP
Amine
Off Gases Off
Gases
Absorber
Make Up
Rich Amine H2
to ARU
Kero-
Stripper
Stabilizer
Fractionator
Make-Up Gas Compressor
Stripper
NAPHTHA Steam
KEROSENE / DHDT Process Flow Diagram
ATF / MTO DIESEL

DESIGN BASIS – HDT – Process Description
The Reactor operates at moderate temperature and pressure, under mixed phase with
reactions occurring on the catalyst are highly exothermic.
The Exotherm is controlled by recycle gas (Quench Gas), between the first and second reactor,
to operate the catalyst beds in an optimized temperature range.
The hot reactor effluents is cooled and sent to separation section.
To avoid ammonium salt deposits and risk of plugging separator section coolers, wash water
injection at the inlet of cooler.
Hydrocarbon liquid from separator section is fed to stripper section to remove H2S using Steam
as stripping media.
Stripped Hydrocarbons are sent to Fractionator for further separation.
Separator off-gases form DHDT is sent to VGO-HDT gas plant for further treatment/separation.
Hydrogen rich gases from High pressure separator is amine washed, compressed and recycled
to reaction section.

DESIGN BASIS – DHDT – Yield
Diesel Hydrotreater Unit

L Kero
H Kero
CDU LGO Lean Stripping
HGO H2 Amine Steam
NAPHTHA (10%)
Diesel To NHT and Storage
VDU
VGO HDT Diesel DHDT

ATF/MTO (6%)
4.2 MMTPA To Final Product Blending
Technology: AXENS
FCC PC LCO
DIESEL (83%)
Naphtha To Final Product Blending
DCU Diesel
Off Rich Sour
Gases Amine Water
LPG DSO Rich
Treaters Stream

UNIT Interconnectivity (DHDT Product)
Sno Product Routing to Units Alternate Routing

Diesel Hydrotreater Unit (507)
1 Diesel Storage (Blending) Slops (DHDT Feed Tank)/Off
Spec Product (dry Slop tank)
2 Naphtha To NHT/LPG Treaters as solvent Slop (dry Slop tank)/Sweet
Naphtha Naphtha Tank/HGU & NHT
Feed Tank/Naphtha Tank
(Blending)
3 Off Gases To VGO-HDT unit HP Flare
4 ATF To Storage Sweet SKO Tank/Slops (dry

Slop tank)
5 MTO MTO Storage Tank
6 Sour Water To VGO-HDT unit
7 Rich Amine To VGO-HDT unit
WHY DHDT?

WHY HYDROTREAT DIESEL
AUTO FUEL POLICY:
In the backdrop of increasing environmental concerns, the Government of India had

constituted a Committee of Experts, to devise a road map for the implementation of the
vehicular emissions norms and the suitable specifications for the auto fuels. The
recommendations of this committee are known as the Auto Fuel Policy.
The road map for the implementation of the Policy is as follows:
Passenger Cars, light commercial

Coverage vehicles & heavy duty diesel 2 / 3 Wheelers
vehicles
Bharat Stage II – 01.04.2005

Entire Country
EURO III Eq. – 01.04.2010 Bharat Stage II – 01.04.2005
11 major Cities ( Delhi/NCR, Mumbai, Bharat Stage II – 01.04.2003 Bharat Stage III – from
Kolkata, Chennai, Bangalore, Hyderabad, EURO III Eq. – 01.04.2005 01.04.2008 to 01.04.2010
Ahmedabad, Pune, Surat, Kanpur & Agra EURO IV Eq. – 01.04.2010

WHY HYDROTREAT DIESEL
Stringency of the Norms from BS-II to EURO-IV
Fuel BS-II EURO-III EURO-IV
Diesel
Sulphur, ppmw 500 350 50
Petrol
Sulphur, ppmw 500 150 50

SALIENT FEATURES
CATALYST
• A catalyst generally consists of a

support (oxides of alumina, silica,
magnesia ...) on which (a) finely
divided metal(s) is (are) deposited.
• The metal is always responsible for
the catalytic action. Very often the
support has also a catalytic action
related to its chemical nature.
• A catalyst is not consumed, but can
be deactivated either by impurities in
the feed or by some of the products
of the chemical reactions involved,
resulting in polymers or coke
deposits on the catalyst.
CATALYST MECHANISM
• In simple terms, Catalyst components Mo, Co, Ni traps the

impurities like Sulfur. Then Hydrogen reacts with these trapped
impurities and forms compounds like H2S which are separated in
downstream equipments and sent to recovery units.
CATALYST MECHANISM
CATALYST POISONS
Impurities Maximum Contaminant type Origin Means of removal
Content
Asphaltene 500 ppm Inhibitor External Restore feed spec
Pollutant
Organic Chloride 100 ppm Inhibitor External Restore feed spec
Pollutant
Existing Gums 5mg/100 Temporary Poison Storage Regeneration
ml
Inorganic chloride and Nil Permanent Poison External
other Mineral Salts Pollutant
Caustic Nil Permanent Poison External
Pollutant
As, Pb, Sb 500 ppb Permanent Poison Cracker Feed
Si 2 ppm Permanent Poison External
Pollutant
Water Free Water Temporary Poison External Hot H2 Stripping
Pollutant
"External pollution" will usually be temporary and then the total quantity of contaminant
deposited is the significant parameter
CATALYST LOADING

DENSE CATALYST LOADING
Catalyst Loading

Catalyst Loading

REACTOR INTERNALS

MAJOR EQUIPMENTS IN DIESEL HYDROTREATERS

REACTOR INTERNALS

REACTOR INTERNALS EQUI FLOW DISTRIBUTOR
To ensure the mandatory near to perfect gas/liquid distribution for this very severe
service, Equiflow gas/liquid distributors are installed at the top of each bed

COMPRESSORS
RECYCLE GAS COMPRESSOR
 SuppliesH2 required for reaction and also quenches the overall exotherm in order to limit &
to operate the catalyst beds in an optimized temperature range.
 Design Capacity: 25789Kg/Hr
 Suction/Discharge Pressure: 58.4/ 77.7kg/cm2g
 Power requirement: 2550 KW
 Failure of Recycle Gas Compressor leads to shutdown of unit.
MAKE-UP GAS COMPRESSOR
 Supplies Hydrogen which is consumed in reaction and controls pressure of reaction section
 Design Capacity: 6544 Kg/Hr
 Suction/Discharge Pressure: -19.4 /77.7 kg/cm2g
 Power requirement: 4950 KW
Failure of Make-Up Gas Compressor leads to decrease in reactor pressure and possible coke on
catalyst due to Hydrogen shortage to saturate the cracked material.
43
August 1, 2019
COMPRESSORS
EMERGENCY DEPRESSURIZATION
To prevent run-away reaction and or temperature excursion, the Reaction Section is equipped
with a depressurization system which allows depressurizing from initial conditions to 50
percent of Cold HP Separator design pressure (34.85 kg/cm2 g) within 15 minutes.
HP section is depressurized via Emergency depressurization valve on Cold HP Separator
overhead.
Note: care must be taken during this operation as it leads to very high velocity in flare line and
may possibly lead to fire-balls in Flare stack.
44
August 1, 2019
Special Precaution
Hydrogen:
Hydrogen is a flammable gas at concentrations from 4.1 to 74% volume in air. When heated above its
ignition temperature by pressure release from high pressure, the hydrogen gas starts to burn in presence
of air
Care must be taken to purge the air out of the unit as required before start-up and to purge hydrogen
out of the unit for shut-down. Tightness tests are to be made before all start-ups on every vessel
containing hydrogen. Each operator must continually inspect equipment and flanges for leaks.
Hydrogen Sulfide:
The explosive range of hydrogen sulfide in air is from 4.5 - 45 %. The ignition temperature is around
250°C. The maximum safe concentration of hydrogen sulfide is about 13 ppm.
Early symptoms of poisoning are slight headache, burning eyes, and clouded vision. Hydrogen sulfide in
its toxic action attacks nerve centers.
Personal protection
Gas mask of appropriate type or positive air mask should be used.
45
August 1, 2019
Special Precaution
Carbon Monoxide:
 Carbon monoxide is most often found during catalyst regeneration.
Carbon monoxide has the ability to replace oxygen in the blood; too high a concentration in the body
may cause death in a short period of time. Maximum allowable concentration in air is in the range of 100
ppm. CO burns readily and is dangerous when exposed to heat or flames.
Its explosive limits range from 12.5 % to 74 % volume. The auto-ignition temperature is 650 °C. Mixture
of CO and air in certain proportions are flammable.
Carbonyl:
Formed by combining the (CO) group and metal, in particular Ni, Fe, Co, Mo (present in Catalyst), in
presence of carbon monoxide.
The toxicity of carbonyls depends in on their easy decomposition which releases carbon monoxide.
Symptoms are due in part to CO and in part to direct irritating action of the carbonyl with concentration
as low as 1 ppb is toxic.
46
August 1, 2019
IMPORTANT CONTROL SYSTEMS
Pressure control– Reaction section

The pressure is controlled at the Cold HP Separator Drum overhead by two pressure controllers:
1) Aacting on the make-up gas compressor control system (spill-back)
2) On the HP purge line (purging of gas from the overhead of HP Amine Absorber) .
Temperature Control– Reaction section

Another critical parameter to control is the reaction temperature. This is achieved through:
1) Governing the firing rate on Reactor Feed Heater
2) Governs the gas quench between the 1st and the 2nd beds of DHDT Reactor 507-R-001.
47
August 1, 2019
COMMISSIONING & START UP

UTILITIES
DEGREASING OF AMINE
COMMISSIONING
SECTION
UNIT/EQUIPMENT
PARALLEL ACTIVITIES
INSPECTION
REACTOR HEATER &
CATALYST LOADING
UNIT PRE- REACTION SECTION
COMMISSIONING. DRYING (with Internals)
DCS AND
NSTRUMENT  Reaction section vacuum
test, inerting and tightness
CHECKS.
FRACTIONATOR REBOILER test with nitrogen
LEAK TEST WITH DRY-OUT LP Sections leak test and
AIR/NITROGEN inerting
49
August 1, 2019
START-UP OF MAKE-UP GAS COMPRESSOR
Naphtha
Circulation
Reaction Section leak Pressurization of LP Start-Up of recycle gas
test with Hydrogen Section. compressor
Diesel Circulation and Catalyst activation

catalyst wetting (Sulphiding)
Wash Water circulation
Start-up amine circulation
Design Feed In and Products Out of Diesel

Through-put adjustment Hydrotreater Unit
50
August 1, 2019
The DHDT Catalyst is supplied is non active because the metals, nickel and molybdenum, are
under oxide forms. Therefore, the catalyst must be sulfided (Activated) prior to use in order to
become fully active. The principle of catalyst sulfiding is the transformation of inactive metal
oxides in active metal sulfides by action of H2S on metal oxides according to the following
reactions:
3NiO + 2H2S + H2 Ni3S2 + 3H2O
MoO3 + 2H2S + H2 MoS2 + 3H2O
H2S for the above reaction is generated from decomposition under hydrogen atmosphere of
the sulfiding agent, dimethyldisulfide (DMDS) that is injected at the suction of the feed pumps.
H2S is produced following the reaction which is activated around 180°C:
CH3-S-S-CH3 + 3 H2 2 H2S + 2 CH4
51
August 1, 2019
Neglecting to carry out the sulfiding procedure prior to the hot hydrogen circulation of the first
start-up phases, results in a reduction of the metal oxides, in sintering of the metal and poor
sulfiding later. The consequences would be a reduced catalyst activity. The decomposition of
the sulfiding agent and H2S absorption is exothermic. To limit the temperature rise, the
sulfiding is done under diesel circulation and with recycle gas rate at 80% of operating pressure.
To minimize H2S loss, the HP purge must be closed and Recycle HP Amine Absorber bypassed
(amine circulation not in service). Two sulfiding steps at two different temperatures are
mandatory to obtain a fully active catalyst:
- First step at ~ 220-230°C
- Second step at high temperature, in the range 330-350°C depending on the unit normal
operating conditions.
The total amount of DMDS required is 65 480 Kg during one catalyst sulfiding.
52
August 1, 2019
THANK YOU

DHDT

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

DHDT

Uploaded by

Copyright:

Available Formats

INTRODUCTION TO

 WHAT IS HYDROTREATING?  PROCESS DESCRIPTION

 HOW TO HYDROTREAT?  FEEDS & PRODUCTS OF DHDT

 WHY HYDROTREATING?  SALIENT FEATURES

 STARTUP & SHUTDOWN

Copyright © HPCL-Mittal Energy Ltd.

• A Process in which Hydrocarbon Feed is treated with hydrogen

• HDT Feeds have high degree of contaminants like sulfur,

• Feed may have high olefin/aromatics content and product

Desirable reactions: i.e. the reactions, which concur in the purpose

Hydrogenation of bond C=O

– Aromatic Saturation (Hydrogenation)

TOLUENE METHYLCYCLOHEXANE (C7H14)

– Olefin Saturation (Hydrogenation)

Copyright © HPCL-Mittal Energy Ltd.

Design Case Crude Processed Blend Percentage Capacity, TPA

Crude Basis Achievable Capacity

Smoke point mm D1322 24.4 21.5 14.5 - - - - -

HYDROGEN MAKE-UP CHARACTERISTICS

Volume of feed at 15°C (per hour)

Copyright © HPCL-Mittal Energy Ltd.

For a reactor with three catalytic beds: catalyst weight WABT

Increase catalyst activity (M1 x WABT1 + M2 x WABT2 + M3 x WABT3)

Copyright © HPCL-Mittal Energy Ltd.

507-R-001 bed 1 outlet temperature, °C 358.0 389.7 358.9 390.2

507-R-001 bed 2 inlet temperature, °C 335.2 373.4 334.0 372.6

507-R-001 bed 3 outlet temperature, °C 357.4 390.8 358.0 391.2

507-R-001 inlet pressure, kg/cm2 g 69.8 72.4 69.8 72.4

507-R-001 outlet pressure, kg/cm2 g 66.0 66.0 66.0 66.0

H2 chemical consumption 0.8476 0.7442 0.9680 0.8400

H2 dissolution 0.1041 0.1013 0.1033 0.1010

H2 mechanical losses (estimated) 0.0470 0.0470 0.0470 0.0470

Copyright © HPCL-Mittal Energy Ltd.

H2 Pure hydrogen ( Sm 3 / hour ) in recycle gas

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Diesel Hydrotreater Unit

VGO HDT Diesel DHDT

Copyright © HPCL-Mittal Energy Ltd.

Sno Product Routing to Units Alternate Routing

3 Off Gases To VGO-HDT unit HP Flare

4 ATF To Storage Sweet SKO Tank/Slops (dry

Copyright © HPCL-Mittal Energy Ltd.

In the backdrop of increasing environmental concerns, the Government of India had

The road map for the implementation of the Policy is as follows:

Passenger Cars, light commercial

Bharat Stage II – 01.04.2005

Copyright © HPCL-Mittal Energy Ltd.

Fuel BS-II EURO-III EURO-IV

Sulphur, ppmw 500 350 50

Sulphur, ppmw 500 150 50

Copyright © HPCL-Mittal Energy Ltd.

• A catalyst generally consists of a

• In simple terms, Catalyst components Mo, Co, Ni traps the

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.

Copyright © HPCL-Mittal Energy Ltd.