Hydrocracking

Fundamentals & Features

Mukesh Mohan
What is Hydroprocessing ?

• It is used to upgrade
naphtha,distillates,heavy oils and
residul stocks by
• Removal of sulfur and nitrogen
• Metals and other contaminants
• Saturation of olefins and
aromatics
 Rise in “Hydroprocessing capacity” in
Refinery IndianOil

Increase in demand of Middle Distillate fuels has

increased the hydroprocessing capacities.

Stringent environmental legislation.

Cetane increase, Density reduction

200 12
200 12
180
160 10
140 7.5
8
120 6
100 6
80 4
53 2.4
60
2
40
20 0
0 2000 2005
2000 2005
HYDROGEN, KNm3/hr REFINERY CAPACITY, MMTPA
3
HYDROPROCESSING CAP, MMTPA
BENEFITS OF HYDROCRACKING

• Produces Low Sulphur Products

• Improves Combustion Quality
– High Cetane
– Low Aromatics/Olefins
– High H2 Content
– Excellent Color Stability - Lowering N2 content
• Improves Downstream Processing
– FCC or RFCC
– Olefins or Aromatics Plant
– Lube Oil Production
 COMPARISON OF ALTERNATE
CRACKING PROCESS

Hydrocracking FCC Thermal cracking

Op. Press. High Low Low
Naphtha Low High Low
Middle Distillates High Moderate Moderate
ATF Yes No No
Product Quality High Low Low
Post treatment of No Yes Yes
products
Capital, Maint Cost High Low Low
 Process Chemistry
• Crude Oil Properties
• Hydrotreating
Crude Oil Composition
• Various colors

• Various
contaminant
levels

• Various
flowing
properties
 Crude Oil Composition
wt%
• Carbon 84-87

• Hydrogen 11-14

• Sulfur 0.1-2.0

• Nitrogen 0.01-0.2

• Metals 0.0-0.1
 Crude Oil Composition
• Paraffins

• Naphthenes

• Aromatics
 H
H
H
c
H Paraffins H H H H
c c c
H H
Ethane C2H8 (Alkanes) H
H
c
H H
c
H
H

• Single bonded hydrocarbons

• Name ending in – ane
• Chemical Symbols
– CnH2n+2
– Ranging from C1 to C50+
• Saturated
– Each molecule contains its full amount of hydrogen
– No double bonds or impurities
– Stable
– Paraffinic / Waxy
 Naphthenes

• Cyclo-paraffins H H H
c H
c
• Symbol - CnH2n H
H c
c
H
H

• Ringed saturated H c
H
c H
H
hydrocarbons
• May have one H
H H
c H
ring or several H
c
c

c
H

combined H
c c
H
H H
• May contain H H
cyclo-hexane
impurities such
as nitrogen and
sulfur
 H H H H
H H H

H
c c
c
c
H
H
Olefins H c
c
H
c
c
H
c
H

Butene H H
C4H8
(Alkenes) Pentadiene C5H8

• Double bonded hydrocarbons.

• Chemical symbols
– CnH2n for 1 double bond
• Diolefins
– 2 double bonds
• Unsaturated
– Lacking some hydrogen due to double bonds
– Formed in refinery processes that crack without the presence of
hydrogen
– Break down readily in treating reactors
 H H
c c
H H
H c c c
c H

H
c
c c
H
Aromatics H c

c c
c H

H H
H H
Toluene • Cyclo-alkene Benzene (aromatic)

– Base is benzene ring

• Can have sub groups
– Methyl, Ethyl H H
c c
• Unsaturated H c c H

– Lacking hydrogen due to 3 double c c

bonds per ring H

c c
H

• PNA’s H
c c
H
polynucleararomatic
– Polynuclear aromatics PNA

– Two or more benzene rings

 Nitrogen Compounds in
Petroleum
Basic Nitrogen
N

NH
H C 2
3 N N
Amine
Pyridine Quinoline Phenanthridine

Non-Basic
NH NH
Indole Carbazole
 Sulfur Distribution
• Sulfur exists throughout the boiling range of petroleum, except the lightest
fractions
• Sulfur concentration increases with increased boiling range
7

5
Sulfur, Wt%

4
CatCanyon
3
Arabian Hvy.
2 SJV Hvy
1

0
<350°C 350-450°C 450-550°C >550°C
Distillation Range
Sulfur Compounds in Petroleum
S S CH3
H3C SH H3C

Mercaptan Disulfide
H3C

S S
Thiophene Benzothiophene

S CH3
CH3 S

Substituted Benzothiophene Dibenzothiophene

 Nitrogen Distribution-
Hondo Crude (California Offshore)

 Nitrogen rises as boiling range increases

1.5

1.2
Nitrogen, Wt%

0.9

0.6

0.3

0
<315°C 315-370°C 370-425°C 425-480°C 480-535°C >535°C
Distillation Range
 Nitrogen Compounds in
Petroleum
Basic Nitrogen
N

NH
H C 2
3 N N
Amine
Pyridine Quinoline Phenanthridine

Non-Basic
NH NH
Indole Carbazole
 Hydrocracking Unit Reactions
• Desired reactions
– Treating to remove contaminants
– Adding hydrogen to unsaturated hydrocarbons
– Cracking to obtain desired boiling range
products

• Undesired reactions
- Coking
- Contaminant poisoning
 Reactions

Treating Cracking

Sulfur To desired
Nitrogen endpoint
Olefins
To desired
Oxygen product
Metals slate
 Hydrotreating Chemistry
Desulfurization
Denitrification
Olefin Saturation
Aromatic Saturation
Metals Removal
Oxygenates Removal
Halides Removal
 Why Pretreat Feedstock

• Improve cracking catalyst

effectiveness
– By reducing organic nitrogen in
cracking reactor feed

• Reduce temperature rise in cracking

beds
– Treating reactions can be very
exothermic
 Treating Reactions Easiest
• Metals removal

• Olefins saturation

• Sulfur removal

• Nitrogen removal
Hardest

• Oxygen removal
 Hydrotreating
• Approximate relative heats of reaction
(per kg or lb)

– Olefin Saturation 100

– Desulfurization 20

– Denitrogenation 2
 Treating By-Products

• Organic Sulfur
H2 S

• Organic Nitrogen
NH3

• Oxygen compounds
H2 O
 Features of HDS
and HDN Reactions
• Hydrodesulfurization (HDS)
– Sulfur removed first then the olefin
is saturated
• Hydrodenitrogenation (HDN)
– Aromatic saturated first then
nitrogen is removed
 Postulated HDS Mechanism

(A) Desulfurization
HC - CH
+2H2 H2C=CH-CH=CH2 + H2S
HC - CH
S

(B) Olefin Saturation

H2C=CH-CH=CH2 + 2H2 H3C -CH2 -CH2-CH3
 HDS Reactions
S
H +H2 + H2S
Heptanethiol Heptane

+2H2 + H2S
S
Thiophene Butadiene
S +2H2 + + H2S
Butylpropyl Sulfide Butane Propane

S CH3+2H2
+ CH4 + H2S
Methylphenyl Sulfide Benzene Methane
 Reaction Rate Equation
for Desulfurization
• At high conversion levels, desulfurization
reactions follow first-order kinetics
• The rate constant for “easy” sulfur-
containing
molecules may vary greatly from “hard”
• Gas oils contains a variety of sulfur
compounds that vary greatly in their ease
of sulfur removal (different rate constant)
 Thiophene Sulfur is Most
Difficult Approx. Factor of Difficulty
CH3CH2SCH3CH2+ 2H2 2C2H6 + H2S Base = 1
Diethylsulfide (B.P. 92°C)

+ 2H2 + H2S 5
S
Thiophene (B.P. 84°C)

+ 2H2 + H2S 15
S
Benzthiophene (B.P. 221°C)

+ 2H2 + H2S 14
S
Dibenzthiophene (B.P. 315°C(est.))
 Nitrogen Removal
H
Amine C-C-C-C-N + H2 C-C-C-C + NH3
H

C C
Pyrrole C C + 4H2 C-C-C-C (and C-C-C) + NH3
N
C
C
Pyridine C C + 5H2 C-C-C-C-C (and C-C-C-C-) + NH3
C C C
N

C C C
Quinoline C C C + 4H2 C C-C-C-C + NH3
C C C C C
C N C
 Nitrogen Distribution
in Middle-Eastern Crudes
Arabian Hvy Kuwait Crude
2000 1500
1500  Nitrogen concentrates in the 1200
900
1000

500
heavier portions of a crude 600
300
0 0
50 55 60 65 70 50 55 60 65 70
 As boiling range increases,
Mid. wt-% on Crude Mid. wt-% on Crude

Dubai Crude the complexity of the organic Murban Crude

6000 1200
5000 nitrogen molecules also 1000
800
4000
3000
2000
increase, making the nitrogen 600
400
1000
0 50 60 70
more difficult to hydrotreat
80 90
200
0
65 70 75 80 85 90
Mid. wt-% on Crude Mid. wt-% on Crude

 Nitrogen: Dubai > Arabian

Heavy > Kuwait > Murban
 Postulated HDN Mechanism

(A) Aromatic Hydrogenation

CH CH2
HC CH H2C CH2
+ 3H2
HC CH H2C CH2
N N
(B) Hydrogenolysis
CH2
H2C CH2
+ H2 CH3-CH2-CH2-CH2-CH2-NH2
H2C CH2
N
(C) Denitrogenation
CH3-CH2-CH2-CH2-CH2-NH2 + H2 CH3-CH2-CH2-CH2-CH3+NH3
 Thermodynamic Effects on
HDN Reactions
 HDN proceeds through aromatic saturation
H2

+ NH3
N N
“A”
 The overall reaction is rate (not equilibrium) limited in all ordinary
conditions
 Aromatic saturation equilibrium decreases with increasing temperature
 Rate of NH3 production depends on concentration of intermediates
such as “A”, which decrease with increasing temperature
 Raising temperature is less effective at EOR
Implications of HDN Chemistry
• Complexity makes HDN more difficult than HDS
• Saturation of aromatic rings requires more H2 for
HDN than HDS (On a molar basis)
• Higher H2 consumption releases more heat
• Aromatic saturation is equilibrium controlled at
high temperature (> 400 °C or > 750 °F)
• Desired aromatic saturation requires a narrow
range of temperature applicability
Typical Olefin Saturation
Reactions

+H2
1-Heptene n-Heptane

+H2

Cyclohexene Cyclohexane

+H2

3-Ethyl-2-Pentene 3-Ethylpentane
Typical Aromatics Saturation
CH
Reactions CH
3 3
+ 3H2

Toluene Methylcyclohexane

+ 2H2

Naphthalene Tetralin
(Tetrahydronaphthalene)

+ 3H2

Tetralin Decalin
(Decahydronaphthalene)
 Thermodynamic Equilibrium for
Aromatics Saturation
H2
C
H2 C CH2
+ 3H2
H2 C CH2
C
H2
Benzene Keq Cyclohexane
Temperature, °C Keq
150 2 x 106
205 2200
260 7.1
315 0.14
370 0.063
• At 1 ATM H2, equilibrium favors benzene at temperatures >315°C (600 oF)
• This is why naphtha catalytic reforming works
• For most aromatic compounds at 70-140 Kg/cm2 (1,000-2,000) H2 PP,
aromatics are favored above 400°C (750 oF)
 Aromatic Saturation
Aromatic Saturation
Temperature Effect

Temperature
 Metals Removal

Organo-Metallic Adsorption
(Metal + Catalyst) + Hydrocarbon
Compounds Reaction

Catalyst
Pill

Pore
 Halides Removal
C
C
C C-C-C-C-Cl
C C-C-C-C
C + H2 HCl +
C
C C C
C

HCl + NH3 NH4Cl

 HYDROCRACKING
• The process of converting higher molecular weight
hydrocarbons into more valuable lower molecular
weight hydrocarbons
• C22 H46 + H2 → C16H34 + C6H14

In presence of Hydrogen

at high temperatures(290 – 455 deg C) & high
pressures (105-190 Kg/cm2g)
in presence of a catalyst

The products are clean, saturated & high in value

 Hydrocracking Reactions
• Addition of hydrogen to aromatic centers
• Addition of hydrogen to olefinic double bonds
• Acid-catalyzed cracking of paraffins and side
chains on aromatics
• Acid-catalyzed isomerization of paraffins
• Formation of coke on the surface of catalyst
• Removal of coke by addition of hydrogen
 Hydrocracking Reactions
Feed Hydrogen

Treating Reactions
+ 6H 2 H 2S +
S
+ 7H 2 NH 3 +
N
Polyaromatics Hydrogenation

+ 2H 2 + 3H 2

Monoaromatics Hydrogenation
R R
+ 3H 2
Hydrodealkyalation
R R
+ H2 + RH + H2 + RH
Hydrodecyclization
R +H R H+R H
2 1 2
+ H2 + C 2H 6
Hydrocracking
C nH 2n+2 + H 2 C aH 2a+2 + C bH 2b+2
Hydroisomerization R
R 1 - CH 2 - CH 2 - R 2 CH 2 - CH 2 - R 2
R
Products Hydrogen

Sequence of reactions taking place down the height of a trickle bed hydrocracker
employing amorphous catalyst
 Hydrocracking Reactions

• Bi-functional mechanism

• Requires two distinct types of

catalytic sites to catalyze
separate steps in the reaction
sequence
 Bi-Functional Mechanism
• Metal Function:
– Generates olefin or cyclo-olefin
• Acid Function:
– Generates carbenium ion from olefin
by proton transfer
– Carbenium ion cracks
– Converts carbenium ion to olefin by
proton transfer
• Metal Function:
– Saturates olefins
 Postulated Hydrocracking Mechanism of a
Paraffin
(A) Formation of Olefin CH3
Metal
R-CH2-CH2-CH-CH3 R-CH =CH-CH-CH3
CH3

(B) Formation of Tertiary Carbenium Ion CH3

Acid
R-CH=CH-CH-CH3 R-CH2-CH2-CH-CH3
+
CH3

(C) Isomerization and Cracking

+ Acid +
R-CH2-CH2-C-CH3 R-CH 2+ CH2= C-CH3
CH3 CH3

(D) Olefin Hydrogenation

CH3 CH3
Metal
CH2=C-CH3 CH3-CH-CH3
H2
 N-Paraffins Hydrocracking

• Adsorption on metal sites

• Dehydrogenation (olefin forms)
• Desorption from metal sites and diffusion to acid
sites
• Skeletal isomerization and/or cracking of olefins
on acid sites through carbenium ion
intermediates
• Desorption of olefins from acid sites and
diffusion to metal sites
• Hydrogenation of these olefins on metal sites
• Desorption of resulting olefins
 Hydrocracking Reaction Mechanism

H + H
R c H H H
c H
H R c
c + R c
c H H
H R
3. Diffusion to H H
acid sites
H
4. Crack H H c H H
R c R
R c 5. Hydrogenation
c
R H
c c H H H
H H
H
ACID SITE 2. Olefin METAL SITE
formation
1.
Dehydrogenation

H H
H H c
c R
c
R H
H

Hydrocracking Science and Technology; Julius Scherzer, A.J. Gruia. \ Organic Chemistry 5th addition TW Graham Solomons.
 Effect of Chain Length
on Hydrocracking Conversion

100

n-Decane
Degree of Conversion,%

80
n-Nonane
n-Octane
60 n-Heptane
n-Hexane

40

20

0
240 260 280 300 320 340
Temperature, °C
Influence of reaction temperature on hydrocracking
conversion of n-alkanes with different chain length
Figure From: J. Weitkamp, ACS. SYMP.SER. 20,6, (1975)
 Postulated Hydrocracking
Mechanisms
• Naphthene cracking
• Multiring aromatic cracking
• Dealkylation
• Isomerization

• All proceed through bi-functional

mechanism
Heavy PNA Formation & Coking
Raw Feedstocks Contain
Precursors

Condensation
Reactions

Large PNAs Formed

on Catalyst Surface

HPNAs in Reactor Coke

Effluent Formation
Possible Pathways for Multiring Aromatics

Metal Acid

Acid

R
Acid
 HYDROCRACKING

– TYPICAL HYDROCRACKER
FEEDSTOCKS
• Naphtha
• Heavy Vacuum gas oil
• Thermally or catalytically cracked gas oil

– TYPICAL HYDROCRACKER PRODUCTS

• Middle distillates(HSD, KERO/ATF)
• Naphtha
• LPG
HYDROCRACKING

UNIT CONFIGURATIONS

• Once Through Type

• Single Stage with Recycle
• Two stage
BENEFITS OF HYDROCRACKING

• Middle Distillate yield is 80% as compared to 45% in

FCCU
• Entire feed stock can be converted to the product range
i.e. no coke or by products
• Low Sulphur, Nitrogen and Aromatic content in
Products
 HYDROCRACKING
– HISTORY OF HYDROCRACKING
• Initial units came up during World War II for supplying
gasoline to Europe & America
• Initial catalysts used were natural clays & operating
pressures were about 250 kg/cm2g
• Continuous developments in catalyst has resulted in
lower pressure operation to produce desired quality
products
• At present more than 150 units are operating in the
world.
HYDROCRACKER UNITS OPERATING IN INDIA

SR.NO. REFINERY COMPANY COMMISSIONING

YEAR

1 GUJARAT REFINERY IOCL DECEMBER 1993

2 MANGLORE REFINERY MRPL JULY 1996
3 PANIPAT REFINRY IOCL APRIL 1999
4 MANGLORE REFINERY MRPL NOVEMBER 1999
5 MATHURA REFINREY IOCL JULY 2000
6 NUMALIGARH REFINERY NRL NOVEMBER 2000
7 CPCL 2004
8 PANIPAT REFINERY IOCL DEC 2005
PROCESS CHEMISTRY

HYDROTREATING REACTIONS

Rate of Reaction (Relative) Heat

Liberation
Olefin Saturation Easiest & Rapid 2
Desulfurisation 1
DeNitrification 1
Aromatic Satrn Most Difficult 1
OTHER Reactions are Demetalisation , Oxygen & Halides Removal
 PROCESS CHEMISTRY
HYDROCRACKING REACTIONS

Rate of Reaction
Heteroaromatic Easiest
Multiring aromatic
Monoaromatic
Multiring Naphthene
Mononaphthene
Paraffin Most Difficult
• All the Hydrocracking Reactions are highly
exothermic in nature
 CATALYST
• HYDROTREATING
– Metal based catalyst
– Ni-Mo for higher severity
– Co-Mo for lower severity
• HYDROCRACKING
– Bifunctional Silica - Alumina catalyst
– Acidic sites for cracking reactions
– Metal sites for hydrogenation, dehydrogenation
– Two types of hydrocracking catalysts
• Amorphous for producing middle distillates
• Zeolites for producing naphtha, LPG
 CATALYST

• Catalyst poisons
–Temporary
» Ammonia
» Coke
–Permanent
» Metals
 CATALYST IN OHCU & HCU
PR-OHCU PREP-HCU
SL.NO. CATALYST FUNCTION
Catalyst Bed Type of loading Qty(MT) Catalyst Bed Type of loading
For even disrtibution of
1 TK-10 R1B1 Sock 1.5 TK-10 R1B1 Sock
catalyst & FeS removal
TK-711 R1B1 Sock 3.64 TK-711 R1B1 Sock

2 Metal removal from feed HC-DM R1B1 Sock 3.3 HC-DM R1B1 Sock

3 Hydrotreating HC-K R1B1,B2, B3 Sock/Dense* 94.051 HC-T R1B1,B2,B3 Dense

R2 B1,B2,
4 Hydrocracking HC-22 R3B1,B2 Sock 229.632 DHC-32 R2B1, B2 Dense

5 Post treatment HC-K R3B2 Sock 6.846 HC-K** V-003 Sock

* One bed is sock loaded & the other two beds are dense loaded.
** Future requirement
REACTOR INTERNALS
IMPORTANT PROCESS VERIABLES

 REACTOR TEMPERATURE
 FEED QUALITY
 RECYCLE GAS RATE
 HYDROGEN PARTIAL PRESSURE
 HYDROGEN PURITY
 WASH WATER RATE
 PREP HCU - FEED QUALITY
HYDROCRACKER BLEND FEED PROPERTIES
COMPONENT UNIT BLEND calculated VGO CGO
FLOW RATE MT/YEAR 1,700,000 1,360,000 340,000
FLOW RATE m3/hr 229 184 45
vol % 100 80.41 19.59
wt % 100 80 20
API 21.2 22 18.1
SPECIFIC GRAVITY @15 OC 0.9625 0.9218 0.9459
TOTAL SULPHUR wt % 3.29 3.00 4.44
NITROGEN wppm 1800 1400 3400
HYDROGEN estimated wt % 11.86 12.02 11.22
CONRADSON CARBON wt % 0.59 0.50 0.97
C7 INSOLUBLES wt % 0.05 < 0.05 < 0.12
C7 asphaltene content wppm < 500
BROMINE NUMBER 2.40 0.00 12.00
METALS wppm
Ni+V 1.0 1.0 1.0
Si 0.6 3.0
OTHERS 0.8 1.0
O
ANILINE POINT C 80.2 82 73
O
POUR POINT C 32
UOP K calculated 11.81 11.88 11.56
O
C
IBP 315 320 317
5% est. 370 364 362
10% 390 390 388
30% est. 429 430 425
ASTM DISTILLATION (D-1160)
50% 458 460 452
70% est. 485 485 482
90% 525 525 528
95% est. 545 537 541
EP 574 570 574
 PRE HCU
PRODUCT SPECIFICATIONS
PRODUCT PROPERTY SPEC
Vapour Pres.@ 65 OC Max 16.87 kg/cm2
LPG Vaporisation @2 OC & 760 mmHg 95% min
Copper Strip Corrosion Not worse than 1
Reid Vapour Pressure Max 0.4 kg/cm2 (a)
Light Naphtha
Sulphur Content Max 5 ppmw
Sulphur Content Max 5 ppmw
Heavy Naphtha
Nitrogen Content Max 1 ppmw
ASTM D86 VOL% 10 / FBP Max 205OC / 300 OC
Kerosene Sulphur Content Max 30 ppmw
Freezing Pt/Flash Pt /Smoke Pt -51OC/40OC/21mm
Cetane Number 56 min
HSD
Sulphur Content Max 50 ppmw
COMPARISON OF OHCU & HCU
EXISTING PREP
NO AREA
HYDROCRACKER HYDROCRACKER
1 PROCESS ONCE THROUGH RECYCLE MODE
FULL CONVERSION
2 CONVERSION 60%
(97%)
3 FEED QUALITY VGO VGO+Hy COKER GAS OIL
UNIT CAPACITY 1.5 ON HS VGO
4 1.7 ON VGO+HCGO
(MMTPA) 1.7 ON LS VGO
5 NO.OF REACTORS 3 2
CATALYST OPERATING
6 18 MONTHS 24 MONTHS
CYCLE
HYDROTREATING
7 HC-K HC-T
CATALYST
HYDROCRACKING
8 HC-22 DHC-32
CATALYST
HIGH PRESSURE
9 SINGLE TWO
SEPARATORS
RECYCLE GAS AMINE
10 NO YES
TREATMENT
STRIPPER COLUMN HEAT MP STEAM DIRECT
11 REBOILER FURNACE
SOURCE INJECTION
COMPARISON OF OHCU & HCU
EXISTING
NO AREA PREP HYDROCRACKER
HYDROCRACKER
VACUUM COLUMN AND
12 YES NO
VACUUM FURNACE
TWO : ONE EACH FOR
POWER RECOVERY
13 ONE : ON CHARGE PUMP CHARGE PUMP AND LEAN
TURBINE
AMINE PUMP.

MUG COMPRESSOR
14 INDIVIDUAL STAGE COMMON
SPILLBACK CONTROL
MUG COMPRESSOR ONLY FOR FIRST STAGE
FOR EACH STAGE & FOR
15 SUCTION KNOCK OUT AND COMMON FOR ALL
EACH COMPRESSOR
DRUMS COMPRESSORS
RECYCLE GASCOMPRESSOR (RGC)
FULLY CONDENSING (HP BACK PRESSURE TYPE ( HP
STEAM TURBINE
STEAM SUPPLY) to LP )
16 SEAL OIL SEAL DRY GAS SEAL
SUCTION OF RECYCLE GAS DISCHARGE OF RECYCLE
MAKE UP GAS JOINING AT
COMPRESSOR GAS COMPRESSOR

17 BUFFER GAS COMPRESSOR YES NO

COMPARISON OF OHCU & HCU
YIELD PATTERN (Wt%)
E X IS T . PREP
PRODUCT
OHCU HCU
GAS 1 .3 7 1 .6 1

LPG 1 .2 1 2 .4 1

L IG H T N A P H T H A 2 .1 6 1 3 .2 4

HEAVY NAPHTHA 4 .3 1 3 .3 4

KEROSENE 2 5 .1 1 2 3 .9 4

D IE S E L 2 5 .6 4 4 8 .7 6
U N C O N V E R T E D O IL /
3 9 .2 2 .9 5
BOTTOM S
 REACTOR CATALYST LOADING
DETAILS
Reactor - 1 Reactor - 2

Inlet Diffuser Inlet Diffuser

Liquid Distributor Liquid Distributor

3
Bed 1A TK-10, 1.75 m , Sock, 115mm 6mm Dia Ceramic, Sock, 75mm
Bed 1B 3
TK-711, 10.58 m , Sock, 680mm
Bed 1C 3
HC-DM, 10.58 m , Sock, 680mm
Bed 1D 3
HC-DM, 10.58 m , Sock, 680mm
Bed 1E 3
HC-T, 13.26 m , Dense, 1140mm Bed 1 3
DHC-32, 96.27 m , Dense, 6415mm
3mm Dia

6mm Dia Ceramic, Sock, 75 / 75mm

Liquid Distributor
3mm Dia
6mm Dia Ceramic, Sock, 75mm
Ceramic, Sock, 75 / 75mm
6mm Dia

Bed 2 3
HC-T, 29.58 m , Dense, 2545mm

3mm Dia Liquid Distributor

6mm Dia Ceramic, Sock, 75 / 75mm

6mm Dia Ceramic, Sock, 75mm

Liquid Distributor

6mm Dia Ceramic, Sock, 75mm

Bed 3 3
HC-T, 59.16 m , Dense, 5140mm Bed 2 3
DHC-32, 96.27 m , Dense, 6465mm

3mm Dia
3mm Dia
6mm Dia Ceramic, Sock, 75 / 75mm
6mm Dia Ceramic, Sock, 75 / 75mm
Ceramic, Sock, 19mm Dia
Ceramic, Sock, 19mm Dia
Outlet Collector
Outlet Collector
 REACTOR FACTS & FIGURE
THICKNES SIZE OPERATING DESIGN Wt(Ton)
S Erec/Ope
rating
EQ. Shell/ Dia Leng Press Press VEND
SERVICE head (ID) th Temp Kg/c Tem Kg/cm MOC
NO. OR
mm (TT) (deg m2 g p 2g
mm C) (deg
C)

R- REACTOR 1 261/133 445 1300 431 174.1 454 189.5/F SA 336 GR KOBE 584/920.9
001 HYDROTREATIN 0 0 (max) V F22V + SS 347 Steel,
G WO(Shell) JAPA
N
SA 832 GR22V
+SS 347
WO(Head)

R- REACTOR 2 256/130 445 1340 429 171 454 186/FV SA 336 GR KOBE 588/942.2
002 HYDROCRACKI 0 0 (max) F22V + SS 347 Steel,
NG WO (Shell) JAPA
N
SA 832 GR22V
+SS 347 WO
(Head)

V- HOT 204/105 410 8200 164.5 400 169/FV SA 336 GR KOBE 282/341.7
003 SEPARATOR/ 0 271( F22V (Shell) Steel,
REACTOR(Futur max) JAPA
e) SA 832 GR22V N
(Head)
 REACTOR CATALYST LOADING
DETAILS
Reactor - 1 Reactor - 2

Inlet Diffuser Inlet Diffuser

Liquid Distributor Liquid Distributor

3
Bed 1A TK-10, 1.75 m , Sock, 115mm 6mm Dia Ceramic, Sock, 75mm
Bed 1B 3
TK-711, 10.58 m , Sock, 680mm
Bed 1C 3
HC-DM, 10.58 m , Sock, 680mm
Bed 1D 3
HC-DM, 10.58 m , Sock, 680mm
Bed 1E 3
HC-T, 13.26 m , Dense, 1140mm Bed 1 3
DHC-32, 96.27 m , Dense, 6415mm
3mm Dia

6mm Dia Ceramic, Sock, 75 / 75mm

Liquid Distributor
3mm Dia
6mm Dia Ceramic, Sock, 75mm
Ceramic, Sock, 75 / 75mm
6mm Dia

Bed 2 3
HC-T, 29.58 m , Dense, 2545mm

3mm Dia Liquid Distributor

6mm Dia Ceramic, Sock, 75 / 75mm

6mm Dia Ceramic, Sock, 75mm

Liquid Distributor

6mm Dia Ceramic, Sock, 75mm

Bed 3 3
HC-T, 59.16 m , Dense, 5140mm Bed 2 3
DHC-32, 96.27 m , Dense, 6465mm

3mm Dia
3mm Dia
6mm Dia Ceramic, Sock, 75 / 75mm
6mm Dia Ceramic, Sock, 75 / 75mm
Ceramic, Sock, 19mm Dia
Ceramic, Sock, 19mm Dia
Outlet Collector
Outlet Collector
 Unit’s Reaction Philosophy
A. HydroTreating Metal-Catalysed Co-Mo / Ni-Mo Catalyst
B. HydroCracking Acid-Catalysed-cum- Low Zeolite with Metals
Metal-Catalysed

HT Reactions: Rate of Reacn (Rel) Heat Librn/ H2 consu

Olefin Saturation Easiest & Rapid 2
Desulfurisation 1
DeNitrification 1
Aromatic Satrn Most Difficult 1
OTHER Reactions are Demetalisation , Oxygen & Halides Removal

HC Reactions: Rate of Reacn Net Exothermic in nature

Heteroaromatic Easiest
Multiring aromatic followed by Hydrogenation
Monoaromatic reactions for Saturation of
Multiring Naphthene cracked unsaturated molecules
Mononaphthene
Paraffin Most Difficult
 Introduction: PREP UOP’s HCU

Unit Design Capacity 1.7 MMTPA [212.5 TPH Fresh Feed]

• Licensor UOP , USA

• PMC EIL , INDIA
• LSTK Contractor DICL , KOREA
• Main Sub-contractor Toyo , Japan
• Construction Agencies involved Punj Lloyd , Petron , others

DCS Implementation (on Conventional Mode)

• PMC EIL , INDIA

• DCS YIL , INDIA
• PLC Triconex , USA
• Vibrn Monitoring Bently Nevada , USA
 Major Equipments & Vendors
• R 001, R 002, V 003 KOBE STEEL, Japan
• Heaters (F 001 & F 101) Petron [designed by EIL]
• HP B-L HE (20 nos) IMB, Italy [designed by ABB HT]
• Feed Filter ( 6 x12 cartridges) Ronnigen Peter , USA
• All AFCs GEI HAMON Industries Ltd, Bhopal
• MUG Compressor (K2A/B/C) THOMASSEN C S, ……
(each @ 50% of Normal Process Load, with single common Spillback)
Motor (each 4.7 MW) ASI Robicon, ……
• RGC with HP LP Turbine BHEL(4448 kW, 11670 max cont rpm)
(DG Seal by Burgman)
• Feed & Amine Pumps & PRTs EBARA, Japan
Feed / Amine Motors (3.7/1.55 MW) Toshiba, Japan
• Wash Water Pump PERONI POMPE SpA, Italy
• PF Bottom Pump KSB
 Salient Features of the Unit
• Single Stage Distillate Unicracker [HSD mode, along with LPG maxn]
• Liquid Recycle with Full Conversion [Design Conversion = 97 wt% on FF]
• Designed for High ‘S’ & High ‘N’ content feedstocks
• Designed to process 20 wt% ‘HCGO’ in combined FRESH FEED
• MPT of REACTOR 38 oC
• Low & High Rate Depressurization levels of 7 & 21 Kg/cm2
• Employs Hot HP Separator & RG H2S Absorber (using DEA or MDEA), and
deletion of Vacuum Tower [features differing from existing OHCU]
• Liquid phase Catalyst Sulfiding procedure
• 2 yrs min operating cycle between Cat Regen
• Unit Turndown ratio being 50% of Design Capacity
• Unit tripping based on high reactor skin/ bed temp. (454 C)
 Design Feed Characteristic

Design based on following Feedstocks –

A. 100% KEC 80:20 :: VGO:HCGO

B. 50:50 :: AL:AH AMC 42:30:20:8 :: LVGO:HVGO:HCGO:HGO

Both Feedstocks bearing similar characteristics –

‘S’ content wt% 3.3

Total N ppmw 1800
Broad TBP cut oC 370 – 550
Metals [Ni+V / Total] ppmw 1.0 / 2.0 (max)

CCR wt% 0.5 (VGO) / 1.0 (HCGO)

C7 insolubles wt% 0.05 (VGO) / 0.12 (HCGO)
 Product Characteristics
LPG Vap Pr @ 67oC 16.87 kg/cm2g
Vaprsn @ 2oC, 760 mmHG 95 LV% (min)
Cu Strip Cor (1 hr @38oC) Not worse than No. 1
LN S 5 ppmw (max)
RVP 0.4 kg/cm2A (max)
HN S 5 ppmw (max)
Kero / ATF S 30 ppmw (max)
kV @ -20oC 8 cSt (max)
Color (Saybolt) 20 (min)
Freez / Flash / Smoke pt -51oC / 40oC / 21mm(min)
HCU Blended HSD Pool Cetane no (SOR & EOR) 56 (min) EURO IV
[Total HSD + Total HN + S 50 ppmw (max)
part Kero]
Flash (min) // Pour (max) 36oC // 15/0 oC S/W
kV @ 40oC 2-5 cSt
D86 85/95 LV% 350 / 370 oC (max)
UCO Bleed S 50 ppmw (max)
* UOP to provide Pdt Yield for meeting envisaged 340 oC (max) @ 95 LV% as per EURO IV
Product Yield Pattern , WT% on ( Fresh Feed + MU H2 )

Streams SOR EOR

FF+MU H2 rate, T/h 212.5 + 6.4 212.5 + 6.4
S Ab + DeE offgas 0.63 0.67
CFD offgas 1.40 1.52
OFFGASES 2.03 2.19
LPG 2.41 3.05
DeB Naph 5.66 6.97
PF LN 7.58 8.26
NAPHTHA 13.24 15. 23
PF HN 3.34 3.49
Kero/ATF 23.94 23.74
KERO/ATF 19.15 18.99
HSD 48.76 46.00
HCU DIESEL POOL * 56.89 54.24
UCO Bleed 2.94 2.94
Balance (H2S + others) 3.34 3.35
* Total HSD + Total HN + Part KERO MU H2 @ 6,366 kg/h (or 68,406 NM3/h)
 Catalyst Specifications
Reactors Catalyst Type Loading Catalyst Volume,
Method M3 Weight, Kg
Rx- 1 (75-R-001)
BED-1 TK-10, TK-711 Sock 1.75 TK-10 1410
TK-10, TK-711 Sock 10.58 TK-711 5250
HC-DM (1/10”) Sock 10.58 HC-DM
HC-DM (1/16”) Sock 10.58 11215
HC-T Dense 13.26 HC-T
BED-2 HC-T Dense 29.58
BED-3 HC-T Dense 59.16 91815
Total Catalyst 135.49
Rx- 2 (75-R-002)
BED-1 DHC-32 Dense 96.27 DHC-32
BED-2 DHC-32 Dense 96.27
Total Catalyst 192.54 185020
Rx- 3 (75-V-003)
Future BED HC-K Sock 15.25
 Rx Secn PFD
127.5 42.5
VGO FG
N2 [Split range] Hot ex Units Cold ex Strg
155.3 @ 177 C
3.5 kg 42.5 CGO B/W Surge drum
Liq Recycle 150 C [Ratio Control] 80 C

Feed
Feed Filter SM
Surge
drum 162 C 5 kg
150 C Coalescer
Slop

FCC
P 001 A/B
HS DCU

R 001/002 Design Temp = 454 oC

HFD 413 C, 173.3 KG 419 C, 170.2 KG
R 001/002 Design Pr = 189.5 / 186 kg/cm2g
367.8 T/h PRT P 002
387 C 399 C
197 kg
172.1 kg R 001 169.1 kg R 002
F 001

38 T/h
RG ex E 001 177.5 kg RG
235 C 319 C 337 C Heater 452 C 9.3 T/h 5.8 T/h
E 004 E 002 RG-Q
9.7 T/h RG-Q

264 C 366 C
TC
C/V
E 005 A/B/C E 003 A/B/C
RG-Q
3.4 T/h
Total Rx RG-Q 405 C 409 C
RG-Q
28.2 T/h @ 64 C 169.3 kg 162.2 kg
434 T/h
@ 271 C 325 C 341 C 400 C 409 C
To HS
430 C, 170.4 KG 428 C, 162.8 KG
31.35 DUTY 24.37 DUTY 10.52 DUTY
 RG Loop PFD
RG to F 001, 73 T/h
E 005 A/B/C To Stripper 28.2 T/h Bleed
105 C
MUG Rx Quench
177 C 6.4 T/h
74 C 64 C, 179 kg
RGC
Rx eff ex
Spillback 60 T/h
E 005 A/B/C
157.3 kg 16 T/h @ 66 C
RGC
E 001 E 009 P 113 A/B KOD
EA 001 A-H
A/B Wash water injn DV

HS 201 C 172 C 146 C

23.82 DUTY 45 C *
55 C 154.7 kg
235 C 153.7 kg
RG to
CW E 006
E 004
CS
E 002
F 001 RG
42 C
Scrub RG 226.5 T/h
19 T/h
LC LC KOD Scrub
PRT
LC EA 002
53 C
32 kg *
51 C
31.6 kg To DHDT PRT
LC P 004
HFD CS PRC
269 C CFD
RA to P 003 A/B
ARU
Bleed MUG 1st Suc * 52 C
FRC PRC N2 [Split range]
2 kg
LC LC LC
BFW LA
To SWS
To Stripper
HSS LSS 17.4 T/h Surge
291 T/h 40 C 45 C
S/R drum
LA ex
ARU

Bleed C/V MUG Spillback C/V

 LER PFD
2.7 T/h 0.45 T/h

126 C, 9.5 kg 48 C 17.6 kg

CorInh Sour FG
8.8 kg 1.2 T/h
toDHDT
41 C 81 C 41 C
CW CW
18.3 kg
46 C, 29 T/h
174 C
Ex CFD
SAb
20 T/h
SW 28 T/h SW
ExHFD
STR CW DeB
160 C
268 C 41 C
8.5 kg 55 C, 31 T/h
17 T/h HSD r/d 198 C
UCO
SM @ 3.6 T/h
194 C
346 T/h
246 C Naphtha r/d Unstab Naph
To PF
16.9 kg @ 29 T/h Stab Naph
LPG
0.17 T/h 12.4 T/h
CW 5.94T/h
Sweet FG
33.3 kg
64 C Mixer
16.6 T/h
29.9 kg
29.2 kg PF
CW
LN

161 C
98 C ex LA
Surge
DeE 5.43 T/h
drum
41 C LPG
SW
113 C Sand LPG W/w 45 C Amine
185 C Filter 20 T/h Abs
2 T/h
0.66 T/h
LPG
40 C 110 C
Caustic
wash
49 C

CW
10 Beo RA to ARU
LPG 5.27 T/h RA DMW
Caustic
r/d 40 C, 20 kg
To & Fro
 PF Circuits
285 C 213 C 198 C
To F 101 KERO STR RBLR DeB RBLR SL
CW
PF BOT PUMP 6.4 T/h
359 C, 14 kg 278 C 258 C 225 C 80 C 80 C
UCO Bleed
B B B
E 104

P 105 A/B
246 C 208 C 194 C BFW
155.3 T/h
PF FEED 177 C
Liq Recycle Oil
SM 9.4 T/h SL 8 T/h BFW EA 111
148 T/h IR

7.3 T/h
270 C, 4.6 kg 228 C 191 C 178 C CW
HSD PA HN R/D 164 C, 9 kg HN R/D
170 T/h
169 C
HN to HSD
HSD PA
P 110 A/B @ 7.3 T/h
P 106 A/B 165 C 160 C
DMW
CW Coalescer HSD RD
243 C, 11 kg 214 C 189 C 65 C
B B 45 C 107 T/h 124.5 T/h

HSD R/D
HN STR RBLR DeB FEED KERO to HSD
P 111 A/B
164 C 81 C @ 48 T/h @ 10.5 T/h
STR = SL @ 3.3 t/h
VAP RTN 261 C
CW KERO RD
KERO RD 206 C, 8 kg 65 C 52.4 T/h
42 T/h
F 101 33.82 DUTY P 108 A/B
PF TOP 120 C, 1.055 kg/cm2G
TOP REFLUX @ 192 T/h @ 83 C IR
REFLUX PR @ 0.35 kg/cm2G 234 T/h HN REFLUX @ 214 T/h @ 145 C
181 C, 6 kg 121 C
by FG Split range Controller KERO PA 256 T/h
VAP RTN 157 C
P 107 A/B
PF Bottom STR SL @ 7.2 T/h VAP RTN 195 C
To HGU
KERO PA
 Major Optg Parameters to Monitor

• HCGO ratio in Combined Fresh Feed

• Combined Fresh Feed – C7 Insolubles , Total Metals , Total N
• Each Rx – Temperature values , Bed T’s , Rx P’s , Beds’ Radial Temp
gradient [WABT for monitoring Cat Deactivation rate]
• Gas-to-Oil ratio of each Rx
• R 001 effluent N2 content
• H2 Partial Pressure at Cold Separator
• Wash water injection rate
• Monitoring Ammonium Bisulfide content in HP secn Sour water
• Recycle Gas H2 Purity
• Combined Feed Ratio & Conversion & Yield Pattern

• LP section – Typical optg & QC aspects

 Important Data of the Unit:
• RG before H2S Absorber = 8.32 wt%
• RGC normal Process Load = 59,900 kg/h (or 3,70,841 NM3/h)
RG MW / H2S = 3.62 / Nil
• Wash water injection rate = 18 T/h , and HP Sour Water NH3 / H2S load = 2.61 / 5.38 wt%
• Lean Amine to RG Scrubr = 226.5 T/h (DEA)
Lean Amine to LPG Wash = 19.7 T/h (DEA)
LA / RA H2S load = 0.24 / 2.60 wt%

• CFR = 1.8 [This helps towards LOW TEMP OPRN & Higher HSD Selectivity]
- FF = 212.5 T/h
- LR = 155.3 T/h
Combined Feed = 367.8 T/h
• UCO Bleed = 3 wt% on FF rate
• CPP = 56 wt%

• H2 Ppr at oulet of CS (as per PPkg data) = 144.2 kg/cm2G [CS Pr = 154.7 kg/cm2G]
• H2 Ppr at inlet of E001 A/B (ie. the H2 online analyser location) = 170.9 kg/cm2g
• Gas-to-Oil ratio at the Inlets of R 001 & R 002 = 640 & 976 NM3/M3 , resp

• R 002 each BED avg Temp rise (ie. T) should not exceed 28 oC
R 002 each BED max Temp rise (ie. T) should not exceed 33 oC
R 001 each BED max Temp rise (ie. T) should not exceed 42 oC
• In R 001 or R 002 , IF any Temp pt exceeds its normal level by 28 oC OR, exceeds Rx’s Design Temp level,
THEN Depressuring of the system is to be done @ 21 kg/cm2/min
 Energy saving features like -
• Power generation to the tune of nearly 1630 kW in two numbers of Power
Recovery Turbines.
• Pre heating DM water by using some of the hot streams, thus avoiding
extra cooling by air and water.
• Collection and Recovery System for Steam Traps Condensate .
• Using MP steam as the reboiling medium for the Stripper column instead
of a dedicated furnace.
• Designed to utilize stripped sour water and fractionator o/h boot water as
wash water.
• Common stack and APH for two numbers of furnaces viz.,. Recycle Gas
Furnace and Product Fractionator Feed Heater.
• Designed to handle DEA (Di Ethanol Amine) but in place of DEA
presently MDEA(Methyl Di Ethanol Amine )is being used for scrubbing of
LPG, Offgases and the Recycle Gas.
• Use of dedicated Pump gland Cooling Water System for cooling of glands,
bearings and bridle for Pumps and Compressors, in place of cooling water.
The return water from these Pumps and Compressors are routed back to
cooling water return header.
Thank You