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
180
160
140
120
100
80
60
40

200

12

12
10
8
6
4

53

7.5
6

2.4

2
0

20
0

2000
2000

2005

HYDROGEN, KNm3/hr

2005

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
products

No

Yes

Yes

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

c
H H
Ethane C2H8

Paraffins
(Alkanes)

H
H

H
c

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

c
H

H
H

Naphthenes
Cyclo-paraffins
Symbol - CnH2n
Ringed saturated
hydrocarbons
May have one
ring or several
combined
May contain
impurities such
as nitrogen and
sulfur

H
H
H c
H c
H

H
c
c

H
H
c
H
H

c H
H

H
H
H
H

H
c H
H

c
H

c
c
H

c
H
H

cyclo-hexane

H
c
H
Butene
C4H8

c
H

Olefins
(Alkenes)

H
H c

H
c
c
H

H
c

c
H

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
c

H c

c H
c

H
H

c
H

H
Toluene

H
c

Aromatics

H c

c H
c

c
H

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
H
H
bonds per ring
c
c
c
c
PNAs
H
H
polynucleararomatic
PNA
Polynuclear aromatics
Two or more benzene rings

Nitrogen Compounds in
Petroleum
Basic Nitrogen

N
NH

H C
3

Amine

2
N

Pyridine

Quinoline

Phenanthridine

Non-Basic
NH
Indole

NH
Carbazole

Sulfur Distribution

Sulfur exists throughout the boiling range of petroleum, except the lightest
fractions
Sulfur concentration increases with increased boiling range
7
6

Sulfur, Wt%

5
4
CatCanyon
Arabian Hvy.
SJV Hvy

3
2
1
0
<350C

350-450C 450-550C

Distillation Range

>550C

Sulfur Compounds in Petroleum

H3C

SH
Mercaptan

CH3

H3C
Disulfide

H3C

S
Thiophene

Benzothiophene

CH3

CH3
Substituted Benzothiophene

S
Dibenzothiophene

Nitrogen DistributionHondo Crude (California Offshore)

Nitrogen rises as boiling range increases

1.5
1.2

Nitrogen, Wt%

0.9
0.6
0.3
0
<315C

315-370C 370-425C 425-480C 480-535C

Distillation Range

>535C

Nitrogen Compounds in
Petroleum
Basic Nitrogen

N
NH

H C
3

Amine

2
N

Pyridine

Quinoline

Phenanthridine

Non-Basic
NH
Indole

NH
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
Nitrogen
Olefins
Oxygen
Metals

To desired
endpoint
To desired
product
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
Metals removal

Easiest

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

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
HC - CH

H2C=CH-CH=CH2 + H2S

S
(B) Olefin Saturation
H2C=CH-CH=CH2 + 2H2

H3C -CH2 -CH2-CH3

HDS Reactions
S

H +H2

Heptanethiol

Heptane

+ H2S

+2H2

S
Thiophene

+ H2S

Butadiene

S
Butylpropyl Sulfide

+2H2

S CH3+2H2
Methylphenyl Sulfide

Butane

+ H2S
Propane

+ CH4 + H2S
Benzene Methane

Reaction Rate Equation

for Desulfurization
At high conversion levels, desulfurization
reactions follow first-order kinetics
The rate constant for easy sulfurcontaining
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
Diethylsulfide (B.P. 92C)

2C2H6 + H2S

+ 2H2

S
Thiophene (B.P. 84C)
+ 2H2
S
Benzthiophene (B.P. 221C)

+ 2H2

Dibenzthiophene (B.P. 315C(est.))

Base = 1

+ H2S

+ H2S

+ H2S

15

14

Nitrogen Removal
Amine

C-C-C-C-N

H
C
Pyrrole

C
C

Pyridine

Quinoline

C
C

C
C

C
C

+ H2

C-C-C-C + NH3

C
N
C
N
C
N

C + 4H2

C-C-C-C (and C-C-C) + NH3

C

C + 5H2
C

C-C-C-C-C (and C-C-C-C-) + NH3

C

C + 4H2
C

C
C
C

C-C-C-C + NH3
C

Nitrogen Distribution
in Middle-Eastern Crudes
 Nitrogen concentrates in the
heavier portions of a crude

1500
1000
500
0

Kuwait Crude

Arabian Hvy

2000

1500
1200
900
600
300

50 55 60 65 70
Mid. wt-% on Crude

Dubai Crude
6000
5000
4000
3000
2000
1000
0 50

 As boiling range increases,

the complexity of the organic
nitrogen molecules also
increase, making the nitrogen
more difficult to hydrotreat

60 70
80 90
Mid. wt-% on Crude

 Nitrogen: Dubai > Arabian

Heavy > Kuwait > Murban

1200
1000
800
600
400
200
0

50

55 60 65 70
Mid. wt-% on Crude

Murban Crude

65

70 75 80 85 90
Mid. wt-% on Crude

Postulated HDN Mechanism

(A) Aromatic Hydrogenation
CH

CH2

HC

CH

HC

CH

+ 3H2

CH2

H2C

CH2
N

N
(B) Hydrogenolysis

H2C

CH2
H2C

CH2

H2C

CH2

+ H2

CH3-CH2-CH2-CH2-CH2-NH2

(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

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

Reactions
CH
CH
3

+ 3H2

Toluene

Methylcyclohexane
+ 2H2

Naphthalene

Tetralin
(Tetrahydronaphthalene)
+ 3H2

Tetralin

Decalin
(Decahydronaphthalene)

Thermodynamic Equilibrium for

Aromatics Saturation
H2 C

+ 3H2

Benzene

150
205
260
315
370

CH2

H2 C

CH2
C
H2
Cyclohexane

Keq

Temperature, C

H2
C

Keq
2 x 106
2200
7.1
0.14
0.063

At 1 ATM H2, equilibrium favors benzene at temperatures >315C (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 400C (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-Cl

+ H2

C
C

C-C-C-C

HCl +
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
S
N

+ 6H 2

H 2S +

+ 7H 2

NH 3 +

Polyaromatics Hydrogenation
+ 2H 2

+ 3H 2

Monoaromatics Hydrogenation
R
R
+ 3H 2
Hydrodealkyalation
R
R
+ H2
+ RH
+ H2
Hydrodecyclization
R
+H
R H+R H
2

+ H2

+ C 2H 6

Hydrocracking
C nH 2n+2 + H 2
Hydroisomerization
R 1 - CH 2 - CH 2 - R 2

Products

C aH 2a+2 + C bH 2b+2
R
R

CH 2 - CH 2 - R 2

Hydrogen

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

+ RH

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
R-CH2-CH2-CH-CH3

Metal

CH3
R-CH =CH-CH-CH3

CH3
(B) Formation of Tertiary Carbenium Ion
R-CH=CH-CH-CH3

Acid

CH3

CH3
R-CH2-CH2-CH-CH3
+

(C) Isomerization and Cracking

+
R-CH2-CH2-C-CH3

Acid

+
R-CH 2+ CH2= C-CH3

CH3
(D) Olefin Hydrogenation

CH3

CH2=C-CH3

CH3

Metal
H2

CH3
CH3-CH-CH3

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
c

3. Diffusion to
acid sites
H

H
c

4. Crack
R

c
H

ACID SITE

c
H

c
H

H H

METAL SITE
1.
Dehydrogenation

H
c

H
c
R

5. Hydrogenation

c
H

H H

2. Olefin
formation

H
c
H

H
c

c
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

Degree of Conversion,%

100
80
60

n-Decane
n-Nonane
n-Octane
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
Effluent

Coke
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

GUJARAT REFINERY

IOCL

MANGLORE REFINERY

PANIPAT REFINRY

MANGLORE REFINERY

MRPL

MATHURA REFINREY

IOCL

NUMALIGARH REFINERY

CPCL

PANIPAT REFINERY

MRPL
IOCL

NRL

COMMISSIONING
YEAR
DECEMBER 1993
JULY 1996
APRIL 1999
NOVEMBER 1999
JULY 2000
NOVEMBER 2000
2004

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

Heteroaromatic
Multiring aromatic
Monoaromatic
Multiring Naphthene
Mononaphthene
Paraffin

Rate of Reaction
Easiest

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

SL.NO. CATALYST FUNCTION
1

For even disrtibution of

catalyst & FeS removal

Metal removal from feed

Hydrotreating

Catalyst

PR-OHCU
Bed Type of loading Qty(MT)

Catalyst

PREP-HCU
Bed Type of loading

TK-10

R1B1

Sock

1.5

TK-10

R1B1

Sock

TK-711

R1B1

Sock

3.64

TK-711

R1B1

Sock

HC-DM

R1B1

Sock

3.3

HC-DM

R1B1

Sock

94.051

HC-T

R1B1,B2,B3

Dense

HC-K

R1B1,B2, B3 Sock/Dense*

Hydrocracking

HC-22

R2 B1,B2,
R3B1,B2

Post treatment

HC-K

R3B2

Sock

229.632

DHC-32

R2B1, B2

Dense

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
 FEED

TEMPERATURE

QUALITY

 RECYCLE

GAS RATE

 HYDROGEN

PARTIAL PRESSURE

 HYDROGEN

PURITY

 WASH

WATER RATE

PREP HCU - FEED QUALITY

HYDROCRACKER BLEND FEED PROPERTIES
COMPONENT
FLOW RATE
FLOW RATE
vol %
wt %
API
SPECIFIC GRAVITY
TOTAL SULPHUR
NITROGEN
HYDROGEN estimated
CONRADSON CARBON
C7 INSOLUBLES

UNIT
MT/YEAR
m3/hr

C7 asphaltene content
BROMINE NUMBER
METALS
Ni+V
Si
OTHERS
ANILINE POINT
POUR POINT
UOP K calculated

wppm

@15 OC
wt %
wppm
wt %
wt %
wt %

BLEND calculated
1,700,000
229
100
100
21.2
0.9625
3.29
1800
11.86
0.59
0.05

VGO
1,360,000
184
80.41
80
22
0.9218
3.00
1400
12.02
0.50
< 0.05

CGO
340,000
45
19.59
20
18.1
0.9459
4.44
3400
11.22
0.97
< 0.12

< 500
2.40

0.00

12.00

1.0

1.0
3.0

wppm

O
O

C
C

1.0
0.6
0.8
80.2
11.81

1.0
82
32
11.88

11.56

315
370
390
429
458
485
525
545
574

320
364
390
430
460
485
525
537
570

317
362
388
425
452
482
528
541
574

73

ASTM DISTILLATION (D-1160)

C
IBP
5% est.
10%
30% est.
50%
70% est.
90%
95% est.
EP

PRE HCU
PRODUCT SPECIFICATIONS
PRODUCT
LPG

Light Naphtha
Heavy Naphtha
Kerosene

HSD

PROPERTY
Vapour Pres.@ 65 OC Max
Vaporisation @2 OC & 760 mmHg
Copper Strip Corrosion
Reid Vapour Pressure
Max
Sulphur Content
Max
Sulphur Content
Max
Nitrogen Content
Max
ASTM D86 VOL% 10 / FBP Max
Sulphur Content
Max
Freezing Pt/Flash Pt /Smoke Pt
Cetane Number
Sulphur Content
Max

SPEC
16.87 kg/cm2
95% min
Not worse than 1
0.4 kg/cm2 (a)
5 ppmw
5 ppmw
1 ppmw
205OC / 300 OC
30 ppmw
-51OC/40OC/21mm
56 min
50 ppmw

COMPARISON OF OHCU & HCU

NO

AREA

PROCESS

EXISTING
HYDROCRACKER
ONCE THROUGH

CONVERSION

60%

FEED QUALITY

VGO

UNIT CAPACITY

1.5
1.7
3

4
5
6
7
8
9
10
11

(MMTPA)
NO.OF REACTORS
CATALYST OPERATING
CYCLE
HYDROTREATING
CATALYST
HYDROCRACKING
CATALYST
HIGH PRESSURE
SEPARATORS
RECYCLE GAS AMINE
TREATMENT
STRIPPER COLUMN HEAT
SOURCE

PREP
HYDROCRACKER
RECYCLE MODE
FULL CONVERSION
(97%)
VGO+Hy COKER GAS OIL

ON HS VGO
ON LS VGO

1.7 ON VGO+HCGO
2

18 MONTHS

24 MONTHS

HC-K

HC-T

HC-22

DHC-32

SINGLE

TWO

NO

YES

REBOILER FURNACE

MP STEAM DIRECT
INJECTION

COMPARISON OF OHCU & HCU

NO

AREA

EXISTING
HYDROCRACKER

PREP HYDROCRACKER

12

VACUUM COLUMN AND

VACUUM FURNACE

YES

NO

13

POWER RECOVERY
TURBINE

ONE : ON CHARGE PUMP

TWO : ONE EACH FOR

CHARGE PUMP AND LEAN
AMINE PUMP.

14

MUG COMPRESSOR
SPILLBACK CONTROL

INDIVIDUAL STAGE

COMMON

15

16

MUG COMPRESSOR
FOR EACH STAGE & FOR
SUCTION KNOCK OUT
EACH COMPRESSOR
DRUMS
RECYCLE GASCOMPRESSOR (RGC)
FULLY CONDENSING (HP
STEAM TURBINE
STEAM SUPPLY)
SEAL
OIL SEAL
MAKE UP GAS JOINING AT

17

ONLY FOR FIRST STAGE

AND COMMON FOR ALL
COMPRESSORS
BACK PRESSURE TYPE ( HP
to LP )
DRY GAS SEAL

SUCTION OF RECYCLE GAS DISCHARGE OF RECYCLE

COMPRESSOR
GAS COMPRESSOR

BUFFER GAS COMPRESSOR YES

NO

COMPARISON OF OHCU & HCU

YIELD PATTERN (Wt%)
PRODUCT

E X IS T .
OHCU

PREP
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 /
BOTTOM S

3 9 .2

2 .9 5

REACTOR CATALYST LOADING

DETAILS
Reactor - 2

Reactor - 1
Inlet Diffuser

Inlet Diffuser

Liquid Distributor
Bed 1A
Bed 1B
Bed 1C
Bed 1D
Bed 1E
3mm Dia
6mm Dia

Liquid Distributor

TK-10, 1.75 m , Sock, 115mm

6mm Dia

Ceramic, Sock, 75mm

TK-711, 10.58 m , Sock, 680mm

3

HC-DM, 10.58 m , Sock, 680mm

3

HC-DM, 10.58 m , Sock, 680mm

3

HC-T, 13.26 m , Dense, 1140mm

Bed 1

DHC-32, 96.27 m , Dense, 6415mm

Ceramic, Sock, 75 / 75mm

Liquid Distributor
6mm Dia

Ceramic, Sock, 75mm

3mm Dia
6mm Dia

Bed 2

HC-T, 29.58 m , Dense, 2545mm

Liquid Distributor

3mm Dia
6mm Dia

Ceramic, Sock, 75 / 75mm

Ceramic, Sock, 75 / 75mm

6mm Dia

Ceramic, Sock, 75mm

Liquid Distributor
6mm Dia

Bed 3

Ceramic, Sock, 75mm

HC-T, 59.16 m , Dense, 5140mm

3mm Dia
6mm Dia

Ceramic, Sock, 75 / 75mm

Bed 2

3mm Dia
6mm Dia

Ceramic, Sock, 19mm Dia

Outlet Collector

DHC-32, 96.27 m , Dense, 6465mm

Ceramic, Sock, 75 / 75mm

Ceramic, Sock, 19mm Dia
Outlet Collector

REACTOR FACTS & FIGURE

THICKNES
S
EQ.
NO.

R001

SERVICE

REACTOR 1
HYDROTREATIN
G

SIZE

OPERATING

Shell/
head

Dia
(ID)
mm

Leng
th
(TT)
mm

Temp
(deg
C)

261/133

445
0

1300
0

431
(max)

Press
Kg/c
m2 g

174.1

DESIGN

Tem
p
(deg
C)
454

Press
Kg/cm
2g

189.5/F
V

Wt(Ton)
Erec/Ope
rating
MOC

SA 336 GR
F22V + SS 347
WO(Shell)

VEND
OR

KOBE
Steel,
JAPA
N

584/920.9

KOBE
Steel,
JAPA
N

588/942.2

KOBE
Steel,
JAPA
N

282/341.7

SA 832 GR22V
+SS 347
WO(Head)
R002

REACTOR 2
HYDROCRACKI
NG

256/130

445
0

1340
0

429
(max)

171

454

186/FV

SA 336 GR
F22V + SS 347
WO (Shell)
SA 832 GR22V
+SS 347 WO
(Head)

V003

HOT
SEPARATOR/
REACTOR(Futur
e)

204/105

410
0

8200

164.5
271(
max)

400

169/FV

SA 336 GR
F22V (Shell)
SA 832 GR22V
(Head)

REACTOR CATALYST LOADING

DETAILS
Reactor - 2

Reactor - 1
Inlet Diffuser

Inlet Diffuser

Liquid Distributor
Bed 1A
Bed 1B
Bed 1C
Bed 1D
Bed 1E
3mm Dia
6mm Dia

Liquid Distributor

TK-10, 1.75 m , Sock, 115mm

6mm Dia

Ceramic, Sock, 75mm

TK-711, 10.58 m , Sock, 680mm

3

HC-DM, 10.58 m , Sock, 680mm

3

HC-DM, 10.58 m , Sock, 680mm

3

HC-T, 13.26 m , Dense, 1140mm

Bed 1

DHC-32, 96.27 m , Dense, 6415mm

Ceramic, Sock, 75 / 75mm

Liquid Distributor
6mm Dia

Ceramic, Sock, 75mm

3mm Dia
6mm Dia

Bed 2

HC-T, 29.58 m , Dense, 2545mm

Liquid Distributor

3mm Dia
6mm Dia

Ceramic, Sock, 75 / 75mm

Ceramic, Sock, 75 / 75mm

6mm Dia

Ceramic, Sock, 75mm

Liquid Distributor
6mm Dia

Bed 3

Ceramic, Sock, 75mm

HC-T, 59.16 m , Dense, 5140mm

3mm Dia
6mm Dia

Ceramic, Sock, 75 / 75mm

Bed 2

3mm Dia
6mm Dia

Ceramic, Sock, 19mm Dia

Outlet Collector

DHC-32, 96.27 m , Dense, 6465mm

Ceramic, Sock, 75 / 75mm

Ceramic, Sock, 19mm Dia
Outlet Collector

Units Reaction Philosophy

A.
B.

HydroTreating
HydroCracking

Metal-Catalysed
Acid-Catalysed-cumMetal-Catalysed

Co-Mo / Ni-Mo Catalyst

Low Zeolite with Metals

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
Heteroaromatic
Easiest
Multiring aromatic
Monoaromatic
Multiring Naphthene
Mononaphthene
Paraffin
Most Difficult

Net Exothermic in nature

followed by Hydrogenation
reactions for Saturation of
cracked unsaturated molecules

Introduction: PREP UOPs HCU

Unit Design Capacity

1.7 MMTPA

[212.5 TPH Fresh Feed]

Licensor
PMC
LSTK Contractor
Main Sub-contractor
Construction Agencies involved

UOP , USA
EIL , INDIA
DICL , KOREA
Toyo , Japan
Punj Lloyd , Petron , others

DCS Implementation (on Conventional Mode)

PMC
DCS
PLC
Vibrn Monitoring

EIL , INDIA
YIL , INDIA
Triconex , USA
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)

RGC with HP LP Turbine

ASI Robicon,
BHEL(4448 kW, 11670 max cont rpm)

(DG Seal by Burgman)

Feed & Amine Pumps & PRTs

Feed / Amine Motors (3.7/1.55 MW)
Wash Water Pump
PF Bottom Pump

EBARA, Japan
Toshiba, Japan
PERONI POMPE SpA, Italy
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
B. 50:50 :: AL:AH AMC

80:20 :: VGO:HCGO
42:30:20:8 :: LVGO:HVGO:HCGO:HGO

Both Feedstocks bearing similar characteristics

S content
Total N
Broad TBP cut
Metals [Ni+V / Total]

wt%
ppmw
oC
ppmw

3.3
1800
370 550
1.0 / 2.0 (max)

CCR
C7 insolubles

wt%
wt%

0.5 (VGO) / 1.0 (HCGO)

0.05 (VGO) / 0.12 (HCGO)

Product Characteristics
LPG

LN

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

S
RVP

5 ppmw (max)
0.4 kg/cm2A (max)

HN

5 ppmw (max)

Kero / ATF

30 ppmw (max)

kV @ -20oC

8 cSt (max)

Color (Saybolt)
Freez / Flash / Smoke pt
HCU Blended HSD Pool
[Total HSD + Total HN +
part Kero]

Cetane no (SOR & EOR)

S
Flash (min) // Pour (max)

20 (min)
-51oC / 40oC / 21mm(min)
56 (min) EURO IV
50 ppmw (max)
36oC // 15/0 oC S/W

kV @ 40oC
D86 85/95 LV%
UCO Bleed

2-5 cSt
350 / 370 oC (max)
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

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

13.24

15. 23

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

FF+MU H2 rate, T/h

NAPHTHA
PF HN

* Total HSD + Total HN + Part KERO

MU H2 @ 6,366 kg/h (or 68,406 NM3/h)

Catalyst Specifications
Reactors

Catalyst Type

Loading
Method

Catalyst
Volume,
M3 Weight, Kg

TK-10, TK-711

Sock

1.75

TK-10

TK-10, TK-711

Sock

10.58

TK-711 5250

HC-DM (1/10)

Sock

10.58

HC-DM (1/16)

Sock

10.58

HC-T

Dense

13.26

BED-2

HC-T

Dense

29.58

BED-3

HC-T

Dense

59.16

Rx- 1 (75-R-001)
BED-1

1410

HC-DM
11215
HC-T
91815

135.49

Total Catalyst
Rx- 2 (75-R-002)
BED-1

DHC-32

Dense

96.27

BED-2

DHC-32

Dense

96.27
192.54

Total Catalyst
Rx- 3 (75-V-003)
Future BED

HC-K

Sock

15.25

DHC-32
185020

Rx Secn PFD
127.5

N2 [Split range]

155.3 @ 177 C

Hot ex Units

Liq Recycle 150 C

Feed
Surge
drum

Feed Filter
162 C

FG

Cold ex Strg
B/W Surge drum

CGO

42.5

3.5 kg

42.5

VGO

[Ratio Control]

80 C

SM

5 kg

150 C

Coalescer
Slop
FCC

P 001 A/B

HS

DCU
R 001/002 Design Temp = 454 oC
R 001/002 Design Pr = 189.5 / 186 kg/cm2g

HFD
PRT P 002

367.8 T/h
197 kg

413 C, 173.3 KG

419 C, 170.2 KG

387 C

399 C

172.1 kg R 001

169.1 kg R 002

F 001
38 T/h

RG ex E 001
235 C

177.5 kg
337 C

319 C

E 004
TC
C/V
E 005 A/B/C

434 T/h
@ 271 C

RG
Heater

452 C

E 002

E 003 A/B/C

RG-Q
9.7
T/h

RG-Q

RG-Q

341 C

400 C

3.4 T/h
RG-Q

405 C
169.3 kg

430 C, 170.4 KG
24.37 DUTY

409 C
162.2 kg

409 C

To HS
31.35 DUTY

5.8 T/h

366 C

264 C

Total Rx RG-Q
28.2 T/h @ 64 C
325 C

9.3 T/h

10.52 DUTY

428 C, 162.8 KG

RG Loop PFD
RG to F 001,
E 005 A/B/C

73 T/h
To Stripper
MUG

177 C

Bleed

28.2 T/h
Rx Quench

105 C
6.4 T/h

64 C, 179 kg

74 C

RGC

Rx eff ex

60 T/h

Spillback

E 005 A/B/C
157.3 kg

16 T/h @ 66 C
E 001
A/B

E 009

201 C

HS

P 113 A/B
Wash water injn

EA 001 A-H

DV

172 C 146 C
23.82 DUTY

55 C

235 C
RG to
E 004
E 002
F 001

45 C
*
153.7 kg

154.7 kg
CW E 006
CS
42 C

LC
PRT

RGC
KOD

LC

EA 002

LC

RG
Scrub
KOD

RG
Scrub

19 T/h

226.5 T/h

53 C

32 kg

51 C
31.6 kg
269 C

HFD

LC

CS PRC
Bleed
FRC

MUG 1st Suc

PRC

LSS
S/R

Bleed C/V

RA to
ARU
52 C

LC
HSS

PRT
P 004

CFD

LC
To Stripper
291 T/h

To DHDT

N2 [Split range]
2 kg

LC

BFW

To SWS
17.4 T/h

40 C
LA ex
ARU

MUG Spillback C/V

45 C

LA
Surge
drum

P 003 A/B

LER PFD
2.7 T/h

0.45 T/h

126 C, 9.5 kg

48 C

CorInh

Sour FG
1.2 T/h
toDHDT

8.8 kg
41 C

CW

46 C, 29 T/h

174 C
Ex CFD

81 C
18.3 kg

CW

41 C

SAb

20 T/h
ExHFD

17.6 kg

28 T/h

SW
CW

STR

268 C
17 T/h

41 C
8.5 kg

55 C, 31 T/h

160 C

SW

DeB

HSD r/d

198 C
UCO

SM @ 3.6 T/h
346 T/h
To PF
16.9 kg

194 C
Naphtha r/d
@ 29 T/h

246 C

0.17 T/h
Sweet FG

Unstab Naph
Stab Naph

64 C
29.9 kg
CW

29.2 kg

98 C
DeE
SW

Mixer

16.6 T/h
PF
LN
161 C

ex LA
Surge
drum

5.43 T/h
41 C
113 C
185 C

0.66 T/h
40 C

LPG
5.94T/h
33.3 kg

12.4 T/h

CW

LPG W/w

Sand
Filter

45 C
20 T/h

LPG
Amine
Abs

2 T/h
LPG
Caustic
wash

110 C

49 C
CW
LPG 5.27 T/h
40 C, 20 kg
r/d

10 Beo
Caustic
To & Fro

RA

DMW

RA to ARU

PF Circuits
285 C
To F 101
PF BOT PUMP

213 C
KERO STR RBLR

198 C
DeB RBLR

SL
CW

359 C, 14 kg

278 C
B

E 104
P 105 A/B

258 C
B

246 C
PF FEED

270 C, 4.6 kg

80 C

BFW

194 C

155.3 T/h
Liq Recycle Oil

177 C
SL 8 T/h

228 C

6.4 T/h
UCO Bleed

80 C

208 C

SM 9.4 T/h

148 T/h IR

225 C

BFW

EA 111

178 C

191 C

HSD PA
170 T/h

HN R/D 164 C, 9 kg

169 C
HSD PA
P 106 A/B

165 C

243 C, 11 kg

HSD R/D
P 111 A/B
STR = SL @ 3.3 t/h
VAP RTN 261 C

189 C

HN STR RBLR
164 C

F 101 33.82 DUTY

PF TOP 120 C, 1.055 kg/cm2G
TOP REFLUX @ 192 T/h @ 83 C
REFLUX PR @ 0.35 kg/cm2G
by FG Split range Controller

Coalescer

CW

65 C

45 C

HSD RD
107 T/h

DeB FEED
81 C @ 48 T/h

KERO RD

PF Bottom STR SL @ 7.2 T/h

DMW

214 C
B

7.3 T/h
HN R/D

HN to HSD
@ 7.3 T/h

P 110 A/B

160 C

CW

206 C, 8 kg

124.5 T/h

KERO to HSD
@ 10.5 T/h
CW

65 C

KERO RD

52.4 T/h

42 T/h

P 108 A/B
IR
234 T/h

181 C, 6 kg

P 107 A/B
VAP RTN 195 C
KERO PA

121 C

HN REFLUX @ 214 T/h @ 145 C

KERO PA 256 T/h
To HGU

VAP RTN 157 C

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 Ts , Rx Ps , 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

RGC normal Process Load
RG MW / H2S
Wash water injection rate
Lean Amine to RG Scrubr
Lean Amine to LPG Wash
LA / RA H2S load

CFR

- FF
- LR
Combined Feed
UCO Bleed
CPP

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 Rxs Design Temp level,
THEN Depressuring of the system is to be done @ 21 kg/cm2/min

=
=
=
=
=
=

= 8.32 wt%
= 59,900 kg/h (or 3,70,841 NM3/h)
= 3.62 / Nil
= 18 T/h , and HP Sour Water NH3 / H2S load = 2.61 / 5.38 wt%
= 226.5 T/h (DEA)
= 19.7 T/h (DEA)
= 0.24 / 2.60 wt%

1.8
[This helps towards LOW TEMP OPRN & Higher HSD Selectivity]
212.5 T/h
155.3 T/h
367.8 T/h
3 wt% on FF rate
56 wt%

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