Diesel Hydrotreating and VGO Hydrocracking: M Pramanik General Manager, Indian Oil Corporation Ltd. Paradip Refinery

Diesel Hydrotreating and VGO Hydrocracking
M PRAMANIK
General Manager,
Indian Oil Corporation Ltd.
Paradip Refinery
Agenda
1. Introduction
2. Chemistry
3. Chemical reactions
3. Feed Specification
4. Process description
5. Product Characteristics
6. Catalyst
7. Special Feature/Internals

In today's scenario, hydro processing
involves a major role for meeting.
The quality specification of refinery
products
Increasing refinery margin.

Hydro processing operation involves reaction of
petroleum fraction with Hydrogen mainly for two
applications :
A. Hydrotreating Process :Removal of impurities like
Sulphur/Nitrogen/Metals /saturation of olefins
and aromatics from feed and products.
B.Hydrocracking Process :Cracking of heavier molecule
in presence of hydrogen to obtain valuable high
quality lighter distillates for increasing refinery
margin.

Type of Hydrotreating process :
Naphtha hydrotreating : For removal of sulphur/nitrogen
/oxygen/traces of metals . Hydrotreated naphtha produced as feed
to catalytic conversion process like CCR/Isomerisation
unit/Hydrogen unit etc.
Kerosene Hydrotreating : For ATF production.
Diesel Hydrotreating : For production of Euro-III and Euro-IV diesel
production.
VGO hydrotreating : For producing good quality feed to FCCU for
maximising Propylene production.
Lube oil hydrotreating : Hydrofinishing of Lube oil stocks for
improving quality and eliminate dewaxing process.
Diesel Product Specification

Sl.
No.
Characteristics
Unit
Euro-II/
BS-II
Euro-III
Euro-IV
48
51
51
Cetane Number (CN), min.
Distillation:95% volume recovery

at C, max.
370
360
360
Flash Point (Abel), min.
35
35
35
Sediment, max.
% mass
1.6
0.05
0.05
Density @ 15 C
kg/m3
820-870
820 - 845
820 - 845
Total Sulphur, max.
ppm(wt)
500
350
50
Water content, max.
mg/kg
0.05 % Vol
200
200
Poly-cyclic Aromatic
Hydrocarbon (PAH), max.
% mass
--
11
11
Lubricity, corrected wear scar

diameter (wsd 1,4) @ 60 C,
max.
460
460
m (microns)
460
DHDT-Feed quality
DESIGN CASES (FEED COMPOSITION)
LGO (HS) + Hvy. Kerosene

HGO (HS)
LVGO (HS)
AGO (LS)
FCC TCO
VB Heavy Naphtha
ATF (HS)
HSD from DHDS
Total
DESIGN CASES (FEED PROPERTIES)
CASE 1
CASE 2
33.72
15.83
4.83
8.39
23.56
0.94
12.73
100
30.4
14.3
4.4
26.5
0.8
23.6
100
Specific Gravity @15C

Sulfur, wt.%
Nitrogen, ppmw
Bromine No., gBr2/100g
Aromatics, wt.% (total)
mono
di
tri
Cetane Number (D613)
Flash point, C
Metals, ppm wt.
ASTM D86, C, Vol%
IBP
5
10
30
50
70
90
95
FBP
CASE 1
CASE 2
0.847
1.02
236
9
31
19.7
10
1.3
45
41
0.5
0.856
1.26
298
10
32.1
20
11
1.1
44
42
0.5
104
160
196
262
279
320
361
380
419
104
175
215
280
293
326
363
380
419
DHDT-Process Flow Diagram

HP AMINE ABSORBER
MAKE-UP H2
H2
301-K-01 A/B
HP COLD
SEPARATOR
V -04
FEED
F-01
301-V-01
301-V-07
E- 01
R-01
R-02
MP COLD
SEPARATOR
H2
RECYCLE COMPRESSOR
LEAN AMINE
DIESEL
PRODUCT
DIESEL
STRIPPER
E-07
TO LP. AMINE
ABSORBER
301-C-03
301-V-08
301-V-09
C-01
C-04
NAPHTHA
STABILIZER
NAPHTHA
PRODUCT
Chemistry
DHDT-REACTIONS
HYDRO-DESULFURIZATION
C
C
Thiophene
+ H2
C4H4S
C
C
CCCC + H2S
n-Butane
C4H10
S
HYDRO-DENITROGENATION
+ 5H2 CCCCC + NH3

n-Pentane
Pyridine C5H5N
OLEFIN SATURATION
CCCCCC
C + H2 CCCCCC C
1-Heptene C7 - H14
n-Heptane C7H16
Chemistry
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Chemical Reactions
Catalyst Loading Typical
ACT069,
3.564
mm,
3.564150
m3,mm,
3136
kg m3, 3136 kg
ACT077, 600 mm, 14.25 m3, 7840 kg
HMC868, 19800 kg
kg
HF858,113750
113750
HF858,
kg
Balls, 150 mm, 3.564 m3, 4989 kg

Balls, 150 mm, 3.564 m3, 4989 kg
HR448, 3790 mm, 94.32 m3, 76399 kg
Balls, 150 mm, 3.564 m3, 4989 kg
Balls, 150 mm, 3.564 m3, 4989 kg
HR448, 7660 mm, 180.03 m3, 145824 kg
Balls, 150 mm, 2.761 m3, 3865 kg

Balls, 1215 mm, 12.905 m3, 17422 kg
30
Reactor & Reactor Internals DHDT Unit

Reactor Internals (General Arrangement)
Catalyst & Ceramic Balls
Bed Thermocouples (K1 to K10)
Skin Thermocouples (TST & BST)
Quench Inlet Nozzles
Catalyst Unloading Nozzles

BED - 1
Inlet Device
Lifting Lugs
Test Blocks
Filter Tray
HD Tray
Catalyst Bed
Ceramic Balls
Catalyst Support Grid (CSG)

BED 2, 3 & 4 (each)
Liquid Quench Sparger
HD Tray
Catalyst Bed
Ceramic Balls
Catalyst Support Grid (CSG)

BED 5
Quench Ring
Swirl & Jet Pipes
Quench Tray
Inter Bed PD Tray
HD Tray
Catalyst Bed
Test Blocks
Ceramic Balls
Bottom Basket
UFQ
ISSUES DURING COMMISSIONING & TROUBLE SHOOTING
High Sulphur content in diesel run down(Contd.)
Channel head
was tightened to
190kg torque
DHDT-Design Parameters
Parameters
DESIGN
The design capacity of feed for all the

cases
The catalyst life for the guard bed
The cycle length
The total catalyst life
ASTM D-613 Cetane number for Case 1
The diesel product ASTM D-86 maximum
temperatures for the 95 vol% recovery
The diesel product recoveries for the
design cases 1
The diesel product sulfur content
The flash point of diesel product
Design water content (D1796) in diesel
product
The stabilized naphtha product total sulfur
content
The stabilized naphtha product total
nitrogen content
The stabilized naphtha product RVP (ASTM
D 323)
The H2S content for the sweetened off gas
product
Pure H2 consumption as H2 consumed vs
fresh charge processed
1.8 MMTPA
24 months
24 months min.
72 months min.
56
370C
98.0/ 96.5
<30 ppm.
35C.
200 wt max
5 ppm wt
5 ppm wt
0.4 kg/cm2g max
50 ppm vol (max.)
<1.55 % wt of FF.
DHDT
Typical Operating conditions
Design
SOR/EOR
225.00
27 %
1.28/1.55
97.20
360/390
98/97.6
Typical
Parameters
225
10 %
1.33
99.23
348.51
99.7%
C
C
Kg/cm2
1.36
360/390
410
333/373
368/398
3.0/7.0
1.35
344.60
463.08
322.11
358.77
2.02
hr-1
C
C
C
Kg/cm2
1.13
360/390
352/382
368/398
5.0/8.0
1.12
351.60
345.63
359.14
3.17
Unit
Corrected Feed Rate
TCO Feed Rate
Hydrogen consumed
H2 partial Pr.
Overall WABT
Diesel Yield
Reactor 1
LHSV
WABT
Gas/Oil Ratio at R-01inlet
Reactor Inlet temp
Reactor Outlet temp
Reactor 1 Total DP
Reactor 2
LHSV
WABT
Reactor Inlet Temp
Reactor Outlet temp
Reactor 2 Total DP
TPH
Wt. % of FF
Wt. % of FF
Kg/cm2a
C
%
hr-1
C
DHDT
Reactor DP vs Thruput
DHDT
Reactor WABT vs CETANE No.
DHDT
Feed Cetane vs Product Cetane
Hydrocracking
A Key Catalytic Conversion Process
To
Transform heavy, high boiling, low value and wide
variety of feed stocks to premium quality lower
boiling high value products
By
Carbon- carbon bond scission accompanied with
simultaneous or sequential hydrogenation at high
hydrogen pressure and high temperature
Direct Conversion Technologies

C- Rejection
7
7
7
7
Catalytic &
Thermal
Processes
FCC
Visbreaking
Delayed Coking
Deasphalting
C- rejectionProducts of lower quality

large amount of coke
selectivity poor
Hydrogen
addition
Catalytic
Process
Hydrocracking
7 Fixed Bed
7Ebullated Bed
7Slurry Bed
H2-addition-
Products of higher quality

very high selectivity
Hydrocracking
It is a process of great industrial significance
Products are eco friendly containing mostly
saturated hydrocarbons & low to ultra low sulfur.
So the technology is gaining greater and greater
importance.
Very high flexibility in terms of feed and products
generated & very high selectivity for products.
Wide spectrum of process technology& catalysts
suiting refiners need
HYC a flexible versatile process using

various feeds to give desired products with right
catalyst under suitable conditions
Naphtha
LPG
LCGO/LCO/VBGO
Naphtha
AGO/HCGO/HCO
Naphtha/Middle Dist.
VGO/DAO
Naphtha/Middle Dist/FCC
feed /LOBS/Ethylene feed
Residue give dist.,FCC/Coker feed or low S fuel oil
Hydrocracker feedstocks
Heavy Gas Oils in North America for the production of naphtha.

Vacuum Gas Oils in India & the Middle East.
Specific Gravity:
0.89 0.91
Distillation, ASTM D 1160, Deg C

IBP / 5%
95% / FBP
Asphaltenes, ppm
Metals, ppm
PNA, vol%
Sulphur, ppm
Nitrogen, ppm
340 / 390
550 / 575
< 100 ppm
<1
40 / 25 / 35 (Typical)
3000 5000
400 - 1200
Typical Hydrocracker product pattern, wt%
Feed Streams
Product Streams
VGO
100.0
FG
1.5
Hydrogen
2.25
LPG
4.5
Light Naphtha
12.5
Hy. Naphtha
3.0
Total
102.25
ATF / Kero
39.45
Diesel
39.3
Bottoms
2.0
Total
102.25
Postulated Hydrocracking Mechanism of a

Paraffin
(A) Formation of Olefin
R-CH2-CH2-CH-CH3
CH3
R-CH=CH-CH-CH3
CH3
Metal

Paraffin
(B) Formation of tertiary Carbenium ion
R-CH=CH-CH-CH3
CH3
R-CH2-CH2-C-CH3
CH3
Acid

Paraffin
R-CH2-CH2-C-CH3
CH3
R-CH2 + CH2=C-CH3
CH3
Acid

Paraffin
CH2=C-CH3
CH3
Metal
H2
CH3-CH-CH3
CH3
N-Paraffins Hydrocracking
Adsorption on metal sites
Dehydrogenation (olefin forms)
Desorption from metal sites and diffusion to acid sites
Skeletal isomerisation and/or cracking of olefins on acid
sites through carbenium ion intermediates
Desorption of olefins from acids sites and diffusion to
metal sites
Hydrogenation of these olefins on metal sites
Desorption of resulting olefins
Heavy PNA Formation and Coking

Raw feedstocks Contain
Precursors
Condensati
on
Reactions
Large PNAs formed on Catalyst Surface

HPNAs in Reactor
Effluent
Coke
Formation
Hydrocracker Process flow Diagram

RGC
Makeup H2
MUC
Gas & LN to
recovery sec.
HP Amine
Ex MPU
R-1
R-2
Amine
Scrubber
Ex PSA
Wash Water
F-1
Heavy
Naphth
a
V-1
Feed Filter
V-2
CR
V-3
ATF/Kero
E-1
MPU
To MUC
PRT
AM HVGO
V-8
Feed Preheat Ex
BH HVGO
Unconverted
Oil
V-9
F-2
Diese
l
Hydrocracking configurations
Single Stage Once Through (SSOT):
In this configuration, there is one Hydrocracking reactor. This reactor

is preceded by a Pre Treat reactor for HDS / HDN / HDM of the feed.
This configuration runs on partial conversion mode (65-70 lv%).
The unconverted bottoms is routed as feed to the FCCU.
Once Through Hydrocracker Flow Scheme: Single

Reactor
H2
Feed
Recycle Gas
Gas + LPG
Naphtha
Interbed Quench 1
Reactor
Quench 2
Fractionator
Kerosene
HP Separator
Diesel
HT Bottoms
Hydrocracker Configurations
Single Stage Complete Conversion
Single Pre Treat Stage; followed by,

One Hydrocracking Reactor
Unconverted bottoms from the 1st Pass is recycled back to the

Hydrocracking reactor.
Lower Cost
Lower flexibility
Single Stage Hydrocracker operates at higher temperature levels.
Once through Hydrocracker with Pre Treat Reactor: Part

Gas
& Full recycle
M/up H2
Feed
Recycle Gas
Fractionator
Pre Treat
Reactor
HC
Reactor
Recycle Feed
HP Separator
Naphtha
Kerosene
Diesel
Bottoms
Hydrocracking configurations
Two Stage Units with complete conversion
Two Hydrocracking Reactors

Pre Treat function carried out in the 1st bed of the 1st Stage Reactor.
More expensive in terms of capital cost.

Offers extra operating flexibility.
2nd Stage operates at much lower temperatures in a N free
environment.
Gives an opportunity to fine tune yields.
Two Stage Hydrocracker: Chevron Scheme

RG 1
M/up H2
RG 2
Feed
Q1
Q1
Frac
Q2
Q2
HPS
1
1st Stage
HPS 2
2nd Stage
Bleed
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
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 Catalyst is expensive
Treating Reactions
Metals removal
Olefins saturation
Sulfur removal
Nitrogen removal
Oxygen removal
Aromatic saturation
Easiest
Hardest
Treating By-products
Organic Sulfur
Organic Nitrogen
Oxygen Compounds
H2S
NH3
H2O
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
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 oC )
Desired aromatic saturation requires a narrow range of
temperature applicability
Metals Removal
Organo Metallic
Compounds
Adsorption Reaction
(Metal +Catalyst)
+
Hydrocarbons
Hydrocracking Reactions
Adding of Hydrogen to Aromatic centres
Addition of hydrogen to olefinic double bonds
Acid Catalyzed cracking of paraffins and side
chains on aromatics
Acid-catalyzed isomerisation of paraffins
Formation of coke on the surface of catalyst
Removal of coke by addition of H2
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
Hydrocracking Kinetics
Rate of hydrocracking typically follows first-order
kinetics
Relative reaction rates depend on strength of
adsorption of reactants
Paraffins
Mono-naphthene
Multi-ring naphthene
Mono-aromatic
Reaction
Difficulty
Multi-ring Aromatic
Hetero-aromatic
Heat Release Kcal/m3 H2 (BTU/SCF H2)

Reaction
Heat Release
Desulfurisation
2.1-3.4(50-80)
Denitrogenation
3.0-3.4(70-80)
Deoxygenation
3.0-3.4(70-80)
Olefin Saturation
5.4-6.3(130-150)
Aromatic Saturation
3.0-3.4(70-80)
Hydrocracking
2.1-4.2(50-100)
Major Classes of Reactions in

Hydrocracking
Hydrotreatment Bed
- HDM
- HDO
- HDS
- HDN
- HDA
Hydrocracking Beds
- Isomerization
- Hydrodealkylation
- Naphthene ring
opening
- Paraffin hydrocracking
Coking is side reaction deactivating the catalyst
Typical Hydrocracking Reactions

1-Hydrogenolysis
+ 6 H2
H2S
Benzothiophene
+ 7 H2
NH3
Quinoline
Polyaromatics Hydrogenation
+ 2 H2
Naphthalene
+ 3 H2
Tetralin
Decalin
Monoaromatics Hydrogenation
R
R
+ 3 H2
Hydrodealkylation
R
+ H2
RH
R
+ H2
RH
Hydrodecyclization
R
R1H + R2H
+ H2
+ H2
C2H6
Decalin
Hydrocracking
CnH2n+2
CmH2m+2 +
CpH2p+2 [m+p= n]
Hydroisomerization
R
R1-CH2-CH2-R2
CH-CH2-R2
R
Comparison of Cracking Mechanisms

Mechanism
Activation
Catalyst
Thermal
Thermal
None
Catalytic
Acidic
Hydrocracking
Bi-functional
SiO2/Al2O3/
Zeolite
NiMo, NiW,
noble metal
on
amorphous
or zeolite
Reaction
Intermediate
s
Radicals
Carbenium
Ion
Carbenium
Ion
Selectivity of Cracking Mechanism

Mechanis IsoC1+C2 Olefin
m
paraffin
Thermal
Low
High
High
Aromat iC4
ics and / nC4
Coke
Some Low
Catalytic
Some
Some
High
High
High
Hydrocracking
High
Low
High
Some
High
Hydroprocessing Catalysts
Hydrotreating
Nitrogen and sulfur removal
Non-noble metal on alumina base
Hydrocracking
Hydrogenation Function
Noble Metal
Base Metal
Cracking Function
Amorphous (SiO2/Al2O3 )
Zeolites
Typical Catalyst Components

Hydrogen (metal)
Nickel
Molybdenum
Tungsten
Noble Metals (Platinum, Palladium)
Cracking (acidic, base)

Silica alumina
Zeolites
Unicracking Catalyst
Acid function (provided by support)
Amorphous
Zeolite
Metal function
Active metal
Group VIA (Mo, W)
Promoter metal
Group VIIIA (Co, Ni, Pd, Pt)
Catalyst Support
Amorphous
Large pores
Moderate acidity
Lower surface area
Zeolite
Smaller pores
Variety of structures
High acidity
Acidic Support Materials

Materials
Example
Mixed Metal oxides
SiO2-Al2O3
Zeolite
Y Zeolite
NonZeolitic molecular
sieves
SAPO-5
Cracking Function
Provided by an acidic support
Solid oxide support materials
Amorphous (Al2O3, Al2O3 SiO2)
Zeolite ( Modified Y-zeolite )
Cracking activity determined by :

Acid site strength
Acid site concentration
Catalyst Metals
Base metal
Metal sulfide is the active form
Mo and W sulfides considered Active
Ni and Co sulfides considered Promoters
Combination Active + Promoter metals used
Pd, Pt
Strong hydrogenation function
Sulfur intolerant
Pre Treating Catalyst

Typical Composition
NiO
3 - 10 wt%
MoO3 10-25 wt%
P2O5
1-4 wt%
Al2O3 Remainder
Active Component is MoS2 promoted with NiS

HDN catalysts are also good HDS catalysts; but consume
more H2
Hydrocracking Catalyst is Bifunctional

Acid support provide
Cracking function
Amorphous
SiO2-Al2O3
Low Zeolite
Amorphous
SiO2 Al2O3
High Zeolite
& binder
Metals provide
Hydrogenation function
Non
Noble
Metals
Ni- W/
Ni-Mo/
Co-Mo
Noble
Metals
Like
Pt, Pd
Hydrogenation
Function / Activity
Pt(Pd)
Cracking Function /
Activity
Zeolite
Ni-W
Ni-Mo
Co-Mo
Silica- Alumina
Metal Component
Metal type Non noble transition metals from group
IA ( Mo &W) and group III A (Co, Ni). Noble metals Pt, Pd in
sulfur free environment
Ratio & amount of metals
Base metal atomic ratio is about 0.25 and is equal to
metal grIII / (metal gr III + metal grI)
Noble metal content is < 1 wt %.
Ni or Co oxides = about 3 to 8 wt. %
Mo or W oxides = about 10 to 30 wt. %
Typical Characteristics of Hydrocracking

Catalysts
Metals : Ni-W / Ni-Mo / Pt or Pd

Acidic Support : Amorphous / Zeolite /
Amorphous + Zeolite
Surface Area, m2/g : 260 to 380
Pore Volume, ml/g : 0.35 to 0.5
Shape : Cylindrical or lobed shapes
Diameter,mm
: 1.4 to 2.5
Bulk Density,kg/m3 : 700 to 900
Crush Strength, N/mm : 30 to 45
Catalyst shape and size
Source Axens
Tri lobe
Source- Haldor Topsoe
Catalysts or catalyst support

commonly formed into extrudates,
spheres or pellets. P in fixed bed
reactor affected by catalyst shape
and size. Extrudate length 2 - 4
times its dia (typically F about 1.2
mm). Simplest form of extrudate is
cylinder. Forms like tri lobes /
twisted tri lobes / tetra lobes also
found. Multi lobe cross sections
have higher surface to volume ratio
than cylinders. Shaped catalyst
particles reduce diffusional
resistance, create more open bed
and reduce P
Refiners need better and better catalysts

to have following typical benefits
Higher
1-Activity
2-Selectivity
3-Stability
4-egenerable
Better
product
quality.
Capable
to process
difficult
and heavy
feed
Rugged
to
upsets.
Higher
tolerance
to poisons.
Higher
technoeconomic
returns
Catalyst selection
The selected catalyst system in
Hydrocracker consists of a series of
pretreat catalysts for
hydrodemetallation (HDM),
hydrodenitrogenation (HDN) and
hydrodesulfurization (HDS), followed
by hydrocracking catalysts with both
activity and selectivity tailored to
meet specific conversion objectives.
Pretreatment- A key step in

Hydrocracking
Nitrogen content in the feedstock is
controlled to avoid poisoning of the
hydrocracking catalyst.
Aromatic rings need to be hydrogenated to
facilitate the cracking reactions.
Improvement in hydrotreating catalyst
activity will effect the total catalyst
requirements to carry out given conversion
requirement.
S.N.
Cat.
Shape
Designati
on
Size
TK 10
7hole
tablets
30 20
20 13
16 11
TK 711
Ring
3-lobe
RF 200
HC-H
DHC-32
Shaped
Ex.
Shaped
Ex.
Cylinder 1.6 mm
DHC-8
Sphere
Primary
Function
Inert
Void Bul
Fracti De
on % lb/ft3
55
Ni-Mo, HDM
41
HDM
Ni-Mo,HDS / HDN
Zeolite, Ni-W,
Hydrocracking
1.6 mm Amorphous, Ni-W,
Hydrocracking,
Source S Frazer et al, ARTC,, April 99, Singapore
52.2
44
Typical loading of catalyst in Hydrocracker

Reactor 1
Top Bed of graded cat +
HDM + HDT
Quench
Next Bed of HDT cat
Quench
Bottom Bed of HDT cat
Reactor 2
Top bed HC Cat
Reactor 3
HC cat
Quench
Bottom bed HC Cat
Quench
Next bed- HC cat
Bottom - HDT cat
Typical Hydrocracking Catalysts

Catalyst Metal
Function
ICR106
Ni-W
ICR120
Ni-W
ICR126
Ni-W
ICR 139 Ni-Mo

ICR160 Ni-W
ICR220 Noble
Acid
function
Amorphous
(A)
A
A+
Zeolite(Z)
A+Z
Z
Z
SA,
m2/g
272285
PV
ml/g
0.36
CBD
Kg/m3
881 to
950
285
0.38
285
0.38
881912
926
375
300
380
0.39
0.36
0.62
690
720
545
Catalyst deactivation caused by physical &

chemical processes
Coking / Fouling
Poisoning
Major
Deactivation
Mechanism
Sintering
Typical Additional Reasons for Deactivation

Blocking of catalyst pore by metals or coke
Forming inactive compounds by reaction of active
metals with support.
Destruction / loss of active sites.
Coke composition and formation

Empirical formula for coke Cn Hn to CnH0.5n
Formed during hydrocarbon conversion reactions. It
becomes significant over a long period of time on fixed
bed hydroprocessing catalysts and may block active sites
or plug pores.
In upsets, non catalytic thermal reactions may form
carbon deposits in the interstices of the catalyst particles
or inert material. Such deposits increase the reactor
pressure drop.
Catalytic coke usually do not affect P. The coke affects
activity and selectivity.
Mechanism of Coke Formation

It occurs via complex reactions. Aromatics
alkylation, olefins oligomerization &
dehydrocyclzation, aromatization through
hydrogen transfer & condensation lead to coke.
Polyaromatics may be formed from
monoaromatics through a chain of addition
reactions via carbenium ion mechanism
In bifunctional catalysts, metal and support both

contribute to coking. The intermediate olefins
formed on the metal sites may polymerize on the
acidic support.
Polyaromatics formed on the catalyst get
dehydrogenated leading to coke.
With uniform distribution of coke through the
catalyst, the reactions occur throughout the catalyst
A given amount of coke concentrated at the pore is
more toxic or deactivating than the amount
distributed uniformly.
Catalyst Regeneration
With the progress of cycle, catalyst deactivates approaching EOR
conditions.The product may not meet the specifications, the reactor P
may be high affecting the recycle gas flow rate.
The catalyst activity may be recovered by in situ or ex situ
regeneration. The coke on the catalyst is burnt under controlled
conditions of temperature and air- nitrogen flow. Oxygen
concentration in the reactor I/L nitrogen is monitored & air supply is
strictly regulated to control reactor T. Caustic scrubbing downstream
of air cooler and NH3 injection in effluent exchanger is carried out to
protect against sulfur oxides.
Some of the latest super active catalysts may not regain the high
activity during in-situ regeneration. They are to be properly
regenerated ex- situ.
Unicracking Process Variables
Reactor Temperature
Feed Quality
Feed Rate
Product End Point
Hydrogen Pressure
Liquid Recycle Rate
Recycle Gas Rate
Makeup Hydrogen
Effect of Operating Variables
Increasing the temperature favors conversion.

Decrease in temperature favors heavier product formation.
Aging affects activity and selectivity.
Effect of aging on selectivity is lower for amorphous catalyst compared
to zeolite catalyst.
The aromatic content of middle distillates increases with catalyst age
due to enhancement of temperature.
Increase in temperature increases coking rate
Higher temperature can process difficult feeds.
Increase in temperature reduces cycle length.
H2 partial pressure affects the degree of hydrogenation and the
hydrocracking rate. It also affects HDN Effect on HDS is also there but
to lower extent.
Fresh Feed Properties
Gravity
Boiling Range
Sulfur
Nitrogen
UOP K
Bromine Number
Hydrogen Content
Con Carbon
Heptane insolubles
Color
Metals Content
Fresh Feed Quality

Metals Content
Naturally Occuring: Ni, V, As
High levels may indicate residue entrainment
Upstream processing: Pb, Na, Si, P

Soluble iron naphthenates
Permanent Catalyst poisons

Solid corrosion products (iron sulfide) do not poison
catalyst, but plug the bed
Feed Stock Consideration

High nitrogen feedstock to be processed at higher
pressure and lower SV. Ni + V content should be <
2ppm. CCR < 1% and asphaltenes <0.05%.
Increase in pH2 reduces coking tendency.
Feed Stock Effect on Hydrocracking

Typical Composition of VGO from
different crude sources
Crude Source
Bombay
High
Minas
Arabian
Heavy
Maya California
LV% Yield of
340 540C
API Gravity
LV%, P
N
A
Sulfur Wt. %
Nitrogen ppm
26
37
24
23
24
28
46
23
31
0.5
410
34
44
34
21
0.1
610
22
17
25
58
3.0
150
21
11
29
58
3.1
1880
14
1
42
57
1.0
6470
Source : R. L> Howell et.al., Pet. Ref. Conf. Tokyo
Feed Stock Consideration

Highly paraffinic feed require higher temperature. They
have low coke forming tendency. Produce more
paraffinic higher quality products. They consume less
hydrogen relative to aromatic feed. Longer paraffin
chains can be cracked at lower severity compared to
smaller ones.
Aromatic feed should have hydrogenation activity for
pretreatment as well as conversion catalyst. Acidity
should be moderate.
Polyaromatics have diffusional
problems. Moderate to high acidity required for heavier
feedstocks.
High nitrogen feedstock to be processed at higher
pressure and lower SV. Ni + V content should be < 2ppm.
CCR < 1% and asphaltenes <0.05%.
Increase in pH2 reduces coking tendency.
Weighted Average Bed Temperature

Attribute a weight fraction of the Catalyst bed
to each TI
A=25% catalyst
TI1.
B=35% catalyst
A
TI2
C=40% catalyst eight
B
C
TI3
WABT = 0.25*TI1+0.35*TI2+0.4*TI3
Effect of Feedstock Properties

Property
Endpoint
Sulfur
Nitrogen
Aromatics
Con Carbon
C7 Insoluble
Effect
Reduced Cycle Length
Minimal Effect
(Cracking)
Reduced activity
Metals
Reduced Catalyst Life
Limit
<0.5 wt%
<0.05
wt%
<2 wt
ppm
Comparison of Feedstock Bulk Properties

Property
Feed A
Feed B
Feed C
API Gravity
22.5
20.1
25.7
SG@15.5 oC
0.9188
0.9334
.9001
D1160
Dist,oC
IBP
252
345
285
10%
351
401
357
50%
449
470
418
90%
532
541
483
EP
572
579
511
Feedstock Processability
Prediction from Bulk Properties
Compared to Pilot Plant Data
Property
Feed A
Feed B
Feed C
SOR Temp,
oC
Predicted
Base
+10
-2
Pilot Plant
Base
+11
+3
Deactivation
Rate
Predicted
Base
*1.8
*0.4
Pilot Plant
*3.0
*0.7
Base
Recycle Gas Rate
Ensures H2 availability at catalytic sites

Provides a heat sink
Helps to maintain good flow distribution
Gas/Oil or Hydrogen to Hydrocarbon ratio
Typical Gas/Oil ratios
Treating Inlet > 3000 SCFB (500 Nm3/m3)
Cracking Inlet >7000 SCFB (1200 Nm3/m3)
H2/HC=Gas/Oil * Recycle Gas H2 Purity
H2 to Oil Ratio
It affects bed Dt
Improves distribution of materials.
Reduces over cracking
Suppresses coke formation.
Increase in LHSV
Poorer product properties at same average temperature.
Higher temperature to meet product properties reducing
cycle length.
Pressure
Hydrogen Pressure is key
Required Pressure is determined by:
Feedstock
Desired product quality
Desired Cycle life
Higher pressure or higher purity

Inhibits coke formation
H2 Partial Pressure = Recycle Gas H2 purity *
Pressure
Dependence of catalyst fouling on

hydrogen partial pressure
Increase in hydrogen pressure favors cycle length
reducing fouling rate.
First stage cracking : Fouling rate =
(pH2)4
First Stage HDN
Fouling rate =
(pH2)6
Second Stage cracking Fouling rate =
1
(pH2)4
HPNAs What Are They ?

PNAs = Polymeric Aromatics
Hydrocarbons containing > 2 aromatic rings
HPNAs PNAs with 7+ rings
HPNA
HPNA basic in nature. Adhere strongly to the acid site. The
deposition leads to premature deactivation causing
temperature to be increased to get the activity, again
enhancing HPNA formation. Vicious cycle takes place.
HPNA have low solubility in reactor effluent with precipitation
at lower temperature in F/E exchanger Foulant red brown in
color. The consequences are D P increase and fall in HTC
causing the operation to drop thruput, gas to oil ratio and
higher furnace duty.
Polynuclear Aromatics (PNAs)
Aromatic
Ring Benzene
PCA-9 Rings
Coronene
Heavy PNA
Wash Water
Removes Ammonia from recycle gas
Maintains catalyst activity
Prevents exchanger fouling due to ammonia salt
formation
Required for operation
Catalyst loading methods

Sock Loading
Easiest and Fastest
Must use proper technique
Dense loading
More catalyst in given volume
May be slower than sock loading
Closely monitor to ensure optimum loading
Lower void fraction
Choosing Catalyst Loading Method

Available reactor volume
Pressure drop higher for dense loading
Review pressure drop history, particularly for top bed
Consider recycle compressor head availability and
catalyst support beam system
Flow distribution
Good Flow Distribution

Charecteristics
Good radial temperature profiles
No hot spots
Not sensitive to minor upsets
Results
Minimized risk of temperature excursion
Longer cycle length
Improved selectivity
Reactor Unloading Methods

Gravity Dumping
6-7 m3/hr typical
May not flow readily
Vacuuming
3-5 m3/hr typical
Higher losses (10-30 %)
Combination
Unicracking Metallurgy
Process Factors
High pressure up to 200 kg/cm2 (2850 psi)
Moderately high temperature: 400-455 oC (750-850 oF)
Hydrogen, H2S and NH4HS are present
Materials Properties
Strength
Toughness
Corrosion resistance
Fabrication compatibility
Reactor Metallurgy General MPT Guidelines
2 Cr -1 Mo
93 oC (200 oF)
2 Cr -1
Mo
150 oC
(300 oF)
2 Cr 1 Mo 1/4 V
or
3 Cr 1 Mo
V
Pre 1990 Metallurgy
Newer Metallurgy 66 oC (150 oF)
Reactor Startup Procedure

For heavy wall reactors heat to MPT before
pressurizing above 20% shop test pressure
For older reactors, may need to reduce pressure
and increase temperature if cracks exist
For newer units, lower temperatures may be used
Reactor-Shutdown Procedure
Normal shutdown cooling rates are fine 28oC/hr
(50 oF/hr)
No special degassing procedures required
Excessive cooling rates of heavy wall equipment
could lead to:
Potential H2 stress cracking
Increased overlay disbonding
Typical Examples of Poor Performance and

Trouble shooting of Hydrocrackers
-
Hydro cracker plant problems may sometimes cause

huge economic loss due to
Non utilization of full capacity and consequences on

other units/ ullege problems.
Catalyst activity problem
Selectivity problem
Corrosion, fouling, plugging
Safety aspects.
Reactor Top Bed Pressure Drop

Pleated filters have five times surface area
than the normal cartridge.
Screening Baskets at the top bed may
some time help in controlling pressure
drop.
Efficient graded beds have been
found to be effective.
Typical loaded
scheme found effective in the present
case.
Ammonium Bi-sulfide Corrosion

May be common in conventional hydrocrackers particularly
using demetallized oil. Main source of potential under
deposit corrosion and tube pitting occur by NH4HS.
The Important parameters are :

The NH4 HS concentration is wash water
The fluid velocity in tubes of condenser.

The hydraulic symmetry of the circuit.
The water injection point, water quality and quantity
Condenser outlet temperature
Operational Parameter
Kp Factor
Typical Optimum
Values
0.15
NH4HS wt.% in water
4.8
Wash Water rate, Vol. % of

feed
O2 in wash water, ppm
5.2
Condenser tube velocity,

ppm
0.05
15
Source Al-Naim et al, ARTC,99
Severity of Ammonium Bisulfide Fouling

Depends on Kp factor (mol. % NH3 X mol. %
H2S)
Severe
Kp > 0.5
Moderate
Kp < 0.15
Low
Kp < 0.07
Water Injection Point

Upstream
of
effluent
condenser
with
even
distribution of wash water. Restriction orifices may

be used for good distribution. 20% of injected water
to remain in aqueous phase to avoid acidic dew point
corrosion.
Water Injection Rate

About 5 8 LV% of fresh feed. Concentration of
NH4HS not to exceed 5 wt.%.
Water Injection Quality
Clean stream condensate is good.
chloride
will
be
harmful
as
it
Traces of
will
form
ammonium chloride. Water from open tank has

1-10ppm of O2. So water tank be blanketed with
inert. Only deareated water be used.
Pipings should be symmetrical to ensure equal

distribution of oil, water and vapor phases.
Effluent condenser tubes and piping to have
velocity of 10-20 fps for CS.
Severe
corrosion
by
NH4HS
in
Riyadh
Hydrocracker resulting in loss of production,

high maintenance cost and potential hazard
became
acute
after
revamp
performed
for
overcoming HPNA problem in condenser tubes.
Hydrocracker Runaway
The overall reaction rate is significantly exothermic.
Under some situations the exothermicity may increase
the bed temperature to high level, the heat generated
leading to higher rate and more heat. This can spiral
running out of control and potential loss to vessel or
pipings by excessive temperature.
In normal operation quench sweep the heat. In
emergent situation the depressurization can reduce
and stop reaction. De-pressuring can be fast or slow
based on the use of either of the system deemed
necessary.
Source : E. M. Marszal, Exida
Operator may first try slow system. If

response is not satisfactory he may opt
for fast system.
Safety Integrated Function (SIF) may also
initiate depressuring on detecting high
temperature..
Sorce : E. M. Marszal, Exida
The initiating events that may cause

runaway are
Recycle Compressor Failure

The hydrogen flow decreases.
gas flow stops.
The quench
So heat removal from the
reactor stops. Due to ample hydrogen pressure

the reactions may continue to result in starting
of runaway phenomenon so the SIF may start
slow depressurisation or manual activation of
slow depressurisation.
Source : E. M. Marszal, Exida
2 Reactor Internals Failure

Failure of Cat. Support screens, distribution
boxes
can
Sometimes
help.
initiate
the
temperature
quench
runaway.
management
may
If the damage is severe, it may be
difficult. So depressuring for safe state.
3. Quench Failure
Low or no quench flow due to controller
failure or CV failure.
Sometimes manual
operations of valve from control room/field by

hand jacking the CV.
4. Plugging/
Channeling/
contamination
leading
to
Coking
hot
and
spots
be
leading
to
controlled.
5. Improper
channeling.
catalyst
loading
6. Bed temperature measurement failure

Failure
of
bed
temperature
can
lead
to
runaway if the failure action decreases/ stop

the quench.
Manual operation of CV can
prevent the initiation of runaway.

7. Failure of recycle gas flow controller.
8. Change in feed flow and gas to oil ratio.
9. Failure of fired heater O/L temperature control
leading to high heater O/L temperature.
Special features - Reactor Internals
Feed Diffuser
LIQUID
DISTRIBUTOR
TRAY TRAY
LIQUID
DISTRIBUTOR
TRAY
CATALYST SUPPORT GRID
QUENCH TRAY
H2 QUENCH PIPE
OUTLET COLLECTOR
CATALYST UNLOADING NOZZLE

Thermocouple
nozzle
Reactor Thermocouples
Thank you

Diesel Hydrotreating and VGO Hydrocracking: M Pramanik General Manager, Indian Oil Corporation Ltd. Paradip Refinery

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Diesel Hydrotreating and VGO Hydrocracking: M Pramanik General Manager, Indian Oil Corporation Ltd. Paradip Refinery

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