Chennai Petroleum Corporation Limited

(A group company of IndianOil)

“HYDROCRACKER OPERATION”

Presented by
V.Vasant Kumar
Chief Manager- Process Engineering

RESOT Centre

17th March 2011

 Topics for discussion
z What is a Hydro-cracker?
z What Does a Hydro-cracker Do?
z Hydro-cracker Merits &Demerits.
z History of Hydro-cracking.

z Chemistry of Hydro-cracking.
z Process Configurations.
Topics for discussion (Contd.)
z Process descriptions- General
z Process Variables
z Emergency handling
z Modifications&operational Improvement
done in CPCL – OHCU.
z Case study –CPCL –OHCU.
z Hydro-cracking Licensors
 Process Units
Unit Licensor Capacity

CDU / VDU EIL 3.0 MMTPA

Visbreaker Lummus 1.15 MMTPA

Netherlands

Hydrocracker Chevron Lummus 1.65 MMTPA

Global,USA

CRU Axens, France 225,000 TPA

Hydrogen Technip Benelux 45,000 TPA(56,000)

Netherlands
 Process Units
Unit Licensor Capacity
LPG & UOP, USA 42,000 TPA
Kero Merox 600,000 TPA

Sulphur Recovery EIL / 180 TPD

Delta Hudson, Canada

Amine Regeneration EIL 330 MT/hr

Amine Treating :
a) Fuel gas treating EIL 35,000 TPA
b) LPG treating EIL 60,000 TPA

Sour Water Stripper EIL 60 TPH

 What is a Hydrocracker?

It is a catalytic process for treating and cracking of

H-C feed to lighter products under the condition of
high hydrogen partial pressure and high temperature
in the presence of a catalyst.
What does a Hydrocracker do?
z
z Removes
Removes Metals
Metals (HDM)
(HDM) 100%
100%
z
z Removes
Removes Olefins
Olefins 100%
100%
z
z Removes
Removes Sulfur
Sulfur (HDS)
(HDS) 100%
100%
z
z Removes
Removes Nitrogen
Nitrogen (HDN)
(HDN) 100%
100%
z
z Saturates
Saturates Aromatics
Aromatics (HAD)
(HAD) 50 -95%
50-95%
z
z Convert
Convert Feed
Feed to
to Products
Products 40 -100%
40-100%
z
z H2
H2 Consumption
Consumption 170 -422 Nm3/m3
170-422 Nm3/m3
z
z Operating
Operating Pressure
Pressure 70 -210 kg/cm2G
70-210 kg/cm2G
z
z Operating
Operating Temperature
Temperature 315 -430°C
315-430°C
 HYDROCRACKER MERITS &
DEMERITS
Merits:
i) upgrades heavier fraction of feed to superior quality products.
1. LN has RON, 78-85 - blending stock for the MS pool.
2. HN is excellent feed to reformer. Yields high RON, MS.
3. Jet fuel / SK – low in aromatics & has high smoke point.
4. Diesel - high cetane No, low aromatics, sulfur content
5. Bottom products UCO – Good feed to FCCU and LUBE
plant.
ii) Environmental regulations have imposed limits on the
aromatic and sulfur content of the diesel in order to reduce
emissions of carcinogens and sulfur oxides into the
atmosphere.
iii) More favorable for production of middle distillates when
compared to a FCC unit.
 HYDRO-CRACKER MERITS &
DEMERITS
Demerits:
• High investment cost.
• Frequent mechanical problems with
equipments.
• High energy consumption.(H2 requirement)

NOTE: With the catalyst development, utilization of

suitable metallurgy & experience gained,
Hydro-cracking has become a very reliable
process world-wide.
 History of Hydro-cracking
Early Hydro-cracking (liquid fuel from Coal):

z Used Iron-Based Catalysts

z Very High Pressures (352 kg/cm2G), 426°C
Temperature.
z Used by Germany in WW-II.
z High Gas Make, Low Octane Naphtha, Poor
Quality Diesel (High in Aromatics)
History of Hydro-cracking (contd.)
First
First Modern
Modern Hydro-cracking
Hydro-cracking
z
z 1959:
1959: Chevron
Chevron Demonstrates
Demonstrates Modern
Modern High
High Pressure
Pressure
Process
Process in
in Richmond
Richmond Refinery-iso-cracking.
Refinery-iso-cracking.
z
z Union
Union Oil
Oil Co
Co –– Unicracking.
Unicracking.
z
z UOP
UOP –– lomax
lomax hydro-cracking
hydro-cracking process.
process.
z
z Employed
Employed Amorphous
Amorphous Silica-Alumina
Silica-Alumina Catalysts.
Catalysts.
z
z Rapid
Rapid growth
growth of of hydro-cracking
hydro-cracking after
after development
development ofof
new,
new, Zeolite
Zeolite based
based hydro-cracking.
hydro-cracking.
z
z 1962:
1962: Chevron
Chevron Starts-Up
Starts-Up the
the First
First Hydro-cracker
Hydro-cracker inin
the
the Then
Then Sohio
Sohio Refinery
Refinery in
in Toledo,
Toledo, Ohio
Ohio
z
z 1966:
1966: Chevron’s
Chevron’s Richmond
Richmond Hydro-processing
Hydro-processing
Complex
Complex Starts-Up.
Starts-Up.
History of Hydro-cracking (contd)
State-of-the-Art Hydrocracking
1. Zeolitic Catalysts.
2. Lower Pressures, 70 – 200 kg/cm2G.
3. Moderate Temperatures 340 - 410°C.
 Hydrocracking Licensors
z
z Until
Until Early
Early 1990s,
1990s, the
the Market
Market (~120
(~120 HCRs)
HCRs) Was
Was
Divided
Divided Roughly
Roughly 1/3
1/3 Each
Each Between
Between UOP,
UOP, Unocal
Unocal
and
and Chevron.
Chevron.

z
z In
In 1995,
1995, UOP
UOP Bought
Bought Unocal
Unocal Technology,
Technology, and
and
Now
Now Have
Have 2/3
2/3 of
of the
the World’s
World’s HCRs.
HCRs.

z
z Other
Other Licensors
Licensors (Minor
(Minor Players).
Players).
–– IFP
IFP (Subsidized
(Subsidized by
by French
French Government)
Government)
–– MAKFina
MAKFina (Mainly
(Mainly Compete
Compete inin Mild
Mild HCR)
HCR)
–– Shell
Shell Global
Global (Several
(Several Captive
Captive Shell
Shell Units,
Units,
Criterion
Criterion Cats)
Cats)
 Chemistry of
Hydro-cracking
 Chemistry of Hydrocracking
Typical Hydro-processing & Hydro-cracking
Reactions:
1. De-metallization.
2. De-sulphurization.
3. Denitrification.
4. Olefin Saturation.
5. Aromatics Saturation
6. Hydro-Cracking
7. Sulphiding
8. De-methalization - Thermalcracking
9. Heat Release
 Desulphurisation Reaction
R C CH R
HC CH + 4H2 Catalyst CH 3 CHCH 2CH 3 + H2S
S
Thiophene Branched Paraffin
R
R CH SH+ H2 Catalyst R CH2 R + H2S
Straight-Chain
Thiol Paraffin

Desulfurization reactions convert thiols or thiophenes to

straight-chain or branched paraffins and H2S. The heat of
reaction for desulfurization is about 560 kcal/Nm3 (60 Btu/SCF)
of hydrogen consumed.
RCH2 CH2 CH2 NH2 + H2 RCH2 CH2 CH3 + NH3
CATALYST

AMINE PARAFFIN AMMONIA

Typical hydrotreating reactions with nitrogen

compounds include hydrogenation of pyridines to form
paraffins and ammonia, quinolines to form aromatics
and ammonia, and pyrroles to form paraffins and
ammonia. The heat of reaction of the denitrification
reactions is about 660 kcal/Nm3 (70 Btu/SCF) of
hydrogen consumed.
 Olefins saturation
CATALYST
R-CH2CH =CH2 + H2 RCH2CH2CH3
OLEFIN PARAFFIN

Hydrogenation of olefins is one of the most rapid of the

reactions taking place. All olefins are saturated very
early. The heat of reaction for these reactions is about
1320 kcal/Nm3 (140 Btu/SCF) of hydrogen consumed.
Because the olefin content of the Hydrocracker feed is
significant and because the saturation reactions are
rapid and release a large quantity of heat.
 H H H H
\ / H
R C==== C-H C--------C
+ 3H2 H
\\ // / \ H
C---------C
R C ----------C H
/ \ \ /
H H C --------- C H
AROMATIC / \ /\
H H H H
NAPHTHENE
Hydrogenated to naphthenes heat of reactions vary from about 380-
750 kcal/Nm3 (40-80 Btu/SCF) of hydrogen consumed depending
on the type of aromatic being saturated. In general, higher
pressures and lower temperatures result in a greater
degree of aromatic saturation
 LARGE HC MOLECULES -------> SMALLER MOLECULES

H2 +RCH2 CH2 CH2 CH3 ---------> CH3 CH2 CH3 +RCH3

Catalyst

Paraffin of paraffin of

high carbon no. Catalyst (Ni3S2) less carbon no.

CnH2n+2 + (x-1) H2 x Cn/x H2n/x +2 + Heat

Where x = no. of fragments ( low carbon no. Paraffin molecules),

Cracked from the high carbon no. Paraffin molecule.

The heat release from the hydro-cracking reactions

contribute appreciably to the total heat requirement.
Chemistry of Hydrocracking
Hydro-Cracking Reactions:
z
zLarge Side Chains Easily Removed From
Rings
z
zSaturated Rings Crack Easily.
z
z Paraffins Hard to crack.
z
z Paraffin Products Are Highly Isomerized.
 Chemistry of Hydro-cracking
Hydro-Cracking Reactions (CON):
z In the reactors, sulphur and nitrogen are removed from the
feedstock. In general, the carbon skeleton of the feed
molecule is not altered by heteroatom removal; however,
the boiling point of the molecule decreases by 27-54°C for
sulphur compounds and up to 104°C for nitrogen
compounds. Alkyl aromatics also react in the reaction stage
to give three types of products:
z Aromatic- saturation to give a naphthene.

z Aromatic- dealkylation to give a paraffin and

aromatic- piece.
z Aromatic- condensation to give a polycyclic aromatic.

NOTE:The amounts of each type of product depend on

processing conditions (temperature, catalyst, and hydrogen
partial pressure) and feed composition.
 Chemistry of Hydrocracking
Other
Other Important
Important Reactions
Reactions
zThermal
zThermal Hydrocracking
Hydrocracking oror “De-methylation”
“De-methylation”
–– Undesirable
Undesirable Side
Side Reaction
Reaction Occurring
Occurring at
at >465°C
>465°C
–– Can
Can Occur
Occur at
at Lower
Lower Temperatures
Temperatures With
With Reduced,
Reduced,
Unsulfided
Unsulfided Metals
Metals
–– Produces
Produces Light
Light Gases,
Gases, Mainly
Mainly Methane
Methane
–– High
High H2
H2 Consumption,
Consumption, Uncontrollable
Uncontrollable Heat
Heat
Release
Release
 Catalyst Sulfiding
z Fresh catalyst as well as regenerated catalyst need to be
sulfided so that the optimum catalyst stability and activity
can be obtained before oil feed is introduced.
z The sulfiding process consists of catalyst pretreatment with a
sulfiding agent in the presence of hydrogen. When heated
and passed over the catalyst, the sulfiding agent breaks down
into H2S which reacts with the metal oxides on the catalyst,
thereby generating active metal sites (metal sulfides).
z The reactions taking place during sulfiding are as follows:
(1) Cracking of DMDS (The Sulfiding Agent)
CH3-S-S-CH3 + 3H2 → 2CH4 + 2H2S
This occurs at temperatures between 218–232ºC for
DMDS.
(2) Conversion of metal oxide to metal sulfide
2H2S + 3NiO + H2 → Ni3S2 + 3H2O
 Heat Release/H2 Consumption
From Hydro-crackers
Heat Release,
Reaction H 2 Consumption (Kcal/ Nm 3 H 2)
HDS 3 mols H 2/mol S 565
(17-25 Nm 3/m 3 Per 1% S Removed)
HDN ~5 mols H 2/mol N 610-705
(5-7 Nm 3/m 3Per 1000 ppm N Removed)
Olefin ~1 mol H 2/C=C Bond 1200-1500
Saturation
HDA ~ 3 mols H 2/Ring Saturated 660-800
(2-5 Nm 3/m 3Per 1% Rings Reduced)
Cracking 2-5 Nm 3/m 3 Per 1 LV% Conv. 470-565
Process Configurations
 Process Configurations

z
zSingle
Single Stage - for 100% conversion of feed
into products.
z
zSingle
Single stage - Once -Through operation
Once-Through
–– CPCL ’s design
CPCL’s design configuration
configuration
z
zSingle
Single Stage Recycle
- CPCL
CPCL’s’s initial operation configuration
z
zTwo
Two Stage Recycle
Single -Stage Once
Single-Stage -Through
Once-Through
(SSOT) Hydrocracking
zFeatures
– Low Investment
– Low Hydrogen Consumption
– Very Flexible Plant, Handles a Variety of
Feeds
– Can Handle High End Point, High N
Feeds
– Pretreats VGO for FCC Feed
– Produces High VI Lube Base Stocks
Single Stage (SSOT)
CPCL SSOT YIELDS
CPCL SSOT YIELDS

Yields, Wt % SOR EOR

C1 & C2 0.64 1.11
C3’s 0.67 1.00
C4’s 1.46 2.31
Light Naphtha 3.40 3.60
Heavy Naphtha 5.10 5.10
Kerosene 23.69 23.60
Diesel 21.75 20.02
Bottoms 42.43 42.42
C5+, 96.37 94.75
 Integration of Hydrocracker Unit with
the existing FCCU
z The superior quality of unconverted oil from HCU bottom (sulphur content < 50 ppmw,
N2 content < 1 ppm and metals < 0.1 ppm) is routed to FCCU as feed to derive the
following benefits :
z Improved yield pattern :
Previous Feed (wt.%) Present Feed (wt.%)
(Ref-II VGO) (UCO from HCU)
Gas 2.6 2.5
LPG 13.0 32.0
Gasoline 27.4 49.0
TCO 45.9 10.0
CLO 5.2 2.0
Coke 5.9 4.5

Advantages :
1. Substantial increase in LPG and Gasoline yields.
2. Reduction in CLO and Coke yields.
3. Better quality products with very low sulphur content (MS ‘S’ <10 ppm,
RON 91 and TCO ‘S’ content <100 ppm).
4. Reduction in SO2 emission due to lower sulphur content in feed.
Single -Stage Recycle (SSREC)
Single-Stage
Hydrocracking

zFeatures: Relative to SSOT

–– Can
Can Achieve
Achieve Almost
Almost Full
Full Conversion
Conversion (97%)
(97%)
–– Moderate
Moderate Investment
Investment
–– High
High Quality
Quality Products
Products
–– High
High Hydrogen
Hydrogen Consumption
Consumption
Two Stage Recycle (TSR)
Maximum Liquid Yield and Highest Quality
Make-
Make-Up
Hydrogen Make-
Make-Up Hydrogen
Recycle
Gas

Product
Fresh
Gas
Feed

Recycle
Gas
Light
Naphtha
Heavy
Naphtha
Kerosene

Diesel

First-
First-Stage Second-
Second-Stage Product
Product
 Hydrocracking Configurations
Summary
z
z Single-Stage,
Single-Stage, Once-Through-Liquid
Once-Through-Liquid (SSOT)
(SSOT)
–– Low
Low Conversion
Conversion (35-70%)
(35-70%)
–– Minimal
Minimal Quality
Quality Products
Products (UCO
(UCO toto FCC
FCC UU as
as Feed)
Feed)
–– Relatively
Relatively Low
Low Investment
Investment
z
z Single-Stage
Single-Stage Recycle
Recycle (SSREC)
(SSREC)
–– High
High Conversion
Conversion (90+%)
(90+%)
–– High
High Quality
Quality Products
Products
–– Moderate
Moderate Investment
Investment With
With Easy
Easy Feeds
Feeds
z
z Two-Stage
Two-Stage Recycle
Recycle (TSR)
(TSR)
–– Full
Full Conversion
Conversion
–– Very
Very High
High Quality
Quality Products
Products
–– Moderate
Moderate Investment
Investment With
With Difficult
Difficult Feeds
Feeds
 Product Qualities
Single vs Two stage hydro-cracker

Product Properties VGO HDT SSOT SSREC TSR

Jet Smoke Point, mm 10-15 15-20 20-25 25-30

Heavy Diesel Cetane

50 50-55 60-65 65-70
Number
Feed & products
 Typical Feed stocks

z
zStraight run gas oil.
z
zVacuum Gas Oil (LVGO & HVGO ).
z
zDe-asphalted Oil (DAO).
z
zFCCU cycle oil.
z
zCocker gas oil.
z
zDistillates.
z
zExtracts.
 HYDROCRACKER FEED STREAMS -
CPCL
z HVGO Stream from Ref-II and Ref-III
z DAO
– dist 95%@585°C, vis 33 – 36cst @100°C, asp < 100 ppmw
z Foots Oil
– CCR 0.4%wt, Asp – 40-50 ppmw, Metals*– 3 ppmw
z Slack wax
– CCR - <0.1% wt, Asp – 90 ppmw, Metals – 1 ppmw
z Lube distillate & Lube slop
-CCR – 0.6% wt, Asp – 70 ppmw, Metals – 3.5 ppmw
z VB-VGO

(* Metals = Ni+V+Fe+Na)
 Products from hydro-cracker
z HYDROCRACKER UNIT PRIMARY PRODUCTS:

1. Aviation Turbine Fuel/Superior Kerosene .

2. Diesel
3. LPG
4. Light Naphtha to H2 Unit or gasoline/ LN pool.
5. Heavy Naphtha to Reformer Feed Or diesel pool.
6. Unconverted Oil to FCC Feed or Storage
7. CLPS Off gas to Hydrogen PSA Unit/Fuel Gas
8. Sponge Oil Absorber Sweet Off gas to Fuel Gas

z HYDROCRACKER UNIT BY- PRODUCTS:

1. Filter Back flush to Fuel Oil/ FCC Feed

2. Sour Water to Sour Water Stripper
3. Spent Caustic Solution to Spent Caustic System
4. Blow down from Steam Generators to Storm Water Sewer
CRACKING REACTIONS ARE PERMITTED BY ACID SITES

HYDROGENATION BY METAL SITES

ACID FUNCTION IS SUPPLIED BY CATALYSTS BASES AND

THESE ARE AMORPHOUS SILICA,ALUMINA OR ZEOLITE
CATALYST BASE DEPENDS ON THE TYPE OF PRODUCT
REQUIRED.

METALS SUCH AS MOLYBDENUM, TUNGSTEN, COBALT,

NICKEL, PLATINUM, PALIDIUM ARE DISPERSED ON THE
CATALYST BASE.

NITROGEN IN FEED GETS IS CONVERTED TO AMMONIA

THROUGH REACTIONS AND NH3 SO FORMED PARTIALLY
NEUTRALISES THE ACIDIC SITES THUS REDUCING
CAT.ACTIVITY.
 Catalyst - CPCL Hydrocracker
Loaded Total Requirements for
Densities, Diameter,
3
Catalyst Type Shape kg/m mm Reactors 207-R1, 207-R2
Demetallization Sphere 913 ~4.23 16,130 37.3 203
and Grading
Hydrotreating 977
ICR 134SAQ Asym Quad 2.82 x 2.31 75,022 82.2 551

Hydrocracking
ICR 126 Cylinder 951 2.54 113,348 116 667

ICR 126L Cylinder 977 1.59 12,525 12.8 494

ICR 126N Cylinder 896 2.12 69,547 73.1 438
Support 432
ICR 114ZF Trilobe 2,160 ~4.23 7,075 8 50
 CPCL
CPCL ACTIVE
ACTIVE CATALYST
CATALYST LOADING
LOADING
VOL VOL CAT
M3 % TYPE
207 – R1, Bed 1 37.3 11.6 ICR-122 ZSB, Demet

207 – R1, Bed 2 52.5 16.3 ICR-134 SAQ, HDT

207 – R1, Bed 3 29.6 9.2 ICR-134 SAQ, HDT
30.1 9.4 ICR-126 , HCR
207 – R2, Bed 1 86.0 26.8 ICR-126, HCR
207 – R2, Bed 2 12.8 4.0 ICR-126 N, HCR
73.1 22.7 ICR-126 L, HCR
Total 321.4 100.0

CONFIDENTIAL
Property of Chevron
To be Reproduced and Used only in
accordance with written permission of Chevron.

6/12/2006 mrb G2000829 Krishna 21

207 -R1 Catalyst System
207-R1
Catalyst Function

ICR122ZSB 37.3m3 De-metallization

ICR 114ZF 1.6m3 Support

ICR 134SAQ 82.2m3 Hydro-treating

ICR 114ZF Support
1.6m3
ICR 134SAQ Hydro-treating
13.1m3
ICR 126
46.7m3 Hydrocracking
ICR 114ZF Support
Support Balls
207 -R2 Catalyst System
207-R2
Catalyst Function

ICR 126 Hydrocracking

69.4m3
ICR 114ZF 1.6m3 Support

ICR 126N/126L Hydrocracking

ICR 114ZF 1.6m3 Support

Support Balls
Catalyst Deactivation Caused
By Deposits and
Contaminants
z
z Regenerable
Regenerable
–– Carbon
Carbon Deposits
Deposits or
or “Coke”
“Coke” Caused
Caused by
by Adsorbed
Adsorbed
Condensed
Condensed Polycyclic
Polycyclic Compounds
Compounds
–– Adsorbed
Adsorbed Organic
Organic Nitrogen
Nitrogen Compounds
Compounds Which
Which Tie
Tie Up
Up
Acid
Acid Sites,
Sites, Thus
Thus Lowering
Lowering Cracking
Cracking Activity
Activity
z
z Nonregenerable
Nonregenerable
–– Deposited
Deposited Feed
Feed Metals
Metals -- Ni,
Ni, V,
V, Si,
Si, Fe,
Fe, As,
As, Pb,
Pb, PP
–– Metals
Metals Tend
Tend to
to Deposit
Deposit Near
Near the
the Outer
Outer Edge
Edge of
of the
the
Catalyst
Catalyst and
and Plug
Plug the
the Catalyst
Catalyst Pores
Pores
 Sulfur leaching.
z Normally when H2 is circulated at higher
temperature over the sulphided catalysts the sulphur
will be converted to H2S and the metal sulphides will
be converted to metals, which will reduce the
activities. Fresh or regenerated catalyst will be in
metal oxide, during sulphiding this metal oxides will
become metal suphides. If leaching occur the metal
can not be sulphided again and will result in
reduction of active catalyst volume. In CPCL case,
licenser has noted operating at higher temperature
will effect no leaching. but in the case of hydro-
treaters there is a temperature limit above which we
can not circulate H2 with out oil.
Process description
 Process description
The Hydro-cracker Unit consists of five sections:

1. Feed and Reaction Section

2. Recycle Gas Loop and Oil/Gas Separation Section
3. Fractionation Section
4. Light Ends Recovery Section
5. Make-Up Hydrogen Compression Section
 2
185 kg / cm
3
68,370 Nm / hr.

Make-up H2 Recycle gas Make-up H2

3 compressor Amine
68,370 Nm / hr.
(RGC)
treating from HGU

Quench Make-up H2
H2 Gas compressor
Recycle gas
3 Off-gas to PSA
Feed 2,10,489 nm / hr.
(for
VGO preheating Reactors HP H2 recovery)
feed and Furnace
172.5 Kg/cm2
249.2 filtration gas separator
m3/hr. 3780C
LP
Liquid hydrocarbon gas separator

Fuel gas (to header) 2147 nm3/hr.

Lighter hydrocarbons Light end LPG (to storage) 7.8 m3/hr.
recovery Light Naphtha (to MS pool / HGU) 12.3 m3/hr.
section Heavy Naphtha (to Diesel pool / CRU) 15.5 m3/hr.
Product
Lighter hydrocarbons
stripper

Heavier
hydrocarbons Kerosene / ATF 67.2 m3/hr..
3600C
Furnace Fractionator
Diesel 59.8 m3/hr..

UCO (to FCCU) 115.6 m3/hr..

 H2
from HGU
185 kg/cm2 68,370 nm3/hr.
Feed Feed filter
preheat Reactor feed
furnace
VGO feed Feed
249.2 m3/hr. surge
drum Reactors
PDI
MUGC
207R-1 207R-2

Lean recycle gas

2,10,489 nm3/hr
amine Fuel gas
Feed pump
RGC
Amine Product
absorber stripper
Rich amine C C Quench HPS
to recovery L H H2
P P
To amine absorber
S S
& then to PSA
(for H2 recovery)

Fractionator
feed furnace
Off-gas to
sponge-oil absorber
and then to FG header
2147 nm3/hr.
CW
Fuel gas
and CW
Fuel oil

Kero. P/A

Kero./ ATF R/D

67.2 m3/hr.

Diesel P/A
Diesel R/D
MPS 59.8 m3/hr.

UCO R/D (to FCCU) HN

115.6 m3/hr. LPG (to Diesel pool /
to caustic treatment HGU) LN
12.3 m3/hr. (to MS pool / HGU)
and then to Sphere 12.3 m3/hr.
7.8 m3/hr. Naphtha splitter
Fractionator Deethaniser Debutaniser
 Feed Filter System
z The oil feed must be filtered to remove solids and
particulates which would otherwise lay down on the First
Reactor top bed catalyst, prematurely plugging the top
bed.

- Feed Filters, which remove solids and particulates

from the oil feed. (more than 20micron size
particles are trapped).

z The preheated, combined oil feeds stream enter the feed

filters at 168°C where most of the solids and particulates
are trapped and removed from the reactor oil feed
stream.
 First and Second Reactors
207R-1 and 207R-2
z The purpose of the First and Second Reactors is to provide a
controlled environment for the hydro-cracking and hydro-
treating reactions to take place.

z R1 and R2, reactors and their internals is to promote the

hydro-treating and hydro-cracking reactions at a controlled
rate. Temperature and good flow distribution in the reactors
are the key to controlling reaction rate and achieving good
catalyst utilization.

z Hydro-treating and hydro-cracking reactions are exothermic

and higher temperatures lead to higher reaction rates. In
order to control this temperature rise and, likewise, the rate
of reaction, the catalyst is separated into three beds in the
first reactor and two beds in the second reactor.
 Essential guidelines

•
 Cold High Pressure Separator
(CHPS)
z Cold High Pressure Separator (CHPS), - Separates the reactor effluent
into hydrogen-rich vapor, water, and hydrocarbon liquid reaction
products.

z The CHPS hydrogen-rich vapor steam (recycle gas) is sent to the high
pressure centrifugal separator to ensure no liquid entrainment.
Hydrocarbons make amine foam.

z The relief valve for the high pressure loop is located on the CHPS. The
set pressure of this pilot-operated relief valve is 5% greater than the
normal operating pressure of the CHPS .

z The CHPS temperature is controlled by adjusting the speed of the fans

operating in the reactor effluent air cooler. Lowering separator
temperature will:
1. Increase the recycle gas purity.
2. Lower the recycle compressor horsepower requirement.
3. Make separation of oil from water in the separator more
difficult.
 HP H2S Absorber

z HP H2S Absorber, 207-C4 - Scrubs H2S from the recycle gas stream by
contact with lean amine to help maintain high H2PP.

z The normal operating temperature is 55-68°C.

z The high pressure absorber is designed and operated to keep hydrocarbon

from condensing into the amine. Vapor lines are heat traced and the
amine is kept 5°C hotter than the vapor.

z The temperature of the lean amine must be maintained 5°C hotter than the
feed vapor temperature to prevent and condensation of the vapor on
contacting the lean amine. (This is critical in preventing foaming in the
absorber.)

z A chopper valve will close on low-low flow (20%) to prevent backflow of

high pressure gas on loss of the lean amine charge pumps.
Recycle Gas Compressor
z Recycle Gas Compressor - Supplies the
pressure to move the recycle gas through the
reactor system.
z To maintain H2 partial pressure.
z To remove the heat of reaction.
z To improve oil/gas distribution.
z To remove products from the reactors as
soon as they are formed to prevent
secondary cracking.
 Cold Low Pressure Separator (CLPS)
z Cold Low Pressure Separator (CLPS), - Separates hydrogen-rich
vapor, hydrocarbon liquid, and water phases

z Reactor effluent liquid from the CHPS is let down in

pressure through a level control valve and then flashed in
the CLPS. It is a SS clad carbon steel, vertical vessel with
internals designed to separate hydrogen-rich vapor,
hydrocarbon liquid, and water phases. The CLPS removes
water carried over in the CHPS liquid. The hydrocarbon
liquid is the product stripper feed.
CLPS Vapor H2S Absorber
z It Scrubs H2S from the CLPS Vapor by
contact with lean amine prior to sending
the vapor to the PSA Unit for hydrogen
recovery.
z It is a SS clad carbon steel vessel with a
single packed bed.
z The normal operating temperature is
61°C and pressure is 38kg/cm2g.
 Fractionation Section
z The purpose of the Fractionation Section is to
separate reaction section products into sour
gas, unstabilized naphtha, kerosene, diesel,
and fractionator bottoms.
z The sour gas and unstabilized naphtha are
sent to the Light Ends Recovery Section.
z The kerosene and jet are finished products
and are sent to storage or blending.
z The fractionator bottoms are sent to the FCC
Unit or storage.
SK
STRIPPER

HSD
STRIPPER
 Operating condition
Fresh Feed Rate, BPOD (112% of 37,400
Design)
Fresh Feed Rate, MM MTPA 1.85
LHSV, 1/Hr (Note 1) 0.8
Gross Conversion, Vol % 54
Total Catalyst Life, Yr 5 (With Regeneration)

207-R1 207-R2
2
Reactor Pressure, kg/cm (g)
SOR/EOR
Inlet 172.5/176.0 167.4/167.4
Outlet 169.0/169.0 163.9/163.9
Average Hydrogen Partial Pressure, 145 135
2
kg/cm (a)
Reactor Temperature, ºC
SOR/EOR
Inlet 378/396 378/396
Outlet 411/429 411/429
Maximum 440 440
3 3 845
Gas to Oil Ratio at Reactor Inlet, Nm /m

Number of Reactors 1 1
MAKE-UP H2 PURITY 99.5%
CHEMICAL H2 CONSUMPTION 262nm3/m3 of feed
HYDROGEN BLEED nil
Process variables
Process variables
1. FEED EFFECTS.
2. HYDROGEN EFFECTS.
3. CATALYST EFFECTS.
1. Reactor temperature profile.
2. Catalyst Average Temperature.
4. REACTION SECTION OPERATING
EFFECTS.
5. FRACTIONATION AND LER OPERATION
EFFECTS.
 Process variables
- Feed effects
FEED EFFECTS:
1. LIQUID HOURLY SPACE VELOCITY
(FEED RATE)
2. NITROGEN.
3. ASPHALTENES.
4. METALS
5. POLYCYCLIC AROMATICS
6. SULFUR
7. CHLORIDES
 Process variables- LHSV
Liquid Hourly Space Velocity (LHSV)

Definition: The ratio of reactor feed rate

(m3/hr) to catalyst volume(m3).

Unit is inverse hours (1/hr)

LHSV = (0.234) * (Oil Feed Rate, BPOD)

(Active Catalyst Volume, Ft 3)
 Process variables
variables-- LHSV
zDeterminants
–– Active
Active Catalyst
Catalyst Volume
Volume (Design
(Design Feature)
Feature)
–– Feed
Feed Rate
Rate
zEffects of Higher LHSV
–– Degrades
Degrades Product
Product Properties
Properties at
at Same
Same Catalyst
Catalyst
Average
Average Temperature
Temperature (CAT).
(CAT).
–– Increase
Increase CAT
CAT toto Maintain
Maintain Product
Product
Specifications
Specifications ..
–– Increased
Increased CAT
CAT Increases
Increases Coking
Coking ..
–– Higher
Higher CAT
CAT Reduces
Reduces Cycle
Cycle Length
Length ..
zLHSV Should be Optimized to Meet Product
Properties and Catalyst Life .
Effect of Feed Nitrogen Content
z
z Typical
Typical Nitrogen
Nitrogen Levels
Levels Are
Are <1100
<1100 ppm
ppm
z
z Nitrogen
Nitrogen is
is aa Strong
Strong Poison
Poison for
for Acid
Acid Sites
Sites in
in HCR
HCR
Catalysts.It
Catalysts.It is
is aa temporary
temporary catalyst
catalyst poison.
poison.
z
z It
It neutralise
neutralise the
the active
active site.
site.
z
z Desorption
Desorption rate
rate isis very
very slow.
slow. ItIt will
will take
take several
several days
days to
to
desorb.
desorb.
z
z Higher
Higher N2N2 in
in feed
feed requires
requires higher
higher CATs
CATs toto achieve
achieve aa
desired
desired conversion
conversion this this will
will result
result in
in Shorten
Shorten the
the Cycle
Cycle
Life.
Life.
z
z Higher
Higher NH3
NH3 Levels
Levels WillWill need
need higher
higher Water
Water Wash
Wash Rates.
Rates.
 Effect of Asphaltene in Feed
z Asphaltene content should be less than
100ppm.
z Defficult to crack and saturate.
z Polymerise on the catalyst surface as
carbonaceous deposits.
Note : Asphaltene content can be reduced by
proper operation of upsteam unit.
 Effect of Metals in Feed
z Ni, Va, Na, Ca & Mg -present in the feed. Limit is
1ppm (max).
z Metels are too large to fit inside the catalyst pores.
Deposited on the catalyst and irreversibly destroy its
activity.
z Fe – not only deactivate the catalyst through pore
mouth plugging and cause pressure drop across the 1st
bed of the 1st reactor.
Note : Metal content can be reduced by proper operation
of upsteam unit.
 Effect of polycyclic aromatics
in Feed
z Polycyclic aromatics (PCA) –Coke
precursors.
z It is a large multi-ring aromatic compounds
tend to dehydrogenate on the catalyst,
ultimately forming coke.
z Has a significant effect on catalyst activity
and fouling rate of down stream equipment.
 Effect of Sulfur & chlorides in
Feed
z Higher sulfur content would shorten the life of the
reactor and other critical equipment.
- It increases the H2S content of the recycle gas,
decrease H2 partial pressure and reduce the catalyst
performance.
z Chloride –limit is 1ppm(max).
– The salt, Mgcl2 &Nacl, bulids up at the top of the 1st
reactors.
– Reactor pressure drop will increase. Limit the
feed rate and require a shut down.
– It may cause fouling and stress corrosion cracking in
the feed/effluent exchanger.
 Effect of Feed Boiling Range
z Feed mixture is dependent on the crude oil used and the
operating conditions of the upstream units. The primary
function of the hydrocracker is to crack the large molecules
(VGO-sized) to smaller molecules (naphtha-, kerosene-,
diesel-sized).
z As the feed boiling range increases, the levels of nitrogen,
polycyclic aromatics (PCA), asphaltenes, and metals
increase. A higher feed nitrogen level and higher PCA level
require a higher CAT. High PCA, asphaltene, and metal
levels increase the fouling rate of the catalyst. Therefore,
increasing the feed boiling range shortens the run span by
increasing both the required CAT and the fouling rate.
z Catalyst poisons such as asphaltenes, metals, and nitrogen
increase exponentially with boiling point
 Sources of Contaminants and
Their Effects
Contam inant Source Effect on Isocracking
Catalyst
Ni + V High End Point Feed 1% M etals = 15°F Activity Los
Si Silicone Antifoam Pore M outh Plugging
Na Sodium Hydroxide
Desalting / Flooding 1% = 15°F Activity Loss
(poor de-salter operation)

FeS x Corrosion Products Pore M outh Plugging

As Arsenic in Crude 1% as = 50°F Activity Loss
P Phosphoric Acid in Feed 1% P = 90°F Activity Loss
Asphaltenes Residuum Higher Fouling Rate
 CPCL
CPCL FEED
FEED COMPOSITION
COMPOSITION
SR VB 90% SRVG O
VGO VGO 10% VB VG O
API 2 0 .8 2 0 .7 2 0 .8
S u lf u r , w t % 2 .8 5 .0 3 .0 3
N it r o g e n , p p m 1000 2000 1102
A s p h a lt e n e s , p p m 100 200 110
C C R w t% 0 .6 1 .0 0 .6 4
N i+ V , p p m 1 .0 9 .0 1 .8
Iro n , p p m 0 .0 5 .0 0 .5
D 1160 EP, Deg C 585 500 585

CONFIDENTIAL
Property of Chevron
To be Reproduced and Used only in
accordance with written permission of Chevron.

3/27/2003 mrb G2000829 Krishna 21

FEED PROPERTIES- CPCL-OHCU
Feed S pecifications S R VGO VB VGO
Feedstock S ources CDU/VDU – Bombay Visbreaker
High/Persian Gulf Unit
Quality S pecifications
Distillation, AS TM D 1160, ºC
S tart 320 300
10% 380 324
30% 415 378
50% 440-460 402
70% 490 435
90% 540 473
End Point, Max. 585 500

API Gravity 20.8-34.8 20.7

S pecific Gravity 0.825-0.929 0.93

Asphaltenes, Wt %, Max. 0.01 0.02

Iron, ppm 0 5
Nitrogen, ppmw 1000 2000
S ulfur, Wt % 2.8 5
Kinematic Viscosity at 50ºC, cS t 46.3
Kinematic Viscosity at 100ºC, cS t 9.6
Kinematic Viscosity at 200ºC, cS t 0.6-1.65
Kinematic Viscosity at 250ºC, cS t 0.4-1.1
CCR, Wt % 0.6 1
Nickel + Vanadium, ppm 1 9
 Products Specification
CPCL-OHCU
Product Inspections:
Cut Light Heavy Naphtha Kerosene/ATF Diesel Bottoms
Cut Points, ºC NC hth 95–130 130-260 260-370 370+
5-95
API Gravity 79 54 42.5 36.5 34.8
Density @15° C 670-675 763-768 812-817 820-870 850-855
AS TM, ° C D 86 D 86 D 86 D 86 D 1160
ST 23 102 142 229 337
10 36 107 161 268 394
50 49 114 193 302 473
90 79 128 238 348 548
EP 91 147 266 376 562
S ulfur, ppm <5 <5 10 (Max.) 10 (Max.) <50 (Max.)

Mercaptan S ulfur, ppm 10 (Max.) 10 (Max.)

Nitrogen, ppm <1 <1 <1 (Max.)
Paraffins, LV % (Estimated) 66 30

Naphthenes, LV % 32 62
(Estimated)
Aromatics, LV % (Estimated) 2 8 22

Flash Point, ° C 38 (Min.) 35 (Min.)

S moke Point, mm 21
Cetane Index (D 613) 55 (Min.)
Freeze Point, ° C (-)51
Pour Point, ° C 3 (Max.)
Viscosity @ 40° C, cS t 2 to 5
Viscosity @ 100ºC, cS t 4.2
Viscosity @ -20ºC, cS t 8
Water, ppm 500 (Max.)
Metals, ppm <0.1
Octane Number, Estimated
RONC/MONC 75/76 64/62
2 0.8 (Max.) 0.8 (Max.)
RVP, kg/cm
Process Variables – H2 Effects

– Hydrogen Partial Pressure.

– Recycle gas purity
– Mack-up H2 purity
– Recycle gas rate (Gas/Oil Ratio)
– Catalyst Temperature.
– Catalyst life.
 Process Variables

z Reactor temperature profile.

z Catalyst Average temperature.

Process variables - Make up H2 Purity
z Make-up hydrogen consists of a mixture of hydrogen
and methane. Methane is also produced in the
hydrocracking reaction. The hydrogen is consumed in
the hydrocracking reactions and lost.
z To maintain the desired hydrogen partial pressure and
maintain the purity of the make-up hydrogen (99.5
mole%H2).
z If the make-up hydrogen purity falls below the design
value, a bleed may be required to maintain an
acceptable hydrogen partial pressure.
 Process variables:
Hydrogen Partial Pressure (pH22)
zH
zH22 partial
partial press
press –– can
can be
be increased
increased by
by
–– Increasing
Increasing total
total system
system pressure
pressure (operate
(operate as
as close
close as
as the
the relief
relief
valve
valve set
set press
press located
located on
on the
the CHPS).
CHPS).
–– Increasing
Increasing Make-Up
Make-Up Hydrogen
Hydrogen Purity.
Purity.
–– Increasing
Increasing Recycle
Recycle Gas
Gas Purity
Purity (Bleed,
(Bleed, Treating)
Treating)
–– Recycle
Recycle Gas
Gas Rate.
Rate.
–– Decreasing
Decreasing CHPS
CHPS temperature.
temperature.
zHigher
zHigher PH
PH22 Effects
Effects
–– Improves
Improves Product
Product Properties
Properties (Jet
(Jet Smoke
Smoke Point,
Point, Diesel
Diesel
Cetane
Cetane Number).
Number).
–– Increases
Increases Cycle
Cycle Length.
Length.
 MAKE-UP HYDROGEN QUALITY

Parameter Hydrogen Specifications

Hydrogen Purity, Mole % 99.5(Min.)
CO + CO2, Mole 20 ppm (Max.)
Nitrogen, Mole 50 ppm (Max.)
Water, Mole 50 ppm (Max.)
Chlorine + Chlorides, Mole 1ppm (Max.)

Note: Co- more than 30ppm and reactor temp less than 200°c, the
chances of nickel corbonyl formation is more. Which is highly toxic
 Example: Effect of Increased Make-Up
Make-Up
Hydrogen Purity on Product Properties
and Cycle Length
SSOT Operation, System Pressure= 169 kg/cm2

2 2 2
Make -Up Purity, % 85 96 99.9
Recycle Gas Purity, % 75 86.5 90
Hydrogen Partial Pressure, 125 136 140
kg/cm 2G
Jet Smoke, mm 18 20 21
Diesel Cetane Number 50 53 55
Cycle Length, Months 14 24 29
Process variables:: Recycle
Recycle Gas
Gas Rate
Rate (Gas/Oil
(Gas/Oil
Ratio)
Ratio)

z
z Effects
Effects of
of High
High Recycle
Recycle GasGas rate
rate (Gas/Oil
(Gas/Oil Ratio)
Ratio)
z
z Decreases
Decreases Catalyst
Catalyst Fouling
Fouling
z
z Maintains
Maintains High
High Hydrogen
Hydrogen Partial
Partial Pressure
Pressure inin Reactors.
Reactors.
z
z Providing
Providing aa heat
heat sink
sink for
for high
high heat
heat of
of reaction
reaction in
in the
the
bed.
bed.
z
z Helps
Helps Distribution
Distribution ofof Reactants
Reactants Over
Over the
the Catalyst
Catalyst
Bed.
Bed.
z
z Limits
Limits Bed
Bed Temperature
Temperature Rise.
Rise.
z
z Increases
Increases Catalyst
Catalyst Activity
Activity
z
z Minimizes
Minimizes "Overcracking"
"Overcracking" of of Products
Products by
by carrying
carrying
them
them out
out of
of the
the reactors
reactors before
before they
they can
can re-crack.
re-crack.
(Higher
(Higher Liquid
Liquid Yields)
Yields)
Process variables:: Recycle
Recycle Gas
Gas Rate
Rate
(Gas/Oil
(Gas/Oil Ratio)
Ratio)

zTypical Design Guideline

–– Four
Four to
to Five
Five Times
Times Chemical
Chemical Hydrogen
Hydrogen
Consumption
Consumption
zRecycle Gas Rate Should Be Maximized
Within Plant Mechanical Constraints.
zminimum of 845 Nm3 reactor inlet gas per
m3 of fresh feed.
Process variables - Recycle Gas Purity
Effects of Recycle Gas Purity:
1. Yields high hydrogen partial pressures.
2. Minimizes catalyst fouling.
Depends mainly on:
1. Make-up hydrogen purity.
2. The yield of methane in the reactors.
3. Gas bleed from CHPS.
4. CHPS inlet temperature.
ACTION TO BE TAKEN:
Taking a bleed, which results in an increase in the make-up hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
partial pressure. Lowering the CHPS temperature will improve purity
because more light hydrocarbons will condense out of the recycle gas and
because less hydrogen dissolves at lower levels.
NOTE;
The design purity of the recycle gas is approximately 90.7 mole % H2 at
SOR and 85.6 mole % H2 at EOR. The recycle gas purity
 Process
Process variables
variables;; Reactor
Reactor Temperature
Temperature
Profile
Profile
1.
1. Level
Level Average
Average Temperature
Temperature (LAT)(LAT)
2.
2. Bed
Bed Average
Average Temperature
Temperature (BAT)(BAT)
3.
3. Catalyst
Catalyst Average
Average Temperature
Temperature (CAT)(CAT)
Temperature
Temperature Profile:
Profile:
1.
1. The
The LAT
LAT is is the
the simple
simple arithmetic
arithmetic average
average forfor aa set
set of
of thermocouples
thermocouples at at one
one
level
level in
in aa catalyst
catalyst bed.
bed.
2.
2. The
The BAT
BAT is is the
the simple
simple arithmetic
arithmetic average
average of of the
the bed
bed inlet
inlet and
and outlet
outlet LATs.
LATs.
3.
3. The
The CAT
CAT is is the
the weighted
weighted average
average ofof the
the BATs.
BATs.
There
There are
are three
three types
types ofof profiles:
profiles:
1.
1. AA flat
flat temperature
temperature profile
profile means
means thethe BATs
BATs areare equal.
equal.
2.
2. An
An ascending
ascending profile
profile means
means that
that each
each successive
successive BAT BAT isis higher
higher than
than the
the bed
bed
above.
above.
3.
3. AA descending
descending profile
profile means
means that
that each
each successive
successive BATBAT is is lower
lower than
than the
the bed
bed
above.
above. ThisThis profile
profile is
is rarely
rarely used
used (or
(or achievable).
achievable).
Note:
Note: BAT,
BAT, CAT, CAT, and and temperature
temperature profiles
profiles areare all all used
used to to monitor
monitor reactor
reactor
performance.
performance. The The CAT
CAT determines
determines how
how hard
hard thethe catalyst
catalyst isis working
working andand the
the
temperature
temperature profile
profile describes
describes how
how the
the work
work isis distributed
distributed over
over the
the reactor.
reactor.
 Process variables
variables-- catalyst
effects

zCatalyst Average Temperature (CAT )

–– Indicates
Indicates How
How Hard
Hard Catalyst
Catalyst is
is Working.
Working.
zReactor Temperature Profile
–– Indicates
Indicates How
How Work
Work is
is Distributed
Distributed Through
Through the
the
Reactor.
Reactor.
Catalyst Average Temperature

z Higher Catalyst Average Temperature Allows

– Higher Feed Rates at Constant Product Qualities.
– Better Product Qualities at Constant Feed Rate.
– More Difficult Feeds (Higher S, N) at Constant Product
Qualities and Feed Rate.
z But “There is No Free Lunch”
– Higher CATs Increase Coking Rate.
– Higher CATs Reduces catalyst Life due to increased
Fouling Rate.
Process variables-catalyst life
The table below summarizes the effects of changing each
of the process variables on catalyst life.

Variable Change Effect on

Catalyst
Life
Feed Rate Increase Decrease
Conversion Increase Decrease
Hydrogen Partial Increase Increase
Pressure
Make-Up Gas Purity Increase Increase
Reactor Pressure Increase Increase
Recycle Gas Rate Increase Increase
Recycle Gas Purity Increase Increase
WASH WATER INJECTION
z Wash water is continuously injected into fin coolers to remove
ammonium salts.
z Although incolloy tubes were selected for the reactor air
cooler, they may be subject to corrosion by deposition of
ammonium bisulfide (NH4HS) salts formed from the
combination of NH3 and H2S in the reactor and/or ammonium
chloride (NH4Cl) salts formed by the combination of NH3 and
HCl (from the chlorides in the feed).
z The sublimation range for ammonium bisulfide is generally
about 66-93°C. The sublimation range for ammonium chloride
begins at higher temperatures generally about 191-204°C.
z Therefore, NH4Cl will begin to sublime upstream of the
reactor air cooler.
z Reactor air cooler corrosion is minimized by limiting the
chlorides in the feed in the make-up hydrogen, by use of high
alloy material, by balanced flow, and by continuous injection
of water at the air cooler inlet.
 Summary of Process Variables
z
z Process Variables have a significant impact on
Catalyst Life, Yields, and Product Properties
z
z Understanding Process Variable Effects and
how these are related coupled with the
recognizing the constraints is critical to
maximizing Hydrocracker and Refinery
Profitability
THANK YOU