Hydro Cracker Unit

A PRESENTATION FOR RESOT CORE

COURSE PARTICIPANTS.
PARTICIPANTS

MONDAY-19TH JUNE-06

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.
Hydro cracking
z Chemistry
y
z Process

of Hydro-cracking.
y
g

Configurations.

Topics for discussion (COND)

z

Process descriptions- General

Process Variables

Emergency handling

Modifications& operational Improvement

done in CPCL OHCU.

Case study CPCL OHCU.

H d
Hydro-cracking
ki Licensors
Li

3 MMTPA Refinery Expansion cum

Modernization Project
Scope

: Expansion by 3 MMTPA &

quality / yield improvement
by modernisation

Approved Cost

: Rs. 2360.38 crore

Date of Approval

: 27.07.2000
27 07 2000

Sch. Date of Completion

: 26.07.2003

Completion
All units except OHCU
Hydro cracker

: Mar 2004
: 4th Aug 04

Process Units
Unit

Licensor

Capacity

CDU / VDU

EIL

3 0 MMTPA
3.0

Visbreaker

Lummus
Netherlands

1.15 MMTPA

Hydrocracker
y

Chevron Lummus
Global,USA

1.65 MMTPA

CRU

Axens, France

225,000 TPA

Hydrogen

Technip Benelux

45,000 TPA(56,000)

Netherlands

Process Units
Unit

Licensor

Capacity

LPG &
Kero Merox

UOP USA
UOP,

42,000
42
000 TPA
600,000 TPA

Sulphur Recovery

EIL /
180 TPD
Delta Hudson, Canada

A i Regeneration
Amine
R
ti

EIL

330 MT/hr
MT/h

Amine Treating :
a) Fuel gas treating
b) LPG treating

EIL
EIL

35,000 TPA
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
C feed
f d to lighter
li h products
d
under
d the
h condition
di i off
high hydrogen partial pressure and high temperature
i the
in
h presence off a catalyst.
l

What does a Hydrocracker do?

z Removes

Metals (HDM)
z Removes Olefins
z Removes Sulfur (HDS)
z Removes Nitrogen (HDN)
z Saturates Aromatics (HAD)
z Convert
C
t Feed
F d to
t Products
P d t
z H2 Consumption
z Operating
O
i Pressure
P
z Operating Temperature

100%
100%
100%
100%
50-95%
40 100%
40-100%
170-422 Nm3/m3
70 210 kg/cm2G
70-210
k / 2G
315-430C

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.
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
HYDRO&DEMERITS

Demerits:
i) High investment cost.
ii) Frequent mechanical problems with
equipments.
iii) High energy consumption.(H2 requirement)

NOTE: With the catalyst

y development,
p
, utilization of
metallurgy's & experience gained, Hydrocracking has become a very reliable process

History of HydroHydro-cracking
Early Hydro-cracking (liquid fuel from Coal).
z Used Iron
Iron-Based
Based Catalysts
z Very High Pressures (352 kg/cm2G), 426C
T
Temperature.
t
z Used by Germany in WW-II.
z High Gas Make, Low Octane Naphtha, Poor
Quality
Q
y Diesel ((High
g in Aromatics))

History of HydroHydro-cracking (cond)

Fi t Modern
First
M d
Hydro-cracking
H d
ki
z 1959: Chevron Demonstrates Modern High Pressure
Process in Richmond Refinery-iso-cracking.
Refinery-iso-cracking
z Union Oil Co Unicracking.
z UOP lomax hydro
hydro-cracking
cracking process.
process
z Employed Amorphous Silica-Alumina Catalysts.
z Rapid
ap d growth
g owt of
o hydro-cracking
yd o c ac g after
a te development
deve op e t of
o
new, Zeolite based hydro-cracking.
z 1962: Chevron Starts-Up the First Hydro-cracker in
the Then Sohio Refinery in Toledo, Ohio
z 1966: Chevrons Richmond Hydro-processing
Complex Starts-Up.
Starts Up

History of HydroHydro-cracking (cond)

State-of-the-Art Hydrocracking
y
g
1. Zeolitic Catalysts.
2 Lower Pressures
2.
Pressures, 70 200 kg/cm2G
kg/cm2G.
3. Moderate Temperatures 340 - 410C.

Hydrocracking Licensors
z Until Early 1990s, the Market (~120 HCRs) Was
Divided Roughly 1/3 Each Between UOP, Unocal
and Chevron.
z In 1995, UOP Bought Unocal Technology, and
N H
Now
Have 2/3 off the
h W
Worlds
ld HCRs.
HCR
z Other Licensors (Minor Players).
IFP (Subsidized by French Government)
MAKFina (Mainly Compete in Mild HCR)
Shell Global (Several Captive Shell Units,
Criterion Cats)

Chemistry of HydroHydro-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
g
Heat Release

C
HC

CH
CH + 4H2

R
Catalyst CH 3 CHCH 2CH 3

+ 2S
H
Branched Paraffin

S
Thiophene
R
R

CH

SH+ H2

Catalyst

CH2 R + H2S
Straight-Chain
Thiol
Paraffi
n
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.
GO TO ANIMATION

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 py
pyrroles to form p
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
R-CH2CH
OLEFIN

RCH2CH2CH3
PARAFFIN

Hydrogenation of olefins is one of the most rapid of the

reactions
ti
t ki place.
taking
l
All olefins
l fi are saturated
t
t d 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
g
and because the saturation reactions are
rapid and release a large quantity of heat.

H
H
\
/
R C====
C
C-H
C
H
\\
//
C---------C
/
\
H
H

C--------C
H
/
\
H
R C ----------C H
\
/
H
C --------- C
/ \
/\
AROMATIC
H H H H
NAPHTHENE
Hydrogenated to naphthenes heat of reactions vary from about 380
380750 kcal/Nm3 (40-80 Btu/SCF) of hydrogen consumed depending
on the type of aromatic being saturated. In general, higher
+ 3H2
3 2

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.

CnH2n+2

Catalyst (Ni3S2)
+

(x-1) H2

less carbon no.

x C n/xH2n/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 Large
L
Side
Sid Chains
Ch i E
Easily
il Removed
R
d From
F
Rings
z Saturated Rings Crack Easily.
z Paraffins Hard to crack.
z Paraffin Products Are Highly Isomerized.

Chemistry of HydroHydro-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 27-54C for
sulphur compounds and up to 104C 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.
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 Important Reactions
zThermal Hydrocracking or De-methylation
De-methylation
Undesirable Side Reaction Occurring at >465C
Can Occur at Lower Temperatures With Reduced
Reduced,
Unsulfided Metals
Produces Light Gases,
Gases Mainly Methane
High H2 Consumption, Uncontrollable Heat
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.
introduced
The sulfiding process consists of catalyst pretreatment with a
sulfiding agent in the presence of hydrogen. When heated
and
d passed
d over th
the catalyst,
t l t th
the sulfiding
lfidi agentt b
breaks
k d
down
into H2S which reacts with the metal oxides on the catalyst,
thereby generating active metal sites (metal sulfides).
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 218232C for
DMDS.
(2) Conversion of metal oxide to metal sulfide
2H2S + 3NiO + H2 Ni3S2 + 3H2O

Heat Release/H2 Consumption

From HydroHydro-crackers
Reaction

H 2 Consumption

Heat Release,
(Kcal/ Nm 3 H 2)

HDS

3 mols H 2/mol S
(17-25 Nm 3/m 3 Per 1% S Removed)

565

HDN

~5 mols H 2/mol N
(5-7 Nm 3/m 3Per 1000 ppm N Removed)

610-705

Olefin

~1 mol H 2/C=C Bond

1200-1500

~ 3 mols H 2/Ring Saturated

(2-5 Nm 3/m 3Per 1% Rings Reduced)

660-800
660
800

2-5 Nm 3/m 3 Per 1 LV% Conv.

470-565

Saturation
HDA
Cracking

Process Configurations

Process Configurations
zSingle Stage - for 100% conversion of feed
into products.
zSingle stage - Once-Through operation
CPCLs design configuration

zSingle Stage Recycle

- C
CPCLs
C s initial ope
operation
o co
configuration
gu o
zTwo Stage Recycle

Single-Stage OnceSingleOnce-Through
(SSOT) Hydrocracking
z Features

Low Investment
Low Hydrogen
d
C
Consumption
i
Very Flexible Plant, Handles a Variety of

Feeds
Can Handle High
g End Point,, High
g N
Feeds
Pretreats VGO for FCC Feed
Produces High VI Lube Base Stocks

CPCL SSOT YIELDS

CPCL SSOT YIELDS
Yields,
Yi
ld Wt %
C1 & C2
C3ss
C4s
Light Naphtha
Heavy Naphtha
Kerosene
Diesel
Bottoms
C5+,

SOR
0.64
0.67
1.46
3.40
5.10
23.69
21 75
21.75
42.43
96.37

EOR
1.11
1.00
2.31
3.60
5.10
23.60
20 02
20.02
42.42
94.75

Integration of Hydrocracker Unit with

the existing
g FCCU
z

The superior quality of unconverted oil from HCU bottom (sulphur content < 50 ppmw,
N2 content < 1 ppm and metals < 0.1 ppm) will be routed to FCCU as new feed to derive
the following benefits :
Improved yield pattern :
Present Feed (wt.%)
Previous 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
52
5.2
20
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
S content <100 ppm).
4. Reduction in SO2 emission due to lower sulphur content in feed.

Single--Stage Recycle (SSREC)

Single
H d
Hydrocracking
ki
z

Features: Relative to SSOT

Can Achieve Almost Full Conversion (97%)
Moderate Investment
High Quality Products
High Hydrogen Consumption

Two Stage Recycle (TSR)

Maximum Liquid Yield and Highest Quality
Make-Up
MakeHydrogen

Make--Up Hydrogen
Make
Recycle
Gas
Product
Gas

Fresh
Feed
Recycle
Gas

Light
Naphtha
Heavy
Heavy
Naphtha
Kerosene
Diesel

First--Stage
First
Product

Second--Stage Product
Second

Two Stage Recycle

Hydrocracking
z

Features Relative to SSREC/SSOT

Flexibility to Go to Highest Conversion Levels - (100%).
(100%)
Higher Investment.
Can Process Tougher Feeds.
Clean Second Stage:
z Most C5+ Yield (Least Gas Make).
z Least Hydrogen Consumption.
z Most Product Yield Flexibility.
(
(e.g.,
Can
C S
Switch
it h tto M
More JJet/
t/ L
Less Di
Diesell and
d Vi
ViceVersa).
z Product Quality Best.
z Minimum Bleed Rate.

Hydrocracking Configurations
Summary
z Single-Stage, Once-Through-Liquid (SSOT)
Low Conversion (35-70%)
Minimal Quality Products (UCO to FCC U as Feed)
Relatively Low Investment
z Single-Stage Recycle (SSREC)
High Conversion
Con ersion (90+%)
High Quality Products
Moderate Investment With Easy Feeds
z Two-Stage Recycle (TSR)
Full Conversion
Very High Quality Products
Moderate Investment With Difficult Feeds

Product Qualities
Single vs Two stage hydro
hydro--cracker
Product Properties

VGO HDT

SSOT

SSREC

TSR

Jet Smoke Point, mm

10-15

15-20

20-25

25-30

Heavy Diesel Cetane

Number

50

50-55

60-65

65-70

Feed & products

Typical Feed stocks

z Straight

run gas oil.

z Vacuum Gas Oil (LVGO & HVGO ).
z De-asphalted
D
h lt d Oil (DAO).
(DAO)
z FCCU cycle oil.
z Cocker gas oil.
z Distillates.
z Extracts.

HYDROCRACKER FEED STREAMS CPCL

z

HVGO Stream from Ref-II and Ref-III

DAO
dist 95%@585C, vis 33 36cst @100C, asp < 100 ppmw

Foots Oil
CCR 0.4%wt, Asp 40-50 ppmw, Metals* 3 ppmw

Slack wax
CCR - <0.1%
<0 1% wt,
wt Asp 90 ppmw,
ppmw Metals 1 ppmw

Lube distillate & Lube slop

-CCR 0.6% wt, Asp 70 ppmw, Metals 3.5 ppmw

z VB-VGO
((* Metals = Ni
Ni+V+Fe+Na)
V Fe Na)

Products from hydrohydro-cracker

z

HYDROCRACKER UNIT PRIMARY PRODUCTS:

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

HYDROCRACKER UNIT BY- PRODUCTS:

1.
2.
3.
4
4.

Filter Back flush to Fuel Oil/ FCC Feed

Sour Water to Sour Water Stripper
Spent Caustic Solution to Spent Caustic System
Bl d
Blow
down ffrom St
Steam G
Generators
t
tto St
Storm W
Water
t S
Sewer

HYDROCRACKING
CATALYST

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.
REQUIRED
METALS SUCH AS MOLYBDENUM, TUNGSTEN, COBALT,
NICKEL, PLATINUM, PALIDIUM ARE DISPERSED ON THE
CATALYST BASE.
NITROGEN IN FEED GETS CONVERTED TO AMMONIA
THROUGH
OUG REACTIONS
C ONS AND
N N
NH3
3 SO FORMED
O
PARTIALLY
NEUTRALISES THE ACIDIC SITES THUS REDUCING
CAT.ACTIVITY.

Catalyst--CPCL
Catalyst
Catalyst Type

Shape

Loaded
Densities,
3
kg/m

Demetallization
and
dG
Grading
di

Sphere

913

Hydrotreating
ICR 134SAQ

Total Requirements for

Diameter,
mm
~4.23

16,130

37.3

203

2.82 x 2.31

75,022

82.2

551

Reactors 207-R1, 207-R2

977
Asym Quad

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

~4.23

7,075

50

Support
ICR 114ZF

432
Trilobe

2,160

CPCL
CPCL ACTIVE
ACTIVE CATALYST
CATALYST LOADING
LOADING

G2000829

CAT

M3

TYPE

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

ICR-126 L,

HCR

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

VOL

207 R1, Bed 1

Total

6/12/2006

VOL

Krishna

21

73.1

22.7

321 4
321.4

100 0
100.0

207--R1 Catalyst System

207
Catalyst

Function

ICR122ZSB 37.3m3
D
t lli ti
37 3 3 De-metallization
ICR 114ZF
ICR 134SAQ
ICR 114ZF
ICR 134SAQ
ICR 126

1.6m3

82.2m3
16 3
1.6m3

Support
Hydro-treating
Support

13.1m3

Hydro-treating

46 7 3
46.7m3

Hydrocracking

ICR 114ZF

Support
Support Balls

207--R2 Catalyst System

207
Catalyst

Function

ICR 126

69.4m3
ICR 114ZF
ICR 126N/126L
ICR 114ZF

1.6m3

Hydrocracking

Support
Hydrocracking

Support
1.6m3
1
6m3
Support Balls

Catalyst Deactivation Caused

By Deposits and
Contaminants
z

Regenerable
Carbon Deposits or Coke Caused by Adsorbed

Condensed Polycyclic Compounds

Adsorbed Organic Nitrogen Compounds Which Tie Up
Acid Sites
Sites, Thus Lowering Cracking Activity
z

Nonregenerable
Deposited Feed Metals - Ni,
Ni V
V, Si
Si, Fe
Fe, As
As, Pb
Pb, P
Metals Tend to Deposit Near the Outer Edge of the

Catalyst and Plug the Catalyst Pores

Sulfur leaching.
z

Normally when H22 is

i
circulated
i
at higher
i
temperature over the sulphided catalysts the sulphur
will be converted to H2S and the metal sulphides
p
will
be converted to metals, which will reduce the
activities. Fresh or regenerated catalyst will be in
metal oxide,, duringg sulphiding
p
g 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 hydrotreaters there is a temperature limit above which we
can not circulate H2 with out oil.

P
Process
d
description
i ti

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
5.

1.FEED AND REACTION SECTION

z

Oil feed is p
preheated, filtered, and p
pumped
p
to reactor
system. In let pressure is -176 kg.
- Filter element filters above 20 micron
particles.

Oil feed is mixed with hydrogen, further preheated

(378C(SOR) 396C(EOR)) and
(378C(SOR)-396C(EOR))
d sentt to
t the
th Reactors.
R t

Initial cooling of the reactor effluent occurs in the Reactor

Feed/Effluent Exchangers, 207-E3A/B. which is

supplying more than 80% of the required heat duty

andd furnace
f
provides
id 20%.
20%

1.FEED AND REACTION SECTION

(cond)
z

Feed to Multistage feed pump operating at 65 - 230C.

Discharge pressure can vary from 200-220 kg/cm2G,
depending upon feed rate
Pumped feed mixes with makeup and recycle H2, and is
preheated
h t d in
i the
th reactor
t feed/effluent
f d/ ffl t HeX
H X (~80%
( 80% off
necessary heat is provided ).
Final reactor feed temperature is controlled by feed
furnace ( 22-28C dT across furnace minimum is
allowed).
Feed & H2 gas mix enters the top of the down-flow
reactor. Heat is released due to exothermic reactions.
Quench gas is used to control bed in let temperatures.
temperatures
Most reactors have 4-5 beds and 3-4 quench points.

1.FEED AND REACTION SECTION

(
(cond)
d)
z

z
z

Reactor effluent is cooled by exchanging heat with reactor

feed fractionator feed product stripper feed
feed,
feed, steam
generation, and an Reactor Effluent Air Cooler (REAC).
Prior to entering the REAC, water is injected to dissolve
NH4S formed, to avoid corrosion and plugging REAC tube.
The 3-phase stream, enters the cold high pressure separator
(CHPS) and is separated. Hydrogen-rich vapor leaves
through the top nozzle, Sour water through bottom nozzle,
and liquid hydrocarbons through side nozzle
nozzle.
Vapor from CHPS flows to recycle compressor to be
recycled
y
back to reactor inlet and to quench
q
ppoints.

2. RECYCLE GAS LOOP AND OIL/GAS

SEPARATION SECTION
z

Hydrogen-rich gas is separated from the

reactor effluent.
z The g
gas is compressed
p
and recycled
y
back
through the high pressure reactor loop.
z Separate oil from the reactor effluent to
be sent for product separation section.

3.
3 FRACTIONATION SECTION
Separates reaction products into
1. Sour gas.
2. Unstabilised naphtha.
3. Superior kerosene.
4. Diesel.
5. Fractionator bottom - Unconverted oil.

4. LIGHT ENDS RECOVERY

SECTION
Takes sour gas and Unstabilised naphtha
from the Product stripper and Fractionator
overheads and produces the following
products.
z
z
z
z

Sweet Fuel Gas

LPG
Light Naphtha
Heavy Naphtha

5. MAKEMAKE-UP H2 COMPRESSION
SECTION
1.

Supplies high purity hydrogen to the

reaction Section as required for the hydrocracking and hydro-treating reactions.

2.

HP System pressure is controlled by

MUGC discharge pressure.

Feed Filter System

y
z

The oil feed must be filtered to remove solids and

particulates which would otherwise layy down on the First
p
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).

The preheated, combined oil feeds stream enter the feed

filters at 168C where most of the solids and particulates
are trapped and removed from the reactor oil feed
stream.

First and Second Reactors

R1 and R2
z

The purpose of the First and Second Reactors is to provide a

controlled environment for the hydro-cracking
y
g and hydroy
treating reactions to take place.

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.

Hydro-treating
y
g and hydro-cracking
y
g 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
fi t reactor
first
t and
d two
t beds
b d in
i the
th second
d reactor.
t

Essential guidelines

GO TO ANIMATION

Cold High Pressure Separator

(CHPS)
z

Cold High Pressure Separator (CHPS), - Separates the reactor effluent

into hydrogen
hydrogen-rich
rich vapor,
vapor water,
water and hydrocarbon liquid reaction
products.

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

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 .

The CHPS temperature

Th
t
t
i controlled
is
t ll d by
b adjusting
dj ti the
th speed
d off the
th fans
f
operating in the reactor effluent air cooler. Lowering separator
temperature will:
1.
Increase the recycle
y g
gas p
purity.
y
2.
Lower the recycle compressor horsepower requirement.
3.
Make separation of oil from water in the separator more
difficult.

Go to CHPS
Animation file

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.

The normal operating temperature is 55-68C.

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 5C hotter than the vapor.

The temperature off the lean amine

i must be maintained
i i
5C
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.)

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

z
z
z
z

Recycle Gas Compressor - Supplies the

pressure to move the recycle gas through the
reactor system.
To maintain H2 partial pressure.
pressure
To remove the heat of reaction.
T improve
To
i
oil/gas
il/
di ib i
distribution.
To remove products from the reactors as
soon as they
th
are formed
f
d to
t preventt
secondary cracking.

Cold Low Pressure Separator

p
(CLPS)
(
)
z

Cold Low Pressure Separator (CLPS), - Separates hydrogen-rich

vapor, hydrocarbon liquid, and water phases

Reactor effluent liquid from the CHPS is let down in

pressure through
th
h a level
l l control
t l valve
l and
d then
th flashed
fl h d in
i
the CLPS. It is a SS clad carbon steel, vertical vessel with
g
to separate
p
hydrogen-rich
y
g
vapor,
p
internals designed
hydrocarbon liquid, and water phases. The CLPS removes
water carried over in the CHPS liquid. The hydrocarbon
liquid is the product stripper feed.
feed

CLPS Vapor
p H2S Absorber
z

It Scrubs H2S from the CLPS Vapor by

contact
t t with
ith lean
l
amine
i prior
i to
t sending
di
the vapor to the PSA Unit for hydrogen
recovery.
recovery
z It is a SS clad carbon steel vessel with a
single packed bed.
bed
z The normal operating temperature is
61C
61
C and pressure is 38kg/cm2g.
38kg/cm2g

Fractionation Section
z

The purpose of the Fractionation Section is to

p
reaction section p
products into sour
separate
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
F hF
Fresh
Feed
dR
Rate, BPOD (112% off D
Design)
i )
Fresh Feed Rate, MM MTPA
LHSV, 1/Hr (Note 1)
Gross Conversion,, Vol %
Total Catalyst Life, Yr

37 400
37,400
1.85
0.8
54
5 (With Regeneration)
207-R1

207-R2

172.5/176.0
169.0/169.0
145

167.4/167.4
163.9/163.9
135

378/396
411/429
440

378/396
411/429
440

Reactor Pressure, kg/cm (g)

SOR/EOR
Inlet
Outlet
Average Hydrogen Partial Pressure,
2
kg/cm (a)
Reactor Temperature, C
SOR/EOR
Inlet
Outlet
Maximum
3

Gas to Oil Ratio at Reactor Inlet, Nm /m

Number of Reactors

MAKE-UP H2 PURITY
CHEMICAL H2 CONSUMPTION
HYDROGEN BLEED

845
1

99.5%
262nm3/m3 of feed
nil

Process variables

Process variables
1.
2.
3.

FEED EFFECTS.
HYDROGEN EFFECTS.
CATALYST EFFECTS.
1. Reactor temperature profile.
2. Catalyst Average Temperature.

4
4.
5.

REACTION SECTION OPERATING

EFFECTS.
FRACTIONATION AND LER OPERATION
EFFECTS.

Process variablesvariables-Feed
effects
FEED EFFECTS:
1. LIQUID HOURLY SPACE VELOCITY
(FEED RATE)
2. NITROGEN.
3 ASPHALTENES.
3.
ASPHALTENES
4. METALS
5 POLYCYCLIC AROMATICS
5.
6. SULFUR
7. CHLORIDES

Process variablesvariables- 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 variablesvariables- LHSV

zD t
zDeterminants
i t
Active Catalyst Volume (Design Feature)
Feed Rate

zEffects of Higher LHSV

Degrades Product Properties at Same Catalyst
Average Temperature (CAT).
Increase CAT to Maintain Product
Specifications .
Increased CAT Increases Coking .
Higher CAT Reduces Cycle Length .

zLHSV Should be Optimized to Meet Product

Properties and Catalyst Life .

Effect of Feed Nitrogen Content

z
z
z
z
z

Typical Nitrogen Levels Are <1100 ppm

Nitrogen is a Strong Poison for Acid Sites in HCR
Catalysts.It is a temporary catalyst poison.
It neutralise the active site.
site
Desorption rate is very slow. It will take several days to
desorb.
Higher N2 in feed requires higher CATs to achieve a
desired conversion this will result in Shorten the Cycle
Life
Life.
Higher NH3 Levels Will need higher Water Wash 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
deposits.
Note : Asphaltene content can be reduced by
proper operation of upsteam unit.
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
p
on the catalyst
y and irreversiblyy destroy
y 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

p
precursors.
z It is a large multi-ring aromatic compounds
tend to dehydrogenate on the catalyst,
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 andd other
h critical
i i l equipment.
i
- It increases the H2S content of the recycle gas,
decrease H2 partial pressure and reduce the catalyst
performance.
pp (
)
z Chloride limit is 1ppm(max).
The salt, Mgcl &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).
A the
As
th feed
f d boiling
b ili range increases,
i
th levels
the
l l off nitrogen,
it
polycyclic aromatics (PCA), asphaltenes, and metals
increase. A higher feed nitrogen level and higher PCA level
require
i a higher
hi h CAT.
CAT High
Hi h PCA,
PCA asphaltene,
h lt
and
d metal
t l
levels increase the fouling rate of the catalyst. Therefore,
increasing the feed boiling range shortens the run span by
i
increasing
i both
b th the
th required
i d CAT and
d the
th fouling
f li rate.
t
Catalyst poisons such as asphaltenes, metals, and nitrogen
increase exponentially with boiling point

Sources of Contaminants and

Their Effects
Contaminant

Source

Effect on Isocracking Catalyst

Ni + V

High End Point Feed

1% Metals = 15F Activity Loss

Si

Silicone Antifoam

Pore Mouth Plugging

N
Na

Sodium
S
di
Hydroxide
H d id
Desalting / Flooding
(poor de-salter operation)

1% = 15F Activity Loss

FeSx

Corrosion Products

Pore Mouth Plugging

As

Arsenic in Crude

1% as = 50F Activity Loss

Phosphoric Acid in Feed

1% P = 90F Activity Loss

Asphaltenes

Residuum

Higher Fouling Rate

CPCL
CPCL FEED
FEED COMPOSITION
COMPOSITION
SR

VB

90% SRVG O

VGO

VGO

10% VB VG O

2 0 .8

2 0 .7

2 0 .8

2 .8

5 .0

3 .0 3

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

API
S u lf u r , w t %
N it r o g e n , p p m

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
PROPERTIES-- CPCLCPCL-OHCU
Feed Specifications
Feedstock Sources

SR VGO
CDU/VDU Bombay
High/Persian Gulf

VB VGO
Visbreaker
Unit

End Point, Max.

320
380
415
440-460
490
540
585

300
324
378
402
435
473
500

API Gravity
Specific Gravity

20.8-34.8
0.825-0.929

20.7
0.93

0.01
0
1000
2.8

0.02
5
2000
5
46.3
9.6

Quality Specifications
Di till ti
Distillation,
ASTM D 1160,
1160 C
Start
10%
30%
50%
70%
90%

Asphaltenes, Wt %, Max.
Iron, ppm
Nitrogen, ppmw
Sulfur, Wt %
Kinematic Viscosity at 50C, cSt
Kinematic Viscosity at 100C, cSt
Kinematic Viscosity at 200C, cSt
Kinematic Viscosity
y at 250C, cSt
CCR, Wt %
Nickel + Vanadium, ppm

0.6-1.65
0.4-1.1
0.6
1

1
9

Products Specification
CPCL--OHCU
CPCL
Product Inspections:
Cut
Cut Points, C
API Gravity
Density @15 C
ASTM, C
ST
10
50
90
EP
Sulfur, ppm
Mercaptan Sulfur, ppm
Nitrogen, ppm
Paraffins, LV % (Estimated)
Naphthenes, LV %
(Estimated)
Aromatics, LV % (Estimated)
Flash Point, C
Smoke Point, mm
Cetane Index (D 613)
Freeze Point, C
Pour Point, C
Viscosity @ 40 C, cSt
Viscosity @ 100C, cSt
Viscosity @ -20C, cSt
pp
Water,, ppm
Metals, ppm
Octane Number, Estimated
RONC/MONC
2

RVP, kg/cm

Light
NC hth
5-95
79
670-675
D 86
23
36
49
79
91
<5

Heavy Naphtha

Kerosene/ATF

Diesel

Bottoms

95130

130-260

260-370

370+

54
763-768
D 86
102
107
114
128
147
<5

42.5
812-817
D 86
142
161
193
238
266
10 (Max.)

36.5
820-870
D 86
229
268
302
348
376
10 (Max.)

34.8
850-855
D 1160
337
394
473
548
562
<50 (Max.)

10 (Max.)
<1
66
32

10 (Max.)
<1
30
62

<1 (Max.)

22
38 (Min.)
21

35 (Min.)
55 (Min.)

(-)51
3 (Max.)
2 to 5
4.2
8
500 ((Max.))
<0.1
75/76
0.8 (Max.)

64/62
0.8 (Max.)

Process Variables H2
Effects
HYDROGEN EFFECTS:
Hydrogen Partial Pressure.
Recycle gas purity
Mack-up H2 purity
Recycle
R
l gas rate
t (Gas/Oil
(G /Oil Ratio)
R ti )
Catalyst Temperature.
Catalyst
C l life.
lif

Process Variables
z

Reactor temperature profile.

z Catalyst Average temperature
temperature.

Process variables - Make up H2

z

Purity

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.
To maintain the desired hydrogen partial pressure and
minimize the amount of impurities fed to the system,
the purity of the make-up hydrogen should be kept at
the design value (99.5 mole%H2).
If the
h make-up
k
h d
hydrogen
purity
i falls
f ll below
b l
the
h design
d i
value, a bleed may be required to maintain an
acceptable hydrogen partial pressure.
pressure

Process variables: Hydrogen Partial Pressure

(pH2))
(p

zH2 partial press can be increased by

Increasing total system pressure (operate
(
t as close
l
as
the relief valve set press located on the CHPS).

Increasing
g Make-Upp Hydrogen
y g Purity.
y
Increasing Recycle Gas Purity (Bleed, Treating)
Recycle Gas Rate.
Decreasing CHPS temperature.

zHigher PH2 Effects

Improves Product Properties (Jet Smoke Point,
Diesel Cetane Number).
Number)
Increases Cycle Length.

MAKE--UP HYDROGEN QUALITY

MAKE
Q
MAKE-UP HYDROGEN QUALITY
Parameter
Hydrogen Purity,
Purity Mole %

Hydrogen Specifications
99 5(Min )
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 200c, the
chances
h
off nickel
i k l corbonyl
b
l formation
f
ti iis more. Whi
Which
h iis hi
highly
hl toxic
t i

Example: Effect of Increased MakeMake-Up

Hydrogen
y g Purity
y on Product Properties
p
and Cycle Length
SSOT Operation,
Operation System Pressure = 169 kg/cm

2G

Make -Up
p Purity,
y, %

85

96

99.9

Recycle Gas Purity, %

75

86.5

90

Hydrogen Partial Pressure,

k /
kg/cm
2G

125

136

140

Jet Smoke, mm

18

20

21

Diesel Cetane Number

50

53

55

Cycle Length, Months

14

24

29

Process variables: Recycle Gas Rate (Gas/Oil

Ratio))
z Effects of High Recycle Gas rate (Gas/Oil Ratio)
Decreases Catalyst Fouling
zMaintains High Hydrogen Partial Pressure in Reactors.
Providing a heat sink for high heat of reaction in the
zProviding
bed.
zHelps Distribution of Reactants Over the Catalyst
Bed.
zLimits Bed Temperature Rise.
zIncreases Catalyst Activity
zMinimizes "Overcracking" of Products by carrying
them out of the reactors before they can re-crack.
(Higher Liquid Yields)

Process variables: Recycle Gas Rate

((Gas/Oil Ratio))

zTypical Design Guideline

Four to Five Times Chemical Hydrogen
Consumption

zRecycle Gas Rate Should Be Maximized

Within Plant Mechanical Constraints.
zminimum of 845 Nm3 reactor inlet gas per
m3 off fresh
f
feed.
f

Process variables-Recycle Gas

Purity
Effects of Recycle Gas Purity:
1.
Yields high hydrogen partial pressures.
2.
Minimizes catalyst
y fouling.
g
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:
T ki
Taking
a bleed,
bl d which
hi h results
lt in
i an increase
i
i the
in
th make-up
k
h d
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
b
because
more light
li ht hydrocarbons
h d
b
will
ill condense
d
outt off the
th recycle
l gas and
d
because less hydrogen dissolves at lower levels.
NOTE;
g p
purity
y of the recycle
y ggas is approximately
pp
y 90.7 mole % H2 at
The design
SOR and 85.6 mole % H2 at EOR. The recycle gas purity

Process variables; Reactor Temperature

Profile
Level Average Temperature (LAT)
2.
Bed Average Temperature (BAT)
3.
Catalyst Average Temperature (CAT)
Temperature Profile:
1.
The LAT is the simple arithmetic average for a set of thermocouples at one
level in a catalyst bed.
2.
The BAT is the simple arithmetic average of the bed inlet and outlet LATs.
3.
The CAT is the weighted average of the BATs.
There are three types of profiles:
1.
A flat temperature profile means the BATs are equal.
2.
An ascending profile means that each successive BAT is higher than the bed
above.
3.
A descendingg profile
p
means that each successive BAT is lower than the bed
above. This profile is rarely used (or achievable).
Note: BAT, CAT, and temperature profiles are all used to monitor reactor
performance. The CAT determines how hard the catalyst is working and the
temperature profile
fil describes
d
ib how
h the
h workk is
i distributed
di ib d over the
h reactor.
1
1.

Process variablesvariables- catalyst

effects
ff t
zCatalyst Average Temperature (CAT )
Indicates How Hard Catalyst is Working.

zReactor Temperature Profile

Indicates How Work is Distributed Through the
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 variablesvariables-catalyst life

The table
Th
bl b
below
l summarizes
i
the
h effects
ff
off changing
h
i each
h
of the process variables on catalyst life.
Variable

Feed Rate
Conversion
Hydrogen Partial
Pressure
Make-Up Gas Purity
Reactor Pressure
Recycle Gas Rate
Recycle Gas Purity

Change

Increase
Increase
Increase

Effect on
Catalyst
Life
Decrease
Decrease
Increase

Increase
Increase
Increase
Increase

Increase
Increase
Increase
Increase

WASH WATER INJECTION

z
z

z
z

Wash water is continuously injected into fin coolers to remove

ammonium salts.
Although
g incolloyy 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
hl id (NH4Cl) salts
lt formed
f
d by
b the
th combination
bi ti off NH3 and
d
HCl (from the chlorides in the feed).
The sublimation range for ammonium bisulfide is generally
about 66-93C.
66 93C The sublimation range for ammonium chloride
begins at higher temperatures generally about 191-204C.
Therefore, NH4Cl will begin to sublime upstream of the
reactor air cooler.
cooler
Reactor air cooler corrosion is minimized by limiting the
chlorides in the feed in the make-up hydrogen, by use of high
alloy material,
material by balanced flow,
flow and by continuous injection
of water at the air cooler inlet.

Summary
y of Process Variables
z

Process Variables Have a Strong Impact on

Catal st Life
Catalyst
Life, Yield Structure,
Str ct re and Product
Prod ct
Properties
z Understanding
d
di Process Variable
i bl Effects
ff
andd
How These Effects are Related to Refinery
Operating
i Objectives
bj i
andd Constraints
i is
i
Critical to Maximizing Hydrocracker and
Refinery
fi
Profitability
fi bili

Reactors consideration

Reactor considerations.
Reactor Pressurization
z

The reactors should be pressurized according to the

temperature and pressure restrictions recommended by the
manufacturer. The 2-1/4 Cr-1 Mo alloy steel used to build the
high
i pressure reactors has good high
i temperature strength and
good resistance to hydrogen attack. However, this steel can
become increasingly
g y brittle at ambient temperatures
p
after
long-term exposure to normal reactor operating temperatures.

This loss of low temperature toughness is known as temper

embrittlement. For this reason, pressurization restrictions are
prevent the p
possibility
y of brittle fracture duringg
necessaryy to p
startup and shutdown when the reactor shell is cold.

Reactor considerations
Reactor pressurization (cont):
z

Chevrons recommended practice is to limit the reactor

section pressure to 25% of thick-wall vessel design
pressure (reactors), when the internal process, external
skin, or external nozzle temperature at any location on the
reactor below the minimum pressurization temperature
(MPT). (reactors are cold, and should not be allowed to
exceed 25% of design pressure until all skin points are
above the MPT (assumed to be 38
38C)
C) to prevent severe
damage due to brittle fracture. )
For the reactors designed for this unit, 25% of the design
pressure [[185.3 kg/cm2
p
g
(g)] is 46.3 kg/cm2
g
(g), and the
recommended MPT is 38C.
Regarding pressurization rate, there are no mechanical
reasons to limit the rate. However,, ggood jjudgment
g
suggests that the rate not exceed ~28 kg/cm2/h

Reactor considerations
De-pressurization:
z During rapid depressurization there is a small possibility
of increased stress on reactor internals caused by high
pressure drop associated with high gas velocity.
z Depressurization rates should be controlled so as not to
exceed a pressure drop of 14 kg/cm2 over the reactors.
z Note that since the reactor inlet pressure drops nearly
simultaneously
i lt
l with
ith the
th reactor
t outlet
tl t pressure, a high
hi h
pressure drop across the reactors is unlikely.
z However,, a mechanical obstruction in the reactor
internals, such as a screen failure causing an internal to
fill with catalyst, might cause a high reactor bed pressure
drop during emergency depressurization.

Reactor considerations
Hydrogen Out gassing:
z

When a reactor is in service a small amount of

hydrogen continually diffuses from the inside of the
reactor through the wall to the atmosphere.
The equilibrium concentration that the hydrogen in
the wall reaches depends on the temperature and the
hydrogen partial pressure.
Th higher
The
hi h
the
h temperature and
d hydrogen
h d
partial
i l
pressure, the higher the equilibrium concentration of
hydrogen
y
g in the wall.
During reactor cool down, the solubility of hydrogen in
the reactor steel decreases. In addition, the hydrogen
diffusion rate in the reactor steel is a function of
temperature.

Reactor considerations
Hydrogen Out gassing (cont):
z

As the temperature
p
drops,
p , the rate of hydrogen
y g
diffusion decreases. As a consequence, a rapid cool
down can result in a significant concentration of
hydrogen remaining entrapped in the reactor wall.
wall
It is desirable to minimize the amount of hydrogen
remaining in the reactor wall subsequent to the unit
shutdown.
The entrapped hydrogen can cause existing
fabrication defects to grow. It can also cause
cracking and separation (disbonding) of stainless
steel overlay from the reactor base material.
material

E
Emergency
Handling.
H dli

Emergency in hydrohydro-cracker
Emergency:
1.Loss of Recycle Gas Compressor.
2.Loss of Make-Up Hydrogen.
3L
3.Loss
off R
Recycle
l Gas
G Compressor.
C
4. Make-Up Hydrogen Compressor
5.Loss of Oil Feed
1. Loss of VGO Feed to the Reactor Feed Surge
Drum.
2. Loss of Reactor Feed Pump.
p
6.Reactor Temperature Excursions.
7.Gas Leak or Fire in the High Pressure Reaction
Section
8.Utility Failures
1. Loss of Instrumentation
2 Loss of Electric Power
2.
3. Loss of Cooling Water
4. Loss of High Pressure Steam

Reactor Temperature Excursions

z

The hydrogenation reactions are exothermic (heat

producing); in addition, the reaction rates increase with
increasing temperature. If reactor temperatures are not
controlled properly (furnace temperature, quench gas
control reactor feed/effluent exchanger interaction,
control,
interaction
etc.), temperature increases will increase the reaction
rate, which results in more heat being generated. The
net effect is an accelerating temperature rise.
A gradual temperature increase is usually called an
excursion A faster,
excursion.
faster rapidly accelerating temperature
increase would be called a runaway. In either case, the
emergency
g y actions are the same since an excursion can
become a runaway with little warning.

Reactor Temperature
Excursions(cont)
E
i
(
t)
z

TIs mayy indicate a slow ggradual rise as some of the heat

reaches them, but when the excursion region expands to the
TIs, the temperature will rise suddenly and dramatically.
If reaction temperatures get high enough ((~480C),
480 C), thermal
(not catalytic) hydro-cracking can result, greatly increasing the
heat release.
If thermal hydro-cracking occurs to an
appreciable degree, reactor bed temperatures can increase to
over 800C within minutes.
No temperature point in the reactors, bed or skin, should ever
be allowed to exceed 440C.
440C This provides a 14C safety
margin below the mechanical design limit of 454C to account
for possibly higher temperatures where TIs are not located.
Therefore it is important to respond before a temperature
Therefore,
reaches 440C.

Play
y temp
p excursion
animation file

Go to Emergency
Handling file

Modifications
Hydro Cracker Unit
CPCL-CHENNAI INDIA

Operational
p
Improvements
p
-1
Modification in cold feed line
* Cold Feed and Hot Feed Combines before preheat
exchanger in original design.
design
* After Modification, Hot Feed bypasses first preheat
exchanger (E-01 Kero / Feed) and combines with
Cold Feed.
Resulted in Increased Preheat temperature by
5 8 0C

Modification in cold feed line

Hot VGO
(From Ref-3 & Ref-2)
155 190 0C

O/L -1600C

To 207E-02

Before- 155-159 0C
207E-01

After - 165 169 0C

Kero I/L
2110C
Cold VGO
(From
Storage)
800C

Modified Route up

- Kept closed

Modification in cold feed line

Benefits
* Feed filter inlet temperature increased
(better filter operation)
* Fuel reduction in Reactor (F-01) and
Fractionator ((F-02)) Furnace.
* Improvement in product stripper inlet
temperature and it
itss operation
operation.

Operational Improvements -2
Modification to Provide PCV at Reactor Effluent steam
generator (E-05) O/L
* Steam Generators common Header PCV is being operated at
13.5 ksc to contain heat in Reactor effluent steam generator
(207E 05).
(207E-05).
Resulted in Steam loss in UCO and Diesel PA steam
generator.
generator
* Individual Steam PCV for Reactor effluent steam generator
(207E 05) was proposed and under implementation
(207E-05)
- Steam loss from UCO and Diesel PA steam generator
can be recovered
reco ered

BFW

207C-50

207E-38
SKETCH
FOR
PROVISION OF PCV
IN 207E-05 MPS O/L LINE

PV-3582

207G38

207F-01

To 207C-16

207F-02

Reqd.
Control
Valve

From
CHPS

207E-07

207C-9
CLPS

207E-05

Recycle Gas

BFW

UCO From
207E -11

207E-04

207E-08

To 207E-09

Feed
from

207E-36
G3A/
B
To E 21

Rx. effluent
from R1 to R2

I/L temp. will

raise

207E03

207E-06
To 207E -36

207E-18
From R2 O/L

F 01

To
R1

To C 16

207C14

207E-11
UCO

Fro
m
C-

Modification to Provide PCV

at 207E207E-05 O/L
Expected Benefits
* Improvement in Product stripper operation
* Saving in fuel consumption in Reactor furnace
* Saving in fuel consumption in Fractionator
furnace
* Steam loss from UCO and Diesel PA steam
generators
t could
ld be
b recoveredd

Operational Improvements -4
MODIFYING 207E-04 TCV INTO 207C-09 LCV
* CLPS (207-C-09) outlet flow control valve 207-FIC-2801 bypass
block valve started passing heavily .
* As replacement of this bypass block valve require shut down of
the unit
* A scheme was implemented to utilize 207-E04 (Hot reactor
effluent / CLPS liquid exchanger) split range temperature
controller 207-TIC-2102 for controlling 207-C-09 level.
- This modification sustained the unit

MODIFYING 207E207E-04 TCV FOR 207C

207C--09 LCV

To Product Stripper
CLPS 207C-09
Modification

C
Converted
d iinto LCV
(Earlier TCV)

LCV

Split Range
TCV

207E-04

207E-08

Passing
B
Bypass
valve
l

Retained for TCV

Operational Improvements -3
Auto flushing control scheme for 207-C04 HP
Amine absorber
* Auto flushing scheme was implemented for HP Amine
absorber bypass C/V, which will open up 207-HIC-2502
to 5% MV once in 8hours and remain open for 5minutes
and then will
ill be closed
Benefit
* Avoid corrosion and high risk of fire hazards.

Auto flushing control scheme for 207207-C04

HP Amine absorber
HIC under
d Auto
A t Flushing
Fl hi
H2S Free Recycle gas to RGC

Lean Amine
HP Amine Absorber
H2S Ri
Richh Recycle
R
l gas

Amine LCV

Operational Improvements 4
MUG COOLING WATER MODIFICATION

Day Tank

Cooler

Jacket Cooling Water

Circulating Pump

Compressor

Operational Improvements 4
MUG COOLING WATER MODIFICATION

BENEFITS
z Because
B
off Jacket
J k cooling
li water 'O' ring
i Leak,
L k
H2 Gas entrapped into cooling water system and
caused frequent trip of compressor on cooling
water low pressure. (Due to closed circulation,
time required for the gas to escape was limited)
z After modification no entrapment of H2 gas into
to the cooling water system.
system Gas Leak if any will
be let out to atmosphere before going in for
circulation

Operational Improvements 5
Protection for RGC trip due to suction KOD level
High level alarm in overhead panel for H2S absorber.(70%)
Additional interlock to close the Amine chopper valve at inlet
of H2S absorber level at 80%. For safety of the HP amine
pumps minimum circulation valves will open to maintain the
pumps,
minimum.

Protection for High Pressure pumps

Reactor feed/Injection Water/ HP amine Pump discharge
Chopper Valves open / close interlock is activated by discharge
flow indications of respective Pumps.
Additional interlock provided to close the chopper valves incase
of tripping of pumps. low discharge flow of both feed and amine
circulation Pumps will close the chopper valve (in design).
design)

Operational Improvements 6
FEED FILTER BACK WASH STREAM MODIFICATION
Reactor Feed Filter backwash stream was originally
g
y to be routed
to u/s of UCO R/D cooler. Difficulty in routing was encountered
due to mismatch between Filter backwash Pump discharge
pressure and the system back pressure. Problem was overcome
by modifying the Filter backwash stream routing to d/s of Flow
Control Valve for UCO to storage, which is at d/s of UCO R/D
cooler.
d/s OF CV

TAKE OFF LINE

Operational Improvements 7
INCORPORATION OF ADVANCE CONTROLS
Overall CAT control for maintaining the Reactor bed Temperature
Cold High Pressure Separator hydrocarbon Level Control
Cold High Pressure Separator Boot Level Control.
Cold Low Pressure Separator
p
Level Control
Product Stripper Level Control
Fractionator Top Temperature Control
Fractionator Bottom Level Control (Hot & Cold selection for
(
(FCCU)
)

Operational Improvements 8
IMPLEMENTATION OF AUTOMATIC DUMPING
SYSTEM (ADS)
Incase of Reactor bed temperature runaway or any raise
in Reactor
eacto Skin
S
temperature,
te pe atu e, interlock
te oc control
co t o system
syste iss
provided to open the Dump valves automatically for HP
system depressurisation and to close the Dump valves
as per the control sequence. Schedule is followed to
check the ADS sequence control once in a week for it's
operability.
bilit

PEG and RTJ Flanges

Specified Procedures are to be followed.
Special
p
Tools are required
q
i.e.. Torque
q wrench and tensioner.
Flange preparation lapping.
Check for Proper Gasket Material too hard or soft will
mean trouble.
Skilled manpower is a must.
Improper Installation WILL cause leak in HP circuit
and delay startup
NOTE: PEG - Pressure Energized Gasket (R1 &R2 inlet).
RTJ Ring type joint.

Case study
z Dump

valve failure.
z RGC-trip
RGC trip

OHCU DUMP VALVE FAILURE

SERIOUS EMERGENCY IN OHCU:
DURING RGC TRIP, DUMP VALVES FAILED TO
OPEN.
OPERATING CREW HAD SHOWN EXEMPLARY
COURAGE IN HANDLING THE EMERGENCY.
MAXIMISING FEED & UCO RECYCLE TO
CONTROL TEMP EXCURSION.
RGC SUCTION BLEED WAS THE ONLY OTHER OPTION
AVAILABLE FOR PRESSURE REDUCTION.
MAXIMUM BED TEMP EXPERIENCED WAS 427 degg C.
(METAL DESIGN TEMP 454 deg C)

OHCU DUMP VALVE FAILURE

MEASURES TAKEN TO KEEP OHCU ONLINE WITH DUMP VALVE
FITTED WITH INTERMEDIATE METALLURGY SS1740PH
ONE OF THE DUMP VALVE 2601 TO BE OPERATED FROM DCS

DURING EMERGENCY
DUMP VALVE 2602 IS KEPT OPEN WITH U/S B/V ISOLATED
CONDITION. B/V CAN BE OPENED AS PER THE REQUIREMENT
DURING EMERGENCY.
TIME TAKEN FOR OPENING THE B/V ( FROM OPERATOR CABIN
TILL COMPLETE OPENING OF B/V ) CHECKED BY TIME STUDY
AT OPERATING PRESSURE. TIME : 2.5 MINUTES
UNIT FEED RATE LIMITED TO 170 M3/ HR WITH UCO RECYCLE
50M3/HR
50
3/
AND
N C
CAT : 373 DEG.C
G.C MOC
OC PREPARED

SUBSEQUENTLY DUMP VALVE INTERNALS CANGED

AS PER SPEC AND MAXIMUM THRUPUT ACHIEVED.

OHCU DUMP VALVE FAILURE

R1 IST BED TEMPS

R1 2ND BED TEMPS

R1 3RD BED TEMPS

R2 1ST BED TEMPS

R2 2ND BED TEMPS

Case StudyStudy-RCG
RCG--TRIP

CPCL OHCU MAJOR EVENT

RGC TURBINE SOLO RUN - 18.04.04
MUG SOLO RUN - 07.05.04
HP
HP PR TEST - 19.06.04
19 06 04
MUG LOAD RUN - 23.06.04
207F1--LIGHTT ON - 28.06.04
RGC START - 01.07.04
207F2LIGHT ON - 02.07.04
FURNACE
FURNACE DRY OUT - 03.07.04 TO 07.07.04
H2-PR TEST - 09.07.04
DUMP TEST - 13.07.04
CATALYST
CATALYST LOADING - 17.07.04
17 07 04 TO 22.07.04
22 07 04
CATALYST DRY OUT - 27.07.04 TO 29.07.04
CATALYST SULFIDING - 03.08.04
FEED CUT IN - 04.08.04
PRODUCT OUT - 05.08.04

HYDROCRACKER UNITS IN INDIA

z

REFINERY

GUJARAT REFINERY

MANGALORE REFINERY

MRPL

JULY 1996

PANIPET REFINERY

IOC

APRIL 1999

MANGALORE REFINERY

MRPL

NOV 1999

MATHURA REFINERY

CHENNAI PETROLEUM
COPORATION LID

COMPANY

IOC

IOC

CPCL

COMMISSIONED

DEC 1993

JULY 2000

AUG 2004

CPCL commissioned the entire process

units
i without
ih
any setback
b k and
d iin a safe
f
manner within stipulated time.
Hydro
y
cracker unit was commissioned in
35 days smoothly from pressure test of HP
system in line with the process licensor
schedule of 33 days.

THANK YOU