Refining Processes

S Debnath, Mathura Refinery, IOCL

8/31/2010

Birds Eye View, MR

Beginning of Petroleum Refining in India

In 1890s Crude Oil used to be
distilled in DIGBOI in Cast
Iron pans called Stills.
Bottom portion of one such
still of 9 feet dia is still kept at
Digboi Refinery.
The refinery was
commissioned in 1901 at
Digboi with 500 Barrels per
Day capacity

THE FIRST STILL LIES STILL

OUTLINE
1.
2.
3.
4.
5.
6.
7.
8.

Introduction
Physical Processes
Thermal Processes
Catalytic Processes
Conversion of Heavy Residues
Treatment of Refinery Streams
Lube base stock preparation
Other processes

REFINERY PROCESSES

An oil refinery separates the crude oil in

to different fractions and converts them
into usable products
Maximize Higher value distillates like
LPG, gasoline, ATF, Kerosene and
Diesel
Produce cleaner products
8/31/2010

Composition of Crude Oil

Crude oils is a complex mixture of thousands

of hydrocarbons. (i.e paraffins, Napthenes &
Aromatics)
Brownish black in colour and colloidal in
nature
Contains small amounts of non-hydrocarbon
impurities in the form of organic compounds
of sulphur, oxygen, nitrogen, metals, water
and salts
8/31/2010

Element composition of Crude Oil

Hydro Carbons > 95%
Sl.
no.

Element

Percentage (%)

Carbon

83-87

Hydrogen

11-15

Sulphur

0-3

Oxygen

0-2

Nitrogen

0-0.6

Metals

0-0.1

8/31/2010

Impurities of Crude Oil

1.

Sulphur Compounds :

2.

Nitrogen Compounds : Pyrrole,Pyridine,Quinoline, etc.

3.

Oxygen Compounds :

Naphthenic Acid,Phenol etc.

4.

Metallic Derivatives:

Derivatives of Organic acids with metals

like Ni,Cu,V,Pb,As,Fe etc.

5.

Water and Salt :

Along with water, Soluble inorganic

compounds like Chlorides,Sulphates of
Sodium, Calcium and Magnesium

8/31/2010

H2S, Mercaptans, Thiophenes,

Benzothiophenes

Typical Properties of Crude

Sl.No

Properties

1.

Specific Gravity

0.8868

0.7887

0.8688

2.

Sulphur, % wt

0.1

0.05

0.25

3.

Salt content, Lbs/1000 BBLS

30-35

3-8

4.

Suitability for lubes

No

No

No

5.

Suitability for Bitumen

No

No

No

6.

Lighter Hydrocarbon, wt%

0.8

3.0

1.0

7.

Middle Distillates, wt%

29.2

81

62

8.

RCO , wt%

70

16

37

8/31/2010

North
Gujrat
Crude

Ankaleshwa
r
Crude

Assam
crude

Typical Properties of Crude

Sl.No

Properties

High
Sulphur
Crude

Nig. Crude

Bombay
High Crude

1.

Specific Gravity

0.8735

0.866

0.828

2.

Sulphur, % wt

2.59

0.12

0.12

3.

Salt content, Lbs/1000

BBLS

2.1

2.0

15

4.

Suitability for lubes

Yes

No

No

5.

Suitability for Bitumen

Yes

No

No

6.

Lighter Hydrocarbon, wt%

1.6

0.9

1.3

7.

Middle Distillates, wt%

45.4

58.1

62.7

8.

RCO , wt%

53

41

38

8/31/2010

Critical Quality Parameters of Products

Sl.no

Product

1.

LPG

Evaporation Temperature at 95 % Volume =2 deg C,

Max
Cu Corrosion =not worse than No.1
RVP
=1050 KPa, Max

2.

Motor Spirit

Density
RON
Sulphur
Benzene

3.

ATF

Density
=775-84 Kg/M3
Flash Point = 38 deg c, Min
Sulphur
=0.25 wt %,Max
Smoke Point =20 mm, Min

4.

SKO

Density
=790-820 Kg/M3
Flash Point =35 deg c, Min
Sulphur
= 0.25 wt %, Max
Smoke point = 18 mm, Min

8/31/2010

Key Quality parameters

=720-775 Kg/M3
=91 Min
=150 ppm, Max
=1 Vol. %, Max

Critical Quality Parameters of Products

Sl.no

Product

5.

Diesel

Density
Sulphur
Cetane Number
Recovery at 360 deg C

=820-845 Kg/M3
= 50 ppm
= 51 Min
=95 Min

6.

Fuel Oil

KV@ 50 deg c
Sulphur
Ash

=125 , Max (Winter)

=180 , Max (Summer)
= 4 wt %, Max
= 0.1 wt %, Max

Penetration at 25 deg c
Flash Point
Viscosity at 60 Deg C
Softening Point

=60 (1/10mm) , Min

=175 deg C,Min
= 2400 (min) CP
=45-55 deg C

7.

8/31/2010

Bitumen

Key Quality parameters

Physical and Chemical processes

Physical
Distillation
Solvent extraction
Propane deasphalting
Solvent dewaxing
Blending

Chemical
Thermal
Visbreaking
Delayed coking
Flexicoking

Catalytic
Hydrotreating
Catalytic reforming
Catalytic cracking
Hydrocracking
Catalytic dewaxing
Alkylation
Polymerization
Isomerization

Refinery Operations

PRIMARY PROCESSING UNITS

SECONDARY PROCESSING UNITS

8/31/2010

PRIMARY PROCESSING UNIT

The purpose of Primary unit is to separate the crude
in to different fractions by distillation.
Known as mother unit of the refinery, consist of

CRUDE DISTILLATION UNIT (CDU)

VACUUM DISTILLATION UNIT (VDU)

Commonly referred as Atmospheric and Vacuum
Distillation unit (AVU)

8/31/2010

CDU OPERATIONS
1.

The hydrolysis of salts in crude oil at high temperature produces

HCL and corrodes the Column Internals and overhead system.

2.

The sediments in crude oil fouls the heat exchanger, furnace tubes
and erodes the pipelines by abrasive action.

3.

Desalting approaches
-To reduce soluble salt content
-To reduce suspended solids.
-To reduce residual water

4.

Desalting of crude oil is carried out in a vessel provided with

electrodes under High potential field(15000-18000 Volts)

5.

Desalter Operating condition:

-Temperature range :130-140 deg C
-System pressure :12-14 kg/cm2g

8/31/2010

CDU OPERATIONS
6. The desalted crude is Preheated to about 180-200 deg C and fed to
Prefractionator column
7. The purpose of prefractionator is to separate the lighter hydrocarbons at
relatively lower temperature so as to reduce heat energy requirement across
furnace and to reduce the main fractionator overhead vapour load
8. Prefractinator are typically used in revamps for energy conservation and unit
capacity enhancement
Prefractionator Operating condition
Top Temperature range
Pressure

= 120-130 deg c
= 1.5-3.0 kg/cm2g

9. The Pre- fractionator column bottom is fed to Fractionator column after

heating to 360 370 Deg C in Heat Exchanger train & Furnace.

8/31/2010

CDU OPERATIONS
10.

The main fractionator separates the pre-topped

crude in to different fractions like Naphtha,
Heavy Naphtha, Aviation Turbine Fuel,
Kerosene, Light Gas Oil, Heavy Gas Oil and
Reduced Crude Oil.

Column Operating Condition

Top Temperature Range
Pressure

8/31/2010

=120-135 deg C
=1.0-2.5 Kg/cm2g

Stabiliser Column
11.

Lighter Hydrocarbons from Pre-topping column top is heated

to about 125 deg C and fed to stabiliser column.

12.

The stabiliser stabilize the naphtha by separating the feed in

to LPG and stabilised Naphtha
Column Operating condition
Top Temperature range =66-68 deg C
Pressure
=7.5-10 kg/cm2g

8/31/2010

Atmospheric & Vacuum Distillation Unit Flow Diagram

LPG

S
T

Pr= 40-60 mm Hg a

To Steam Ejector

Stabilized Naphtha

Unstabilised
Naphtha

Light Naphtha
LVGO
Heavy Naphtha

Desalter
T=130-140
Deg C

Crude Oil

8/31/2010

FURNACE
Furnace
T= 370 Deg
C

T= 270280 Deg C

Atmospheric

ATF
Heavy Kero
LGO

LDO
HVGO

Vac Slop
HGO

FURNACE
Furnace

RCO

Vacuum

T=200 Deg C

Pre-topping

SR
T= 415 Deg C

Treatment of CDU Products

Sl.N
o.

CDU
Product

Impurities

Quality

1.

LPG

H2S,
Mercaptans

Cu Corrosion

2.

NAPHTH
A

H2S,
Octane
Mercaptans, Number,
Sulphur
Benzene

Caustic Wash,Merox,
Hydrotreatment, for Low
Octane no. Catilytic
Reforming and
Isomerisation

3.

ATF

Mercaptans

Merox Treatment

8/31/2010

Aromatics,
Freezing
Point

Treatment/Processing
Caustic Wash and Merox
Treatment

Treatment of CDU Products

Sl.N
o.

CDU
Product

Impuriti
es

Quality

4.

SKO

Sulphur,
Mercapta
ns

Smoke Point

Merox, Hydrotreatment,
Furfural Extraction

5.

Diesel

Sulphur

Cetane No.
Pour Point,
Recovery,
Moisture

Hydrotreatment(DHDS &
DHDT) for Sulphur and
Cetane No.,
Salt dryers and vacuum
evaporators for Moisture
treatment
Pour Point and recovery is
Crude Specific and can be
adjusted by optimizing the
fractionator column.

8/31/2010

Treatment

Significance of Vacuum Distillation

RCO from CDU is "heavy", and the separation of this

stream into various fractions would normally require more
energy and higher temperatures.
Higher hydrocarbons promotes coking reactions at more
than 380 deg c at atmospheric pressure fouls the furnace
tubes.
To reduce the amount of energy input required, and to
recover the valuable products from RCO without cracking,
it is distilled under vacuum.
The vacuum condition reduces the boiling point of the RCO
and the fractions are separated relatively at lower
temperature led to energy saving and reduces fouling of
the furnace tubes

8/31/2010

VDU OPERATIONS
1.
2.
3.
4.

VDU objective is to recover valuable product from

RCO relatively at lower temperature.
Feed preparation unit for FCC/HCU/VBU/BBU
The Operating temp. is about 410-420 Deg C
Vacuum is created by steam ejectors.
Column Operating Condition:
Top Temperature range : 50-65 deg C
Pressure
: 25-60 mm Hg (a)

8/31/2010

Secondary processing of VDU Products

Sl.N
o.

VDU Product

1.

LVGO

High S. Low
Cetane no.

2.

LDO

Fluid catalytic unit /

High S.
Hydrocracker unit
Heavy
Hydrocarbons

3.

HVGO

High S.
Fluid catalytic unit /
Heavy
Hydrocracker unit
Hydrocarbons

4.

Vacuum Slop

Visbreaker unit / Coker

Heavy
Hydrocarbons
, Fuel oil
Product

5.

Vacuum
Residue

Residue

8/31/2010

Quality

Processing
Hydrotreatment (DHDT) for
Sulphur and Cetane No.,

Bitumen Blowing Unit / VBU /

Coker

Significance of Secondary Processes

To improve the refinery profit margins by converting

low value heavy ends to high value products like
LPG/Gasoline/ Kerosene/Diesel.
Further processing of straight run products is
necessary to meet the final products specification

8/31/2010

Classification of Secondary Processing Units

Secondary Processing Units

Treatment
Process
Caustic
Wash

Merox

Cracking Process

Diesel /
Naphtha/Ker
o.
Hydrotreatin
g unit

Quality
Upgradati
on

Cat.
Reforming
unit

Other units

Hydrogen
Generation
unit

Isomerisati
on unit

BBU
LUBES
Visbreake
r Unit
8/31/2010

Delayed
Coking

Fluid
Catalytic
Cracking

Hydro
cracking

Sulphur
Recover
y unit

Factors for Selecting Secondary Processes for a

Refinery

Type of Crude
Product Slate
Product specifications
Investment cost
Operating cost
Sophistication of technology

8/31/2010

Cracking process

Fluidized Catalytic Cracking Unit

Hydro Cracker Unit
Visbreaker Unit
Coking unit

8/31/2010

Fluid Catalytic Cracking Unit (FCCU)

Objective : To convert Heavy Vacuum Gas Oil to

valuable distillates like LPG, Gasoline, Diesel by
catalytic cracking in fluidized bed.

Feed : VGO/RCO/VR/HydroCracker Bottom.

Catalyst : Silica & Alumina Zeolite Structure

8/31/2010

FCCU Product Yields and Operating Conditions

1. Typical Product Yields
Sl.no.

Products

Wt%

1.

Fuel Gas

2-4

2.

LPG

10-40

3.

Gasoline

25-40

4.

Hy.
Naphtha+LCO

15-30

5.

CLO

5-15

2. Operating Conditions :
Temperature range : 490-550 DEG C
Pressure
8/31/2010

: 2-3 kg/cm2(g)

Fluid Catalytic Cracking Flow Diagram

FLUE GAS

R
E
A
C
T
O
R

Regen
erator

S
T
A
C
K
ORIFICE
CHAMBER

M
A
I
N

COL OVHD
RECEIVER
HN
FG

C
O
L
U
M
N

LCO

HCO
Recyc
le

LPG
WGC

GAS CON
UNIT

FCCG
MAB

CLO
AIR
CO BOILER

SLURRY
SETTLER

FEED
FURNACE
Furnace

Slurry Recycle

8/31/2010

FCCU Product Qualities & End Users

Sl.No

Product

Qualities

End Users

1.

Gas

H2S rich Off. Gas

Refinery Fuel gas

System after Amine
Wash

2.

LPG

H2S, Mercaptans,
olefins like
Propylene/Butylene

To LPG Pool/
Petrochemical
feedstock

3.

Gasoline

High Octane No. and

high Olefin contents

MS Pool

4.

Hy.Naphtha +
LCO

Low Cetane no. High

S , Unsaturates

Diesel Pool After

Hydrotreatment

5.

CLO

High Aromatics, Good

Cutter Stock

Fuel Oil

8/31/2010

Significance of Gascon section

In Gas con section the separation of LPG and stabilization of
naphtha is achieved in steps as follows

The overhead gas is compressed by WGC to about 13 kg/cm2 g

The LPG component in the compressed gas is absorbed by

overhead naphtha in the absorber and send to stripper

The lighter ends C1 and C2 are stripped off and the stripper
bottom is send to debutanizer

The debutanizer separates the LPG and stabilize the naphtha

8/31/2010

Key aspects of Operation and Maintenance

Catalyst circulation is established by fluidization

Handling of hydrocarbon and air side by side at very
high temperature (500-700 deg c)
Reactor and regeneration section is separated by
delicate pressure balance
Coke deposited on the catalyst is burned off in
regenerator at 700 deg c.
Separation of fine catalyst in hydrocarbon vapours
and in flue gas by cyclones
Erosion is a common phenomena in Cyclone and
slide Valves

8/31/2010

Hydrocracker Unit

Objective : To convert Heavy Vacuum gas oil to valuable

distillates like LPG, Naphtha, ATF, Kerosene and Diesel.

Feed

Catalyst :

8/31/2010

: VGO / Coker Products

Ni/Mo oxides

for Dematalisation
& Hydrotreating
Ni/Mo/W(Tungsten) for Hydrocracking

Various configurations of Hydrocraker Units

1. Single stage Once through Hydrocraker unit (SSOT):
a. Feed and Hydrogen is passed through reactors only
once for 60 80 % of partial conversion.
b. Unconverted Oil is sent to FCCU.
2.

Single stage recycle (SSRec) :

a. Unconverted oil is recycled back to feed for
100% conversion.

3. Two stage Hydrocraker Unit:

a. Unconverted Oil of SSOT is sent to another reactor for
100% conversion
8/31/2010

Single stage Vs Two stage Hydrocraker unit

Recycle
Gas

Makeup
H2

Gases

Recycle
Gas

Fresh Feed
R

Heavy
Naphtha

E
A

RGC

RGC

Kerosene

Diesel

O
R

separator

First stage
Product

Unconverted Oil
Second stage Product

1) Single Stage in Blue

2) Two Stage is Blue and Green Combined
8/31/2010

separator

HCU Product Yields and Operating Conditions

1.

Typical Product Yields

Sl.no Products
.

Wt%

1.

Off. Gas

2-4

2.

LPG

1.5-3

3.

Naphtha

6.5-10

4.

ATF/Kero

27-40

5.

Diesel

29-40

6.

Hydrocraker
Bottom

5- 35

2. Operating Conditions :

8/31/2010

Temperature range

: 370-420 DEG C

System Pressure

: 160-170 kg/cm2(g)

Hydro Cracker Unit Flow Diagram

Ex
MPU

Makeup H2

RGC
MUC

R-1

HP Amine

R-2

Gas & LN to Light

End
Recovery Section

Amine
Scrubber

PSA
Wash Water

Heavy
Naphtha

F-1
G-1

V-1

Feed
Filter

CR
V-2

E-1

V-3

Hydrocracking
Reactor

MPU
PRT

AM
HVGO
BH
HVGO

8/31/2010

Unconverted
Oil

To MUC
V-8

Feed Preheat Ex

ATF/Kero

V-9
F-2

Diesel

HCU Product Qualities & End Users

Sl.No

Product

Qualities

End Users

1.

Gas

H2S rich Off. Gas

Refinery Fuel gas

System after Amine
Wash

2.

LPG

H2S Contents

To LPG Pool after

caustic wash

3.

Naphtha

low Octane No. and

low S contents

To Gasoline Pool /
Hydrogen unit Feed

4.

ATF / Kero

Low S and Low

Aromatics

To ATF/ kero. Pool

5.

Diesel

Low S and High

Cetane

EURO III Diesel

6.

Unconverted
Oil

Low S, High
Saturates

FCCU FEED

8/31/2010

Key aspects of Operation and Maintenance

Reactions are highly exothermic and precise

control of reactor bed temperature is
necessary
High pressure system and all joints are
metallic ring joints.
H2 when leaks get heated up and auto
ignited.
H2 fire is not visible to naked eye.
Shell thickness of the reactor is about 30
cms

8/31/2010

Visbreaker Unit (VBU)

Objective : To reduce viscosity of Heavy Ends i.e.

RCO/Vacuum residue by Thermal Cracking.
Feed : RCO/Vacuum residue
Typical Operating Conditions:
Temperature Range
: 450-470 Deg C
Pressure
: 9-14 kg/cm2(g)
Viscosity of Feed
: 500-1200 cst at 100 Deg C
Viscosity of Product (VBtar) : 50 150 cst at 100 deg C

8/31/2010

Visbreaker Unit Flow Diagram

T=135 0C
P=4.6
Kg/cm2

COL OVHD
RECEIVER

P=10
Kg/cm2 g

M
SA
I
ON

S
O
A
K
E
R

A
C
KO
EL
RU

M
N

SLOP

FEED

Furnace
Furnace

T=450 0C

G
O
S
T
R

GO
steam

V
B
N
S
T
A
B

VB HN

VAP RET

FUEL GAS

VBN
steam
GAS OIL

VB
TAR
STR

LP GAS
TO
FURNACE

VB FO
8/31/2010

VBU Product Yield/Qualities & End Users

Sl.No Product

Yield

Qualities

End Users

1.

Gas

1.82

H2S rich Off. Gas

Refinery Fuel gas

System after Amine
Wash

2.

VB
Naphtha

3.12

H2S, Mercaptons,
high olefins

To FCCU or CRU

3.

VB Gas
Oil

13.9

Low Cetane no,

Highly unsaturated

To DHDS or Fuel Oil

4.

VB Tar

81.16

Lower Viscosity than

feed

Fuel Oil

8/31/2010

Significance of Soaker drum

Required cracking is achieved in soaker by

increasing residence time at relatively lower
temperature
Reduction of heat energy requirement
across furnace.
Soaker internals reduce back mixing thereby
improves yield and product stability
Increase furnace run length
Higher selectivity of middle distillates

8/31/2010

Delayed Coker

Objective : To produce valuable distillate from

Heavy ends by thermal cracking.
Feed : RCO/Vacuum Residue/other heavy ends or
residues
Typical Operating Conditions:
Temperature Range : 495-505 Deg C
Pressure
: 2-3 kg/cm2(g)

8/31/2010

Delayed Coker Unit Flow Diagram

Gas/LPG

FEED

Pre heat Exchanger

F
R
S
OA
C
AT
KI
O
EN
RA
T
O
R

Naphtha
Kero
Gas Oil
Fuel Oil

S
E
P
A
R
A
T
O
R

RFO

Furnace
Furnace

T=505 0C
8/31/2010

C
O
K
E

C
O
K
E

C
H
A
M
B
E
R

C
H
A
M
B
E
R

Delayed Coking Process

Feedstock : Vacuum Residue

Good process for increasing distillates and minimizing black
oil production.
Products Yields

Gas+loss
LPG
Naphtha
LCGO
HCGO
RPC

5%
4%
6%
27%
33%
25%

Gas oil & Naphtha need further treatment.

Delayed Coker Product Yield/Qualities & End

Users
Sl.No Product

Qualities

End Users

1.

Gas

H2S rich Off. Gas

Refinery FG after
Amine Wash

2.

LPG

Mercaptans, unsaturates

To LPG after Merox

/Caustic wash

3.

Naphtha

Low Octane, High Olefins

To FCC or CRU

4.

Kerosene

High unsatuartes

To DHDT Feed

5.

Gas Oil

Low Cetane No. and high

unsaturates

To DHDT & HCU feed

6.

Fuel Oil

Good cutter stock

Fuel Oil

7.

Coke

Low ash, High Sulphur

Gasification/Electrode
Preparation/ cement
ind.

8/31/2010

Key aspects of Operation and Maintenance

A pair of coke chambers operates typically on 24

hrs cycle.
Coke cutting in coke chambers by high pressure
water jets operates at 170 kg/cm2g.
Day to day maintenance activities includes coke
chamber opening, coke cutting, coke disposal,
box up and pressure testing.
Furnace tubes gets fouled by coke deposition
typically in 6-8 months period.
Coke in furnace tubes is removed by steam-Air
decoking.

8/31/2010

Quality Up gradation Process

8/31/2010

Catalytic Reforming unit

Isomerisation Unit
Diesel Hydro Treating unit

Catalytic Reforming Unit (CRU)

Objective : To Upgrade the Naphtha to High

Octane MS Component (Reformate) .
Feed : 85-160 Deg C cut Naphtha /
Visbreaker Naphtha
Catalyst : Ni-Mo Oxides for NHTU Reactor
Pt-Sn or Re for Reforming

8/31/2010

Catalytic Reforming Unit

Main types of reformers are :
1. Semi-regenerative (SR)
The reformer processes feedstock for a time and then
shuts down for regeneration.
2. Cyclic
Any reactor can be isolated for regeneration while the
other reactors are in operation
3. Moving bed or CCR
Catalyst is moved continuous through the reactors,
withdrawn from the last reactor, regenerated in
regeneration section and returned to the first reactor as
fresh catalyst.

8/31/2010

TECHNOLOGY SELECTION
SR vs CCR TECHNOLOGY

In SR type the Catalyst is regenerated at the end of the cycle

length when the reformer unit is shut down
In CCR type the catalyst is continuously regenerated outside
the reaction section and thus the severity of operation is kept
same throughout run length.
Catalyst taken from the last reactor is regenerated in
regenerator by burning off coke. This regenerated catalyst
after correcting the chloride level is sent back to first reactor.
This facilitates the operation of reformer unit at high severity
at low pressure and low hydrogen / hydrocarbon ratio.

8/31/2010

Continuous Catalytic Reforming Unit Flow Diagram

Off Gas to
FG system

LSRN (85-160)
VBN

H2 RICH
GAS TO PSA

Off Gas to
FG system

NHDT

Pr. 17.0
kg/cm2g

COL OVHD
RECEIVER

RGC

Pr. 17.0
kg/cm2g

T =-10 deg c

Recontacting drum
SEPARATOR

S
T
A
B
I
L
I
S
E
R

LPG

Regenerator
T=520-540 Deg C

8/31/2010

Reformate to MS Pool
via RSU

CRU Product Yield and Operating Conditions

1.

Typical Product Yields

Sl.no.

Products

Wt%

Quality

End Users

1.

H2 Rich
gas

6.58.0

94% H2 gas

PSA Unit to
recover H2

2.

LPG

2.512

S free LPG

To MS Pool After
catalytic
Reforming

3.

Reformat
e

80-91

RON- 98, low

S , High Bz.

To MS POOL after
Reformate Splitter

2. Operating Conditions :
Temperature range

: 490-540 DEG C

System Pressure

: 2.0 - 30 kg/cm2(g)

8/31/2010

Isomerisation Unit (PENEX-DIH)

Objective : To Upgrade the Naphtha by increasing its Octane

Number to Higher Octane/Low Benzene/Low Olefins MS
Component (Isomerate) to Meet Euro III / IV MS
Specifications.
Feed : C5-85 Deg C cut Naphtha /FCC gasoline(70-90 deg C
cut)/ Lt. Reformate
Catalyst :

8/31/2010

Co-Mo
Pt
Ni Based

for Hydrotreator Reactor

for Penex Reactor
for Methanation

Isomerisation Unit Flow Diagram

NHDT

FCC H/C (70-90)

H2 Make
up gas

8/31/2010

S
T
A
B
I

Penex
feed dryer

Make up
gas dryer

Pr. 20.3 Kg/cm2g

COL OVHD
RECEIVER

Lt.
reformate

Hydrotreated
Naphtha

Meth nator
reactor

Off Gas to
FG system

Off Gas to
FG system

LSRN (C5-85)

L
I
S
E
R

Feed surge
drum

Penex
Reactors

Temp. = 125-185
Deg C

DIH Recycle

LPG to
Stripper

Pr. 1.3 Kg/cm2g

D
I
H
C
O
L
U
M
N

Total Isomerate

ISOM Product Yield and Operating Conditions

1.

Typical Product Yields

Sl.no.

Products

Wt%

End Users

1.

Off gas

1.4

Refinery fuel gas

System

2.

LPG

11.3

To LPG POOL

3.

Isomerate

87.3

To MS POOL

2. Operating Conditions :
Temperature range

: 126- 145 DEG C

System Pressure

: 33.5 kg/cm2(g)

8/31/2010

Key aspects of Operation and Maintenance

Pt based chlorinated alumina catalyst

and are very Sensitive to impurities
and need careful pretreatment
Even traces of sulphur, moisture and
oxygenates are catalyst poison.

8/31/2010

FCC Gasoline Desulphurization

Feed
: FCC Gasoline
Total Sulphur in Product: 100 ppmw
Technology
: Prime G
Selective Hydrogenation Unit (SHU)
Gasoline Splitter Unit (GSU)
Hydro-desulphurization Unit (HDU)

Objective: Removal of Organic Sulphur from FCC Gasoline

with minimum octane loss in order to meet future EURO IV
norms in MS

FCC Gasoline Desulphurization

Process Flow Diagram (PFD)

Sour FG

HDS Reactor

HtCut

Stabilizer

Htcut
stripper

LCN

Splitter

Hydrogen

SHU lead Reactor

Steam

Off Gas

Feed
HCN
Recycle
H2

HCN

LCN

LCN + HCN
to MS Pool

FCC Gasoline Desulphurization GDU

Yield Patterns
Stream

% Yield (SOR/EOR)

LCN

23

Heart-Cut

15

HCN

62

Feed & Product properties

S/N

Property

Density @ 150C

IBP FBP (ASTM

D86)

Total Sulphur

RON

Unit

Feed

LCN + HCN

Heart cut

Kg/m3

716.5

725

672

0C

41 - 179

43 - 180

62 - 82

ppmw

500

100

80

91

89.4

93

EURO III/IV Specification of MS gasoline

Sl.n
o

Characteristics

BS-III

EU-IV

1.

RON,min

91

91

2.

Sulphur, PPM
max

150

50

3.

Benzene, Vol
%max

4.

Aromatics, Vol %
max

42

35

5.

Olefins, Vol%
max

21

21

6.

RVP@38 Deg C ,
KPa

58 max

58 max

8/31/2010

Treating Process

Caustic wash
Merox Unit
Diesel Hydro Desulphurization Unit
Kero Hydro Desulphurization Unit

8/31/2010

Treating Process
Caustic Washing for removing H2S and light Mercaptans
and suitable for LPG and Naphtha

1.

Merox Process
a. Extractive Merox : Suitable for Lighter fractions
b. Sweetening Merox: Suitable for boiling range upto
350 Deg C

2.

Chemical Reaction: Amb.Temp.

2RSH + O2 Iron group metal
chelates

RSSR + H2O

After Treatment:
The treated stream is given water wash, followed by sand
Bed
Coalescer or salt drier for removing entrained water.
8/31/2010

MEROX Units Mercaptan OXidation

Mercaptans are undesirable in the final products
because it effects their stability, sulfur content,
odour etc.
Objective: Chemical treatment for conversion
of Mercaptans to di-sulphides.
RSH+

+ 1/4 O2

RSSR + H2O

Feed: ATF, Gasoline, VB Naphtha and LPG.

8/31/2010

LPG Merox
Feed / Product properties

Quality

Feed Quality
RSH-S max

Wppm

300

H2S max

Wppm

2100

Product Quality
Cu corrosion

1B max

ATF Merox
Feed / Product properties

Quality

Feed Quality
Sp.Gr

0.79-0.82

RSH-S max

Wppm

150

H2S max

Wppm

10

Saybolt colour Min

25

Product Quality
RSH-S max
Saybolt colour Min

Wppm

10
20

LPG MEROX
Lean
Amine

Lean
Amine

LPG to
Storage
Caustic
Wash

LPG to
PRU

Amine Wash
Columns

Caustic Settler
Sand
Filter
CR LPG

Rich
Amine

ATF MEROX
Air

Caustic
Prewash

Reactors

Caustic
Settler

Coalescer
ATF ex
AVU

Caustic

Salt
Dryer

Clay
Filters

ATF R/D
ASA Dosing

DMW

Water
Wash

Diesel Hydrotreating Unit (DHDT)

Objective : To meet the Euro III/IV diesel quality

requirement ( 350/50 ppm S and Min. 51 Cetane No.)
Feed : Straight run diesel / FCC diesel component/ Coker and
Visbreaker diesel components.
Catalyst : Ni-Mo oxides
Chemical reactions: Desulphurisation and Denitrification
S

H2

N
H2

H2S
NH3

Aromatic compound + H2 --> Napthene Compound

8/31/2010

Diesel Hydrotreator unit Flow Diagram

Off. gas

Fuel gas
H2 Recycle
H2 Make
Up

A
b
s
or
b
er

Temp. 350
Deg C

High Pr.
Separator
Pr. 100-105
kg/cm2g
Feed

Lean
Amine

COL OVHD
RECEIVER
S

Rich
Amine

T
R
I
P
P

Wild
naphtha

E
R

Steam

Furnace

Reactor
8/31/2010

Desulphurized &
Hydro treated Diesel

DHDT Product Yields and Operating Conditions

1.

Typical Product Yields

Sl.no.

Products

Wt%

End Users

1.

Off Gas

2.65

Refinery Fuel gas

system after Amine
Wash

2.

Wild Naphtha

2.8

To Naphtha Pool
after stabilisation

3.

Diesel

96.1

To Diesel Pool

2. Operating Conditions :

8/31/2010

Temperature range

: 320-380 DEG C

System Pressure

: 100-105 kg/cm2(g)

Diesel Hydro-Treatment Unit (DHDT)

Objective : To meet the EURO-III/IV diesel quality

requirement (<350/50 ppm S)
Feed : Straight run diesel / FCC diesel component/
Coker and Visbreaker diesel components.
Catalyst : Ni-Mo oxides

8/31/2010

Diesel Hydro Treatment Unit

Off. gas

Fuel gas
H2 Recycle
H2 Make
Up

A
b
s
or
b
er

Temp. 350
Deg C

High Pr.
Separator
Pr. 35-40
kg/cm2g
Feed

Lean
Amine

COL OVHD
RECEIVER
S

Rich
Amine

T
R
I
P
P

Wild
naphtha

E
R

Steam

Furnace

Reactor
8/31/2010

Desulphurized
Diesel

DHDT Product Yields and Operating Conditions

1.

Typical Product Yields

Sl.no.

Products

Wt%

End Users

1.

Off Gas

1.36

Refinery Fuel gas

system after Amine
Wash

2.

Wild Naphtha

1.04

To Naphtha Pool
after stabilisation

3.

Diesel

97.1

To Euro II Diesel
Pool

2. Operating Conditions :

8/31/2010

Temperature range

: 320-380 DEG C

System Pressure

: 40/ 100 kg/cm2(g)

EURO III/IV Specification of HSD (High Speed Diesel)

Sl.n
o

Characteristics

BS III

BS-IV

1.

Cetane No., min

51

51

2.

Sulphur, PPM
max

350

50

3.

Recovery, % vol
min

95% @ 360 Deg

C

95% @ 360 Deg C

8/31/2010

Preparation of Lubricating Oil Base Stock

8/31/2010

Lubes Plant

Objective : To Produce different grade of Lube oil

base stock for preparation of different grades of
Lube Oil.

Feed

Catalyst : Ni/Mo based

8/31/2010

: Fractions obtained from VDU

For Hydrofinishing

Lubes Product yield/quality and Operating

Conditions
1.

Typical Product Quality

Sl.no Products
.

Quality

1.

Viscosity, High Viscosity

index, Low Pour Point,
Good color and high
Flash point

Lube oil Base Stock

2. Typical Operating Conditions of Hydrofinishing:

Temperature Range
Pressure

8/31/2010

: 340-360 Deg C
: 70 kg/cm2(g)

Relevance of Lubes Process Schemes

Sl.
no.

Process Unit

Process

Significance

1.

Extraction

Extraction of
aromatics by
Furfural/ NMP

To improve Viscosity
Index

2.

Dewaxing

Solvent dewaxing
by MEK

To reduce Pour Point

3.

Hydrofinishing Hydrotreatment in
Presence of
Catalyst

8/31/2010

To improve colour by
removing Nitrogen
and Sulphur

Lube Unit Flow Diagram

Dewaxed Oil

Spindle
Oil (SO)

Raffinate

R
R
A
C

Intermediate
Neutral (IN)

T
I

RCO

Extraction
Unit
FEU/NEU

O
N
A

Hydrofinishing
unit
(HFU)

Heavy
Neutral (HN)

T
O
R

Extract

SR

Solvent
Dewaxing
unit(SDU)

Propane
Deasphaltene
(PDA)

8/31/2010

Bright
Stock

Asphalt

Wax

Lube Oil Base

Stock

Solvent Dewaxing

Wax content is removed by extraction to produce low Pour Point

Dewaxed Oil (DWO). Wax is crystalised in chillers and followed
by filtration in rotary drum vacuum filters
Feed : Furfural extraction unit Raffinate
Solvent Used: Methyl Ethyl Ketone (MEK) and Toluene in the
ratio of 50:50 (V/V)
Solvent to feed ratio : 4:1 to 2:1 V/V
Solvent Dewaxing temp. 10 deg C 20 Deg C
Product Yield: DWO: 65 -72 wt%
Slack Wax produced is sold as a speciality products for
production of microcrystalline wax

8/31/2010

Catalytic Dewaxing

Catalytic dewaxing uses dual function non-noble/noble metal zeolite

catalyst to selective hydro crack the paraffinic (waxy) components.
Ist stage involves Hydrotreatment
2nd stage cracking the normal and near normal paraffins
Cracking is achieved by both acid and metal function of catalyst
Feed : HVGO or Diesel
Product Yield: light gases: 0.5 wt%, Naphtha : 24.5 wt%, DWO:75
wt%
Feed and Product Properties:

8/31/2010

Sl.no

Properties

Feed

Product (DWO)

API

27.7

27.4

VI @ 100 Deg C

4.25

3.63

Pour Point, Deg

C

30

-20

Other Process Units

Hydrogen Generation Unit

Bitumen Blowing Unit
Sulphur Recovery Unit

8/31/2010

Hydrogen Generation Unit (HGU)

Objective : To Meet the Hydrogen requirement for

DHDS/DHDT/OHCU/ISOM/Reforming Units and Other Hydrotreaters.

Feed : Natural Gas / Naphtha and Feed

Catalyst :

8/31/2010

Co-Mo
ZnO/K2Co3
NiO
Ni
CuO
Adsorbents

for Hydrotreater
for H2S and Chloride adsorber
for Preformer
for Reformer
for HT/LT Shift reactors
for PSA Adsorbers

HGU Product Purity and Operating Conditions

1. HGU Product is 99.99% Pure Hydrogen
2. Operating Conditions :

Temperature range
System Pressure

8/31/2010

: 860-870 Deg C
: 20-38 kg/cm2(g)

Hydrogen Generation Unit Flow Diagram

FEED
R-01

R-02A/B

Pre-Reformer
R-03

HYDROGEN
SAT. STEAM
F-001 Reformer

Steam
Drum

DM
water

PSA

De- aerator

R-04

PSV
HP STEAM
Export
condensate

FLUE
GAS
AIR

8/31/2010

OFF GAS as FUEL

Key aspects of Operation and Maintenance

Even traces of sulphur is poison to Reformer Catalyst

Sulphur guard is provided to reduce feed sulphur to <50 ppb

Pre Reformer reduce the load on the reformer by converting the

heavier molecules to methane at relatively lower temperature.

The Shift reactor maximize the H2 production by Shift reaction

(i.e. CO +H2O H2 +CO2)

Sophisticated process Interlocks are provided as reformer operates

at very high temperature and it is prone to coking in absence of
steam
Reformer furnace draft is critically controlled by variable frequency
drive of FD/ID fan

8/31/2010

Bitumen Blowing Unit

Objective : To Produce different grades of Bitumen

by air blowing of vacuum residue at high
temperature.
Bitumen is colloidal solution of asphaltenes and high
molecular gums in the medium formed by oils and
low molecular gums.
Feed : Vacuum Residue

8/31/2010

BBU yield /quality and Operating Conditions

1.

Typical Product Quality

Sl.no.

Products

Wt%

1.

Off gas

0.86

2.

Recovered liquid 0.26

cut (FLO)

3.

Finished
Bitumen

98.88

2. Typical Operating Conditions of Bitumen Blowing Unit:

Temperature Range
Pressure
8/31/2010

: 230-260 Deg C
: 0.5 kg/cm2(g)

Bitumen Blowing Unit Flow Diagram

Air
Off gasTo
Incenerator

Bitumen
reactor
S
E
P
A
R

Furnace

FEED

Furnace

A
T
O
R

Bitumen to R/D
after Cooling
8/31/2010

FLO

Biturox reactor components

ReactorShell
GuidingCylinder
CoalescingCones
Agitator

Reaction
Largeairbubblesenterthru4 pipe
Dispersedtosmallbubblesbyimpeller
blade
Controlledcirculationbyguidingcylinder

Product : Viscosity grade bitumen

Sulphur Recovery Unit

Objective : To Reduce the SO2 emission from the

Refinery by recovering Sulphur from Amine Acid and
Sour Gases produced during various Hydrotreating
Process.
Feed : Amine Acid gases and Sour acid gases

8/31/2010

Chemical Reactions of SRU

Claus Reactions

The main reaction (PARTIAL OXIDATION) in the main burner is :

H2S + 3 O2
2

------>

The major part of the residual H2S combines with the SO2 to form
sulphur, according to the equilibrium reaction :
2H2S + SO2 < ------->

SO2 + H2O + heat

3 S2 + 2H2O - heat
2
By this reaction , known as the Claus reaction, sulphur is formed in
vapour phase in the main burner and combustion chamber.
8/31/2010

Chemical reactions in Superclaus Reactor

In the SUPERCLAUSR stage the remaining H2S is selectively

oxidised to sulphur,

It is essential that the combustion in the main burner is such that

the downstream of the third reactor stage the amount of H2S is
in the range of 0.5 0.7 vol.% and that the SO2 concentration is
as low as possible.

Before it enters the reactor a controlled amount of air is added.

Proper mixing is obtained in a static mixer, in the reactor H2S
reacts with oxygen to sulphur according to the reaction:
2H2S + O2
8/31/2010

2 S8 + 2H2O + heat
8

Sulphur Recovery Unit Flow Diagram

Process gas

H2S/CO2 gas
Rich
amine

MCC

A
R
U

FG AIR

Lean
amine

(Superclaus
reactor/TGTU)

Claus Reactors
1/2/3
T=195-310
Deg C

T= 220 deg C

AIR

Offgas
Off-gas
incineration

H2S / NH3
gas

T= 730 Deg C

Sulphur

Sour
water
S
W
S
U
Stripped
water
8/31/2010

Sulphur
degasification

Product sulphur
handling

To stack

SRU Product Yield and Operating Conditions

1.

Typical Product Yields

Sl.no.

Products

Wt%

End Users

1.

Off gas

0.1

To Stack after
incineration

2.

Sulphur

99.9

Sulphur Yard for

Dispatch

Typical Operating Conditions:

Temperature Range
Pressure

8/31/2010

: 195-320 Deg C
: 0.56 kg/cm2(g)

Flow Scheme of a Modern Refinery

Thank you