The World of Energy

Chapter 4 Crude Oil Refining

4.1. Introduction to Oil Refining

Ch. 4 - 1
An Evergreen Question...

Ch. 4 - 2
Crude Oil Classification

PETROLEUM
Saturates Asphaltics
n-alkanes C5 - C44 nitrogen
branched alkanes
Aromatics oxygen containing compounds
cycloalkanes (napthenes) single ring sulfur
condensed ring

Other
10% Saturates
Asphaltics
25%
8%
Aromatics
7%

Naphthenes
50%
API Gravity = 35o

Ch. 4 - 3
Major Classes of Hydrocarbons in Crude Oils
Paraffins Other hydrocarbons
general formula: CnH2n+2 (n is a Alkenes
whole number, usually from 1 to 20)
general formula: CnH2n
straight- or branched-chain molecules (n is a whole number,
can be gasses or liquids at room usually from 1 to 20)
temperature depending upon the linear or branched chain
molecule molecules containing
examples: methane, ethane, propane, one carbon-carbon
butane, isobutane, pentane, hexane double-bond
Aromatics can be liquid or gas
general formula: C6H5 - Y (Y is a examples: ethylene,
longer, straight molecule that connects butene, isobutene
to the benzene ring) Dienes and Alkynes
ringed structures with one or more rings general formula:
rings contain six carbon atoms, with CnH2n-2 (n is a whole
alternating double and single bonds number, usually from 1
between the carbons to 20)
typically liquids linear or branched chain
examples: benzene, napthalene molecules containing
two carbon-carbon
Napthenes or Cycloalkanes double-bonds
general formula: CnH2n (n is a whole can be liquid or gas
number usually from 1 to 20)
examples: acetylene,
ringed structures with one or more rings butadienes
rings contain only single bonds between
the carbon atoms
typically liquids at room temperature
examples: cyclohexane, methyl
cyclopentane
Ch. 4 - 4
Products from Crude Oil

Coke, 4.1 Asphalt and Road

Oil, 2.9
Still Gas, 4.3 PETROCHEMICAL
Liquefied Refinery FEEDSTOCKS, 2.7
Gases, 4.3
Residual Fuel Oil, 5.2 Lubricants, 1.1
Kerosene Jet Fuel,
9.3 Kerosene, 0.5

Other, 0.7

Distillate Fuel Oil,

20.8
Gasoline, 44.1

Ch. 4 - 5
 Products From Crude Oil
Petroleum Gas
Used for heating, cooking, making
plastics
small alkanes (1 to 4 carbon atoms)
commonly known by the names
methane, ethane, propane, butane
boiling range = 40 deg. C
often liquified under pressure to
create LPG (liquified petroleum gas)
Naphtha or Ligroin
Intermediate that will be further
processed to make gasoline
mix of 5 to 9 carbon atom alkanes
boiling range = 60 to 100 deg. C
Gasoline
Motor fuel, Liquid
mix of alkanes and cycloalkanes (5 to
12 carbon atoms)
boiling range = 40 to 205 deg. C
Kerosene
Fuel for jet engines and tractors;
starting material for making other
products
liquid
mix of alkanes (10 to 18 carbons)
and aromatics
boiling range = 175 to 325 deg. C
Gas oil or Diesel distillate
Used for diesel fuel and heating oil;
starting material for making other
products
Liquid, Alkanes containing 12 or more
carbon atoms
boiling range = 250 to 350 deg. C
Lubricating oil
Used for motor oil, grease, other
lubricants
Liquid, long chain (20 to 50 carbon
atoms) alkanes, cycloalkanes,
aromatics
boiling range = 300 to 370 deg. C
Heavy gas or Fuel oil
used for industrial fuel; starting
material for making other products
Liquid, long chain (20 to 70 carbon
atoms) alkanes, cycloalkanes,
aromatics
boiling range = 370 to 600 deg. C
Residuals
Coke, asphalt, tar, waxes; starting
material for making other products
Solid, multiple-ringed compounds with
70 or more carbon atoms
boiling range = greater than 600 deg. C
Ch. 4 - 6
 Gasoline Prices Are a Function of More than
Just Crude Prices

51% increase in crude price = 21% increase in gasoline price.

Source: USDOE/EIA

Ch. 4 - 7
Gasoline Retail Price Contribution

Retail Price Contributions (per Gallon)

8%
Retail Price $2.23
15%
Distribution & Marketing $0.18

Refining $0.33
20%
Taxes $0.45

Crude Oil $1.27

57%
Refinery Price $1.61

Ch. 4 - 8
Gasoline Will Be Hard to Replace

Fuel Energy per Weight

(MJ/kg)
Hydrogen 114
(10 liquid; 5 compressed gas)
Gasoline 48
Crude Oil 43
Plant Oil (Bio-Diesel) 38
Ethanol 28
Common Coal 22
Natural Gas (STP) 20
Air Dried Wood 15
Potatoes 4
Carbon Fiber Flywheel 0.8
Lithium Batteries (at 400C) 0.2
Lead Batteries 0.1

Ch. 4 - 9
A Picture of an Oil Refinery

Ch. 4 - 10
Advance in Crude Oil Refining
The most up-to-date unit of the refinery Delayed Coker
with a processing capacity of 1 million t heavy fuel oil

Ch. 4 - 11
Oil Refinery is Large & Complex

Ch. 4 - 12
The World of Energy
Chapter 4 Crude Oil Refining

4.2. Refining Processes Fundamentals

Ch. 4 - 13
So, How Do You Make Good Stuff
Out Of That Gooey Crude?

Ch. 4 - 14
 From Crude Oil to Products
Product Usage Composition Boiling range
(Carbon no.) (C)
Petroleum gas used for heating, cooking 1 to 4 Upto 40

Naphta intermediate that will be further 5 to 9 60 to 100

processed to make gasoline
Gasoline motor fuel 5 to 12 40 to 205

Kerosene fuel for jet engines 10 to 18 175 to 325

Diesel oil used for diesel fuel and heating 12 to 20 250 to 350
oil
Lubricating oil used for motor oil, 20 to 50 300 to 370
grease, other lubricants
Heavy or fuel industrial fuel 20 to 70 370 to 600
oil
Residuals coke, asphalt, tar, waxes 70 or more Above 600

Ch. 4 - 15
 Diagram of Refinery Unit
Diagram of Refinery Units

Crude Oil Sulphur

Gas treatment Recovery Sulphur

H2S H2S

Shorter Chain Molecules

Desulphurisation Platformer Petrol

Kerosine
Gas Oil

Diesel
Vacuum Gas Oil
Long Residue

High Vacuum
Distillation

Hyrdrocracker
Separation

Long Chain Molecules

Hydrogen
Waxy Distillate Manufacturing
Hydrogen
Unit
Butane
Bitumen De-asphalting
De-asphalted oil DAO

Roads Asphalt Fuel oil

Ch. 4 - 16
Simplified Petroleum & Petroleum Flowchart

Natural Gas Stove

Gas RX RX
Ethylene Polyethylene (Glad Bags)

Propane &
Butane R Fuel
X Polymers (7 UP Bottles) (Barbeque Grills)

Naphtha Gasoline
(C 5 - C 10) RX
Organic Chemicals (Aspirin, Hair Spray)
RX
More Polymers (Football Helmet, Astro
Turf, Nylon)

Kerosene &
Jet Fuel
Gas Oils (C 10+) Diesel Fuels
Conversions

Purifications
Separations
Oil Crude Separations and Home Heating
Well Oil Oil, Lubricating
Oil, Wax

Coke Fuel
(Carbon Material Similar to Coal)
Steel Making
Graphite Fibers
(Tennis Racquets)
Asphalt
Roads Pot Holes
Purifications remove sulfur and heavy metals
RX = Chemical Reactions

Ch. 4 - 17
Flow scheme of a modern refinery

Ch. 4 - 18
 Typical Oil Refinery Process Units
Refinery Gas
Natural Gas
Fuel
Sulphur
Gas
DePr RG
Syngas and Reformates
Plat
Naphtha Regular Mogas
HDT Split RG H2
RG
Condensates and Low Mogas
Sulphur Crudes Kero Premium Mogas
Blend
High Sulphur Crudes
CDU1 RG
LGO Kero / Avtur
Imported Residues
HDS2
HGO H2
CO2

Long Residue

Automotive Gasoils
and Marine
GasOil
Naphtha Blend
RG
HDS1 HMU
Low Sulphur Crudes Kero H2
H2 Light Fuel Oil
LGO
HCU
High Sulphur CrudesCDU2 HGO RG FuelOil Heavy Fuel Oil

Blend
Bunkers

Imported Residues
HVU2 Refinery Fuel
HVU1 BDU Bitumen 80/100
Long Residue
BBU Bitumen 180/200
Bitumen 45/55

Ch. 4 - 19
Oil Refining Processes
1. Introduction
2. Physical Processes
3. Thermal Processes
4. Catalytic Processes
5. Conversion of Heavy Residues
6. Treatment of Refinery Gas Streams

Ch. 4 - 20
Introduction to Oil Refining

Oil refining is a key activity in the Chemical

Processes Industry (CPI)

Over 600 refineries worldwide have a total

annual capacity of more than 3500 x 106 tonnes

Goal of oil refining is twofold

Production of fuels for transportation, power
generation and heating; and
Production of raw materials for the CPI

Oil refineries are complex plants but are

relatively mature and highly integrated.

Ch. 4 - 21
Refinery Processes Overview
After desalting and dehydration, crude is
separated into fractions by distillation

The distilled fractions can not be used directly

The reason for such a complex set of processes is

the difference between the crude oil properties
and the needs of the market

Another reason for complexity is environmental.

Legislation demands cleaner products and is the
major drive for process improvement and
development of novel processes.

Ch. 4 - 22
The Five Pillars of Refining Crude Oil

While distillation can separate oil into fractions, chemical reactors

are required to create more of the products that are in high
demand.

Refineries rely on four major processing steps to alter the ratios of

the different fractions
Catalytic Reforming
Alkylation
Catalytic Cracking
Hydroprocessing

Each of these methods involves

Feeding reactants to a reactor where they will be partly converted into
products.
The unreacted reactants are then separated from the products with a
distillation column.
The unreacted reactants are recycled for another pass, while the
products are further separated and mixed with existing streams. In this
way complete conversion of reactants can be obtained, even though
not all of the reactants are converted on a given pass through the reactor

The four processing methods, along with distillation, are the

pillars of petroleum refining.

Ch. 4 - 23
5 Basic Refining Operations
Fractionation (distillation)

Conversion Processes

Treatment Processes

Formulating and Blending

Other Refining Operations

light-ends recovery;
sour-water stripping;
solid waste, process-water and wastewater treatment;
cooling, storage and handling and product movement;
hydrogen production;
acid and tail-gas treatment;
and sulfur recovery.

Ch. 4 - 24
5 Basic Refining Operations
Fractionation (distillation)
The separation of crude oil in atmospheric and vacuum distillation towers into
groups of hydrocarbon compounds of differing boiling-point ranges called
"fractions" or "cuts."
Conversion Processes
Change the size and/or structure of hydrocarbon molecules.
These processes include
Decomposition (dividing) by thermal and catalytic cracking;
Unification (combining) through alkylation and polymerization; and
Alteration (rearranging) with isomerization and catalytic reforming.
Treatment Processes
Prepare hydrocarbon streams for additional processing and to prepare finished
products.
Treatment may include removal or separation of aromatics and naphthenes,
impurities and undesirable contaminants.
Treatment may involve chemical or physical separation e.g. dissolving,
absorption, or precipitation using a variety and combination of processes
including desalting, drying, hydrodesulfurizing, solvent refining, sweetening,
solvent extraction, and solvent dewaxing
Formulating and Blending
The process of mixing and combining hydrocarbon fractions, additives, and
other components to produce finished products with specific performance
properties.
Other Refining Operations include:
light-ends recovery;
sour-water stripping;
solid waste, process-water and wastewater treatment;
cooling, storage and handling and product movement;
hydrogen production;
acid and tail-gas treatment;
and sulfur recovery.

Ch. 4 - 25
Auxiliary Refining Operations

Auxiliary Operations and Facilities include:

light steam and power generation;
process and fire water systems;
flares and relief systems;
furnaces and heaters;
pumps and valves;
supply of steam, air, nitrogen, and other plant
gases;
alarms and sensors;
noise and pollution controls;
sampling, testing, and inspecting and laboratory;
control room;
maintenance; and
administrative facilities.

Ch. 4 - 26
Physical and Chemical Processes of a Refinery

Chemical
Physical
Thermal Catalytic
Distillation Visbreaking Hydrotreating
Solvent extraction Delayed coking Catalytic reforming
Propane deasphalting Flexicoking Catalytic cracking
Solvent dewaxing Hydrocracking
Blending Catalytic dewaxing
Alkylation
Polymerization
Isomerization

Ch. 4 - 27
Petroleum Fuel Octane Rating
Petrol fraction consists of straight-chain alkanes
Fuel burns before ignition by the spark plug knock loss of
power, damage to engine
2,2,4-trimethylpentane: Octane =100
N-heptane: Octane = 0
Can increase octane rating for petrol fraction from 50 to 90 by
3 methods:
Cracking
Catalytic reforming
Addition of octane enhancers like TEL, methanol, ethanol and MTBE
Catalytic Converter
In exhaust system of vehicles
Ceramic coated with Rhodium, Platinum and Palladium
Exhaust gases converted:
2NO N2 + O2 (Rhodium)
CO CO2 (Oxygen, Pt, Pd)
2 C8H18 + 25 O2 16 CO2 + 18 H2O

Ch. 4 - 28
The World of Energy
Chapter 4 Crude Oil Refining

4.3. Physical Processes

Ch. 4 - 29
Desalting/Dehydration

Crude oil often contains water, inorganic salts, suspended solids,

and water-soluble trace metals

Step 0 in the refining process is to remove these contaminants so

as to reduce corrosion, plugging, and fouling of equipment and to
prevent poisoning catalysts in processing units

The two most typical methods of crude-oil desalting are chemical

and electrostatic separation, and both use hot water as the
extraction agent

In chemical desalting, water and chemical surfactant (demulsifiers)

are added to the crude, which is heated so that salts and other
impurities dissolve or attach to the water, then held in a tank to
settle out

Electrical desalting is the application of high-voltage electrostatic

charges to concentrate suspended water globules in the bottom of
the settling tank. Surfactants are added only when the crude has a
large amount of suspended solids

A third (and rare) process filters hot crude using diatomaceous

earth.

Ch. 4 - 30
Desalting/Dehydration

The crude oil feedstock is heated to 65-180C to reduce viscosity and

surface tension for easier mixing and separation of the water. The
temperature is limited by the vapor pressure of the crude-oil feedstock

In both methods other chemicals may be added. Ammonia is often

used to reduce corrosion. Caustic or acid may be added to adjust the pH
of the water wash.

Ch. 4 - 31
Desalter/Dehydrator Units

Ch. 4 - 32
The World of Energy
Chapter 4 Crude Oil Refining

4.4. Distillation & Fractionation

Ch. 4 - 33
Oil Refinery
Distillation & Fractionation

The World of Energy

Chapter 4

Ch. 4 - 34
How Does Distillation Work?

Distillation is defined as:

a process in which a liquid or vapour mixture of two
or more substances is separated into its component
fractions of desired purity, by the application and
removal of heat.

Ch. 4 - 35
Boiling Point of Alkanes
5 carbons, pentane, 36 C, 97 F
6 carbons, hexane, 69 C, 156 F boiling point
7 carbons, heptane, 98 C, 208 F
8 carbons, octane,126 C, 259 F 400
9 carbons, nonane, 151 C, 304 F 300
10 carbons, decane, 174 C, 345 F

Boiling Point (C)

11 carbons, 196 C 200
12 carbons, 216 C 100
13 carbons, 235 C
14 carbons, 254 C 0
15 carbons, 271 C 0 2 4 6 8 10 12 14 16 18 20
-100
16 carbons, 287 C
17 carbons 303 C , (577 F) -200
Carbon Number

SOME ARE TOO LIGHT

SOME ARE TOO HEAVY FOR USE IN GASOLINE

Ch. 4 - 36
Typical Crude Assay
CUT wt % ibp(F) ep(F)
Light Gasoline 3.3 90 190
Total gasoline and naptha 17.7 90 330
kerosine distillate 24.4 330 520
Light Gas Oil (A1 & die) 7.1 420 610
Total Gas Oil 14.2 420 800
Non viscous lubricting dist. 14.1% 800
Medium lubricating dist. 8%
Viscous lubricating dist. - 1050
Residuum 20.8%
distillation loss 0.8 %

Ch. 4 - 37
How Does Distillation Work?
Distillation is based on the fact that the vapour of a
boiling mixture will be richer in the components that
have lower boiling points

Thus, when this vapour is cooled and condensed, the

condensate will contain the more volatile components.
At the same time, the original mixture will contain
more of the less volatile components

Distillation is the most common separation technique

and it consumes enormous amounts of energy, both in
terms of cooling and heating requirements

Distillation can contribute to more than 50% of plant

operating costs.

Ch. 4 - 38
How does distillation work?
Distillation columns are classified by the manner in which they
are operated

1. Batch, in which the feed to the column is introduced batch-

wise. That is, the column is charged with a 'batch' and then
the distillation process is carried out. When the desired task is
achieved, a next batch of feed is introduced.

2. Continuous columns process a continuous feed stream. No

interruptions occur unless there is a problem with the column
or surrounding process units. They are capable of handling
high throughputs and are the most common of the two types.

Ch. 4 - 39
Distillation Technology

Ch. 4 - 40
Continuous Distillation Columns
Classified according to

1. Nature of the feed that they are processing:

binary column - feed contains only two components;
multi-component column - feed contains more than two
components

2. Number of product streams they have:

multi-product column - column has more than two product
streams

3. Where extra feed exits when used to help with the

separation:
extractive distillation - where the extra feed appears in the bottom
product stream;
azeotropic distillation - where the extra feed appears at the top
product stream

4. Type of column internals:

tray column - trays of various designs used to hold up the liquid to
provide better contact between vapour and liquid;
packed column - packings are used to enhance vapour-liquid
contact.

Ch. 4 - 41
Schematic of Crude Oil Distillation Tower

Schematic drawing of crude oil distillation tower

Ch. 4 - 42
Separation in Distillation Column

Lower Boiling

Crude

Higher Boiling

Ch. 4 - 43
Crude Distilling Unit (CDU)

Ch. 4 - 44
Crude Oil Refining

AT THE TOP AT THE

OF THE BOTTOM OF
DISTILLATIO THE
N COLUMN DISTILLATIO
N COLUMN
Short carbon Long carbon
chains chains
Light Heavy
molecules molecules
Low boiling High boiling
points points

Gases & very Thick, viscous

runny liquids liquids

Very volatile Low volatility

Light colour Dark colour

Highly Not very

flammable flammable

Ch. 4 - 45
Fractions of Crude Oil & Their Properties

Number of Boiling Point

Name Carbon Atoms (C)
Uses

Bottled Gas
Refinery Gas 3 or 4 below 30
(propane or butane).
Fuel for car
Gasoline 7 to 9 100 to 150
engines.
Solvents
Naphtha 6 to 11 70 to 200
and used in gasoline.

Kerosene Fuel for aircraft

11 to 18 200 to 300
(paraffin) and stoves.

Fuel for road vehicles

Diesel Oil 11 to 18 200 to 300
and trains.
Lubricant for engines
Lubricating Oil 18 to 25 300 to 400
and machines.
Fuel for ships
Fuel Oil 20 to 27 350 to 450
and heating.
Lubricants
Greases and Wax 25 to 30 400 to 500
and candles.
Road surface
Bitumen above 35 above 500
and roofing.

Ch. 4 - 46
 Basic Operation

The feed is introduced somewhere near

the middle of the column to a tray
known as the feed tray.
The feed tray divides the column into a
top (enriching or rectification) and a
bottom (stripping) section.
The feed flows down the column where it
is collected in the reboiler.
Heat (usually as steam) is supplied to
the reboiler to generate vapour.
The vapour from the reboiler is re-
introduced into the unit at the bottom of
the column.
The liquid removed from the reboiler is
known as the bottoms product or simply,
bottoms.

Ch. 4 - 47
Basic operation

Vapour moves up the column, exits the top, and is cooled in a

condenser. The condensed liquid is stored in a holding vessel known
as the reflux drum. Some of this liquid is recycled back to the top of
the column and this is called the reflux. The condensed liquid that is
removed from the system is known as the distillate or top product

Thus, there are internal flows of vapour and liquid within the column as
well as external flows of feeds and product streams, into and out of the
column.

Ch. 4 - 48
Crude Distillation

Step 1 in the refining process is the separation of crude oil into various
fractions or straight-run cuts by distillation in atmospheric and vacuum towers.
The main fractions or "cuts" obtained have specific boiling-point ranges and
can be classified in order of decreasing volatility into gases, light distillates,
middle distillates, gas oils, and residuum.

Atmospheric distillation

The desalted crude feedstock is preheated using recovered process heat

The feedstock then flows to a direct-fired crude charge heater then into the
vertical distillation column just above the bottom, at pressures slightly above
atmospheric and at temperatures ranging from 340-370C (above these
temperatures undesirable thermal cracking may occur). All but the heaviest
fractions flash into vapor.
As the hot vapor rises in the tower, its temperature is reduced.
Heavy fuel oil or asphalt residue is taken from the bottom.
At successively higher points on the tower, the various major products
including lubricating oil, heating oil, kerosene, gasoline, and uncondensed
gases (which condense at lower temperatures) are drawn off.

Ch. 4 - 49
Atmospheric Distillation

Ch. 4 - 50
Simple Crude Distillation

Ch. 4 - 51
Vacuum Distillation

To further distill the residuum or topped crude from the

atmospheric tower without thermal cracking, reduced pressure is
required.
The process takes place in one or more vacuum distillation towers.
The principles of vacuum distillation resemble those of fractional
distillation except that larger diameter columns are used to
maintain comparable vapor velocities at the reduced pressures.
The internal designs of some vacuum towers are different from
atmospheric towers in that random packing and demister pads are
used instead of trays.
A typical first-phase vacuum tower may produce gas oils,
lubricating-oil base stocks, and heavy residual for propane
deasphalting.
A second-phase tower operating at lower vacuum may distill
surplus residuum from the atmospheric tower, which is not used
for lube-stock processing, and surplus residuum from the first
vacuum tower not used for deasphalting.
Vacuum towers are typically used to separate catalytic cracking
feedstock from surplus residuum.

Ch. 4 - 52
Vacuum Distillation

Ch. 4 - 53
Modern Crude Distillation

Ch. 4 - 54
ATMOSPHERIC & VACUUM DISTILLATIONS

Light Ends

ATMOSPHERIC DISTILLATION
Straight Run Gasoline

STRIPPERS
Straight Run Naphtha

Crude Oil Straight Run Kerosene

Gas Oils

DISTILLATION
Vacuum Naphtha

VACUUM
Atmospheric Resid Vacuum Gas Oil
(Straight Run Residue)

Vacuum Resid

Ch. 4 - 55
The World of Energy
Chapter 4 Crude Oil Refining

4.5. Distillation System & Equipments

Ch. 4 - 56
Main Components of Distillation Columns

A vertical shell where separation of

liquid components is done

Column internals e.g.trays/plates

and/or packings which are used to
enhance component separations

A reboiler to provide the necessary

vaporization for the distillation
process

A condenser to cool and condense

the vapour leaving the top of the
column

A reflux drum to hold the

condensed vapour from the top of
the column so that liquid (reflux)
can be recycled back to the
column.

Ch. 4 - 57
Types of Distillation/Fractionaton Trays

1. Sieve plates

2. Bubble-cap plates

3. Valve plates

Ch. 4 - 58
Types of Column Trays

VALVE FOR
TRAYS

BUBBLE CAP
TRAY

VALVES
TRAY SIEVE TRAY

Ch. 4 - 59
Ch. 4 - 60
Valve Tray Deck

Ch. 4 - 61
Sieve Tray

Ch. 4 - 62
Valve Tray

Ch. 4 - 63
Bubble Cap Tray

Ch. 4 - 64
Structured Packing

Fair, J.R., Seibert, A.F., Behrens, M., Saraber, P.P., and Olujic, Z. Structured
Packing Performance-Experimental Evaluation of Two Predictive Models ,
Ind. Eng. Chem. Res. 39 (6), 1788-1796 (2000).

Ch. 4 - 65
Structured Packing Wetted Area

Ch. 4 - 66
Trays and Plates

Bubble cap trays

A riser or chimney is fitted

over each hole, and a cap
covers the riser.
The cap is mounted with a
space to allow vapour to
rise through the chimney
and be directed downward
by the cap
Finally discharging through
slots in the cap, and
bubbling through the liquid
on the tray.

Ch. 4 - 67
 Trays and Plates

Valve trays
Perforations are covered by
caps lifted by vapour, which
creates a flow area and directs
the vapour horizontally into
the liquid.

Sieve trays
Sieve trays are simply metal
plates with holes in them.
Vapour passes straight
upward through the liquid on
the plate. The arrangement,
number and size of the holes
are design parameters.

Ch. 4 - 68
Liquid and Vapour Flows in a Tray Column

Ch. 4 - 69
 Liquid and Vapour Flows in a Tray Column

Each tray has 2 conduits called

downcomers: one on each side.
Liquid falls by gravity through the
downcomers from one tray to the
tray below

A weir ensures there is always

some liquid (holdup) on the tray
and is designed such that the the
holdup is at a suitable height, e.g.
such that the bubble caps are
covered by liquid

Vapour flows up the column and is

forced to pass through the liquid
via the openings on each tray. The
area allowed for the passage of
vapour on each tray is called the
active tray area.

Ch. 4 - 70
Packings

Packings are passive devices designed to increase the interfacial area

for vapour-liquid contact

They do not cause excessive pressure-drop across a packed section,

which is important because a high pressure drop would mean that
more energy is required to drive the vapour up the distillation column

Packed columns are called continuous-contact columns while trayed

columns are called staged-contact columns because of the manner in
which vapour and liquid are contacted.

Ch. 4 - 71
Reboilers

Ch. 4 - 72
 Reboilers
Top Tray
Top Tray

Heating
Heating Medium
Medium

Bottoms Product
Bottoms Product

Circulating Pump

Forced Circulation Vertical Thermosiphon

Ch. 4 - 73
Reboilers

Top Tray
Top Tray

Heating
Heating Medium
Medium

Bottoms Product

Bottoms Product

Kettle Horizontal Thermosiphon

Ch. 4 - 74
Feed Distributors

Ch. 4 - 75
The Real World

Fouled Structured Packing Damaged Valve Tray

Ch. 4 - 76
The Real World

Plugged Distributor Tray Blanking Strips

Ch. 4 - 77
Major Tray Damage

Ch. 4 - 78
Fouling Resistant Design

Ch. 4 - 79
Fouled Bubble Cap Tray

Ch. 4 - 80
Gamma Scan Technology
Tower Scan

Distance from tower top

Tray Number
Ch. 4 - 81
The World of Energy
Chapter 4 Crude Oil Refining

4.6. Other Refinery Processes

Ch. 4 - 82
Propane Deasphalting

Coke-forming tendencies of heavier distillation

products are reduced by removal of asphaltenic
materials by solvent extraction.
Liquid propane is a good solvent (butane and pentane
are also commonly used).
Deasphalting is based on solubility of hydrocarbons in
propane, i.e. the type of molecule rather than RMM as
in distillation.
Vacuum residue is fed to a countercurrent
deasphalting tower. Alkanes dissolve in propane
whereas asphaltenic materials (aromatic compounds),
coke-precursors do not.
Asphalt is sent for thermal processing.

Ch. 4 - 83
Propane Deasphalting

Ch. 4 - 84
Solvent Extraction and Dewaxing

Solvent treating is a widely used method of refining lubricating oils

as well as a host of other refinery stocks.
Since distillation (fractionation) separates petroleum products into
groups only by their boiling-point ranges, impurities may remain.
These include organic compounds containing sulfur, nitrogen, and
oxygen; inorganic salts and dissolved metals; and soluble salts that
were present in the crude feedstock.
In addition, kerosene and distillates may have trace amounts of
aromatics and naphthenes, and lubricating oil base-stocks may
contain wax.
Solvent refining processes including solvent extraction and solvent
dewaxing usually remove these undesirables at intermediate
refining stages or just before sending the product to storage.

Ch. 4 - 85
Solvent Extraction

The purpose of solvent extraction is to prevent corrosion, protect

catalyst in subsequent processes, and improve finished products by
removing unsaturated, aromatic hydrocarbons from lubricant and
grease stocks.
The solvent extraction process separates aromatics, naphthenes,
and impurities from the product stream by dissolving or
precipitation. The feedstock is first dried and then treated using a
continuous countercurrent solvent treatment operation.
In one type of process, the feedstock is washed with a liquid in
which the substances to be removed are more soluble than in the
desired resultant product. In another process, selected solvents
are added to cause impurities to precipitate out of the product. In
the adsorption process, highly porous solid materials collect liquid
molecules on their surfaces.
The solvent is separated from the product stream by heating,
evaporation, or fractionation, and residual trace amounts are
subsequently removed from the raffinate by steam stripping or
vacuum flashing.

Ch. 4 - 86
Solvent Extraction

Electric precipitation may be used for separation of inorganic

compounds.
The solvent is regenerated for reused in the process.
The most widely used extraction solvents are phenol,
furfural, and cresylic acid.
Other solvents less frequently used are liquid sulfur dioxide,
nitrobenzene, and 2,2' dichloroethyl ether.
The selection of specific processes and chemical agents
depends on the nature of the feedstock being treated, the
contaminants present, and the finished product
requirements.

Ch. 4 - 87
Aromatic Solvent Extraction Unit

Ch. 4 - 88
Solvent Dewaxing

Solvent dewaxing is used to remove wax from either distillate or

residual basestock at any stage in the refining process.
There are several processes in use for solvent dewaxing, but all
have the same general steps, which are::
mixing the feedstock with a solvent;
precipitating the wax from the mixture by chilling; and
recovering the solvent from the wax and dewaxed oil for recycling by
distillation and steam stripping.
Usually two solvents are used: toluene, which dissolves the oil and
maintains fluidity at low temperatures, and methyl ethyl ketone
(MEK), which dissolves little wax at low temperatures and acts as a
wax precipitating agent.
Other solvents sometimes used include benzene, methyl isobutyl
ketone, propane, petroleum naphtha, ethylene dichloride,
methylene chloride, and sulfur dioxide.
In addition, there is a catalytic process used as an alternate to
solvent dewaxing.

Ch. 4 - 89
Solvent Dewaxing Unit

Ch. 4 - 90
Solvent Dewaxing Unit

Ch. 4 - 91
The World of Energy
Chapter 4 Crude Oil Refining

4.7. Thermal Processes

Ch. 4 - 92
Blending

Blending is the physical mixture of a number of different

liquid hydrocarbons to produce a finished product with
certain desired characteristics.
Products can be blended in-line through a manifold
system, or batch blended in tanks and vessels.
In-line blending of gasoline, distillates, jet fuel, and
kerosene is accomplished by injecting proportionate
amounts of each component into the main stream where
turbulence promotes thorough mixing.
Additives including octane enhancers, anti-oxidants, anti-
knock agents, gum and rust inhibitors, detergents, etc.
are added during and/or after blending to provide
specific properties not inherent in hydrocarbons.

Ch. 4 - 93
Thermal Processes
When a hydrocarbon is heated to a sufficiently
high temperature thermal cracking occurs. This
is sometimes referred to as pyrolysis (especially
when coal is the feedstock). When steam is
used it is called steam cracking. We will
examine two thermal processes used in
refineries
Visbreaking
Delayed coking

Ch. 4 - 94
Visbreaking

Visbreaking is a mild form of thermal cracking that lowers the

viscosity of heavy crude-oil residues without affecting the boiling
point range.
Residuum from the atmospheric distillation tower is heated (425-
510C) at atmospheric pressure and mildly cracked in a heater.
It is then quenched with cool gas oil to control over-cracking,
and flashed in a distillation tower.
Visbreaking is used to reduce the pour point of waxy residues
and reduce the viscosity of residues used for blending with
lighter fuel oils. Middle distillates may also be produced,
depending on product demand.
The thermally cracked residue tar, which accumulates in the
bottom of the fractionation tower, is vacuum-flashed in a
stripper and the distillate recycled.

Ch. 4 - 95
Visbreaking

Ch. 4 - 96
Visbreaking

Alternatively, vacuum residue can be cracked. The severity of the

visbreaking depends upon temperature and reaction time (1-8
min).
Usually < 10 wt% of gasoline and lighter products are produced.

Ch. 4 - 97
Delayed Coking

Coking is a severe method of thermal cracking used to upgrade

heavy residuals into lighter products or distillates.
Coking produces straight-run gasoline (Coker naphtha) and various
middle-distillate fractions used as catalytic cracking feedstock.
The process completely reduces hydrogen so that the residue is a
form of carbon called "coke."
Three typical types of coke are obtained (sponge coke, honeycomb
coke, and needle coke) depending upon the reaction mechanism,
time, temperature, and the crude feedstock.
In delayed coking the heated charge (typically residuum from
atmospheric distillation towers) is transferred to large coke drums
which provide the long residence time needed to allow the cracking
reactions to proceed to completion.

Ch. 4 - 98
Sponge Coke
Sponge coke derived from a petroleum feedstock that shows abundant pore
structure. Note the flow texture in the coke cell walls.

Ch. 4 - 99
Typical Needle Coke
Typical needle coke derived from a petroleum feedstock. The parallel layers
and linear fractures are distinctive and provide slip planes to relieve stress in
the coke

Ch. 4 - 100
Delayed Coking

Heavy feedstock is fed to a fractionator.

The bottoms of the fractionator are fed to coker drums via a
furnace where the hot material (440-500C ) is held
approximately 24 hours (delayed) at pressures of 2-5 bar, until it
cracks into lighter products.
Vapors from the drums are returned to a fractionator where gas,
naphtha, and gas oils are separated out. The heavier
hydrocarbons produced in the fractionator are recycled through
the furnace.
After the coke reaches a predetermined level in one drum, the
flow is diverted to another drum to maintain continuous
operation.
The full drum is steamed to strip out uncracked hydrocarbons,
cooled by water injection, and de-coked by mechanical or
hydraulic methods.
The coke is mechanically removed by an auger rising from the
bottom of the drum. Hydraulic decoking consists of fracturing the
coke bed with high-pressure water ejected from a rotating cutter.

Ch. 4 - 101
Delayed Coking

Ch. 4 - 102
Catalytic Processes

Fluid Catalytic Cracking (FCC)

Hydrotreating
Hydrocracking
Catalytic Reforming
Alkylation

Ch. 4 - 103
Catalytic Processes

Ch. 4 - 104
Octane Numbers of Pure Hydrocarbons

Ch. 4 - 105
Octane Numbers of Pure Hydrocarbons

Ch. 4 - 106
The World of Energy
Chapter 4 Crude Oil Refining

4.8. Catalytic Processes

Ch. 4 - 107
Catalytic Cracking

Main incentive for catalytic cracking is the need to

increase gasoline production.
Feedstocks are typically vacuum gas oil.
Cracking is catalyzed by solid acids which promote
the rupture of C-C bonds. The crucial intermediates
are carbocations (+ve charged HC ions) formed by
the action of the acid sites on the catalyst.
Besides C-C cleavage many other reactions occur:
- isomerization
- protonation and deprotonation
- alkylation
- polymerization
- cyclization and condensation

Ch. 4 - 108
Catalytic Cracking

Catalytic cracking comprises a complex network of

reactions, both intra-molecular and inter-molecular.
The formation of coke is an essential feature of the
cracking process and this coke deactivates the
catalyst.
Catalytic cracking is one of the largest applications of
catalysts: worldwide cracking capacity exceeds 500
million t/a.
Catalytic cracking was the first large-scale application
of fluidized beds which explains the name fluid
catalytic cracking (FCC).
Nowadays entrained-flow reactors are used instead of
fluidized beds but the name FCC is still retained.

Ch. 4 - 109
Fluid Catalytic Cracking

Oil is cracked in the presence of a finely divided catalyst, which

is maintained in an aerated or fluidized state by the oil vapours.
The fluid cracker consists of a catalyst section and a
fractionating section that operate together as an integrated
processing unit.
The catalyst section contains the reactor and regenerator,
which, with the standpipe and riser, form the catalyst circulation
unit. The fluid catalyst is continuously circulated between the
reactor and the regenerator using air, oil vapors, and steam as
the conveying media.
Preheated feed is mixed with hot, regenerated catalyst in the
riser and combined with a recycle stream, vapourized, and
raised to reactor temperature (485-540C) by the hot catalyst.
As the mixture travels up the riser, the charge is cracked at 0.7-
2 bar.
In modern FCC units, all cracking takes place in the riser and
the "reactor" merely serves as a holding vessel for the cyclones.
Cracked product is then charged to a fractionating column
where it is separated into fractions, and some of the heavy oil is
recycled to the riser.

Ch. 4 - 110
Fluid Catalytic Cracking

Spent catalyst is regenerated to get rid of coke that

collects on the catalyst during the process.
Spent catalyst flows through the catalyst stripper to the
regenerator, where most of the coke deposits burn off at
the bottom where preheated air and spent catalyst are
mixed.
Fresh catalyst is added and worn-out catalyst removed
to optimize the cracking process.

Ch. 4 - 111
Fluid Catalytic Cracking

Ch. 4 - 112
FCC- Fluidized Cat Cracker

Ch. 4 - 113
Fluid Catalytic Cracking

Ch. 4 - 114
Hydrotreating

Catalytic hydrotreating is a hydrogenation process used to

remove about 90% of contaminants such as nitrogen, sulfur,
oxygen, and metals from liquid petroleum fractions.
If these contaminants are not removed from the petroleum
fractions they can have detrimental effects on equipment,
catalysts, and the quality of the finished product.
Typically, hydrotreating is done prior to processes such as
catalytic reforming so that the catalyst is not contaminated by
untreated feedstock. Hydrotreating is also used prior to
catalytic cracking to reduce sulfur and improve product yields,
and to upgrade middle-distillate petroleum fractions into
finished kerosene, diesel fuel, and heating fuel oils.
In addition, hydrotreating converts olefins and aromatics to
saturated compounds.

Ch. 4 - 115
Catalytic Hydrodesulfurization Process

Hydrotreating for sulfur removal is called

hydrodesulfurization.
In a typical catalytic hydrodesulfurization unit, the
feedstock is deaerated and mixed with hydrogen,
preheated in a fired heater (315- 425 C) and then
charged under pressure (up to 70 bar) through a
trickle-bed catalytic reactor.
In the reactor, the sulfur and nitrogen compounds in
the feedstock are converted into H2S and NH3.
The reaction products leave the reactor and after
cooling to a low temperature enter a liquid/gas
separator. The hydrogen-rich gas from the high-
pressure separation is recycled to combine with the
feedstock, and the low-pressure gas stream rich in
H2S is sent to a gas treating unit where H2S is
removed.

Ch. 4 - 116
Catalytic Hydrodesulfurization Process

The clean gas is then suitable as fuel for the refinery

furnaces. The liquid stream is the product from
hydrotreating and is normally sent to a stripping
column for removal of H2S and other undesirable
components.
In cases where steam is used for stripping, the product
is sent to a vacuum drier for removal of water.
Hydrodesulfurized products are blended or used as
catalytic reforming feedstock.

Ch. 4 - 117
Hydrotreating: flow scheme

Ch. 4 - 118
Hydrotreating: Trickle-bed Reactor

Ch. 4 - 119
Other Hydrotreating Processes

Hydrotreating also can be used to improve the quality of

pyrolysis gasoline (pygas), a by-product from the
manufacture of ethylene.
Traditionally, the outlet for pygas has been motor
gasoline blending, because of its high octane number.
However, only small portions can be blended untreated
owing to the unacceptable odor, color, and gum-forming
tendencies of this material.
The quality of pygas, which is high in diolefin content, can
be satisfactorily improved by hydrotreating, whereby
conversion of diolefins into mono-olefins provides an
acceptable product for motor gas blending.

Ch. 4 - 120
Other Hydrotreating Processes

Hydrotreating processes differ depending upon the feedstock

available and catalysts used.
Hydrotreating can be used to improve the burning characteristics
of distillates such as kerosene. by converting aromatics into
naphthenes, which are cleaner-burning compounds.
Lube-oil hydrotreating uses hydrogen to improve product quality.
With mild lube hydrotreating saturation of olefins and
improvements in color, odor, and acid nature of the oil are
achieved. Operating temperatures and pressures are usually
below 315 C and 60 bar. Severe lube hydrotreating (T ~ 315 -
400C and hydrogen pressures up to 205 bar) is capable of
saturating aromatic rings, along with sulfur and nitrogen removal,
to impart specific properties not achieved at mild conditions.

Ch. 4 - 121
Hydrocracking

Hydrocracking is a two-stage process combining catalytic cracking

and hydrogenation, wherein heavier feedstock is cracked in the
presence of hydrogen to produce more desirable products.
The process employs high pressure, high temperature, a catalyst,
and hydrogen. Hydrocracking is used for feedstock that are
difficult to process by either catalytic cracking or reforming, since
these feedstock are characterized usually by a high polycyclic
aromatic content and/or high concentrations of the two principal
catalyst poisons, sulfur and nitrogen compounds.
The process largely depends on the nature of the feedstock and
the relative rates of the two competing reactions, hydrogenation
and cracking. Heavy aromatic feedstock is converted into lighter
products under a wide range of very high pressures (70-140 bar)
and fairly high temperatures (400-800C), in the presence of
hydrogen and special catalysts.

Ch. 4 - 122
Hydrocracking

When the feedstock has a high paraffinic content, the

primary function of hydrogen is to prevent the formation
of polycyclic aromatic compounds.
Another important role of hydrogen in the hydrocracking
process is to reduce tar formation and prevent buildup of
coke on the catalyst.
Hydrogenation also serves to convert sulfur and nitrogen
compounds present in the feedstock to hydrogen sulfide
and ammonia.
Hydrocracking produces relatively large amounts of
isobutane for alkylation feedstock and also performs
isomerization for pour-point control and smoke-point
control, both of which are important in high-quality jet
fuel.

Ch. 4 - 123
Hydrocracking

Preheated feedstock is mixed with recycled hydrogen and

sent to the first-stage reactor, where catalysts convert sulfur
and nitrogen compounds to H2S and NH3. Limited
hydrocracking also occurs.
After the hydrocarbon leaves the first stage, it is cooled and
liquefied and run through a separator. The hydrogen is
recycled to the feedstock.
The liquid is charged to a fractionator.
The fractionator bottoms are again mixed with a hydrogen
stream and charged to the second stage. Since this material
has already been subjected to some hydrogenation,
cracking, and reforming in the first stage, the operations of
the second stage are more severe (higher temperatures and
pressures). Again, the second stage product is separated
from the hydrogen and charged to the fractionator.

Ch. 4 - 124
Hydrocracking Process Configuration

Ch. 4 - 125
Hydrocracking Flow Scheme

Ch. 4 - 126
Catalytic Reforming

Catalytic reforming is an important process used to

convert low-octane naphthas into high-octane gasoline
blending components called reformates.
Reforming represents the total effect of numerous
reactions such as cracking, polymerization,
dehydrogenation, and isomerization taking place
simultaneously.
Depending on the properties of the naphtha feedstock
(as measured by the paraffin, olefin, naphthene, and
aromatic content) and catalysts used, reformates can be
produced with very high concentrations of benzene,
toluene, xylene, (BTX) and other aromatics useful in
gasoline blending and petrochemical processing.
Hydrogen, a significant by-product, is separated from the
reformate for recycling and use in other processes.

Ch. 4 - 127
Catalytic Reforming
A catalytic reformer comprises a reactor and product-
recovery section.
There is a feed preparation section comprising a
combination of hydrotreatment and distillation.
Most processes use Pt as the active catalyst. Sometimes
Pt is combined with a second catalyst (bimetallic catalyst)
such as rhenium or another noble metal.
There are many different commercial processes including
platforming, powerforming, ultraforming, and Thermofor
catalytic reforming.
Some reformers operate at low pressure (3-13 bar),
others at high pressures (up to 70 bar). Some systems
continuously regenerate the catalyst in other systems.
One reactor at a time is taken off-stream for catalyst
regeneration, and some facilities regenerate all of the
reactors during turnarounds.

Ch. 4 - 128
Catalytic Reforming

In the platforming process, the first step is preparation of

the naphtha feed to remove impurities from the naphtha
and reduce catalyst degradation.
The naphtha feedstock is then mixed with hydrogen,
vaporized, and passed through a series of alternating
furnace and fixed-bed reactors containing a platinum
catalyst.
The effluent from the last reactor is cooled and sent to a
separator to permit removal of the hydrogen-rich gas
stream from the top of the separator for recycling.
The liquid product from the bottom of the separator is sent
to a fractionator called a stabilizer (butanizer). It makes a
bottom product called reformate; butanes and lighter go
overhead and are sent to the saturated gas plant.

Ch. 4 - 129
Catalytic Reforming Scheme

Ch. 4 - 130
Semi-regenerative Catalytic Reforming

Ch. 4 - 131
Continuous Regenerative Catalytic Reforming

Ch. 4 - 132
Catalytic Reforming Reactors

Ch. 4 - 133
Alkylation

Alkylation combines low-molecular-weight olefins

(primarily a mixture of propylene and butylene) with
isobutene in the presence of a catalyst, either sulfuric acid
or hydrofluoric acid.
The product is called alkylate and is composed of a
mixture of high-octane, branched-chain paraffinic
hydrocarbons.
Alkylate is a premium blending stock because it has
exceptional antiknock properties and is clean burning. The
octane number of the alkylate depends mainly upon the
kind of olefins used and upon operating conditions.

Ch. 4 - 134
Sulphuric Acid Alkylation Process
In cascade type sulfuric acid (H2SO4) alkylation units, the
feedstock (propylene, butylene, amylene, and fresh
isobutane) enters the reactor and contacts the
concentrated sulfuric acid catalyst (in concentrations of
85% to 95% for good operation and to minimize
corrosion).
The reactor is divided into zones, with olefins fed through
distributors to each zone, and the sulfuric acid and
isobutanes flowing over baffles from zone to zone.
The reactor effluent is separated into hydrocarbon and
acid phases in a settler, and the acid is returned to the
reactor. The hydrocarbon phase is hot-water washed
with caustic for pH control before being successively
depropanized, deisobutanized, and debutanized. The
alkylate obtained from the deisobutanizer can then go
directly to motor-fuel blending or be rerun to produce
aviation-grade blending stock. The isobutane is recycled
to the feed.

Ch. 4 - 135
Sulphuric Acid Alkylation Process

Ch. 4 - 136
Sulphuric Acid Alkylation Process

Ch. 4 - 137
Alkylation

With H2SO4 in Stratco contactor with Autorefrigeration

Ch. 4 - 138
Oil Refinery
Heavy Residue Conversion Processes

The World of Energy

Chapter 4

Ch. 4 - 139
Conversion of Heavy Residue

Processing of light crude, even in a complex refinery with FCC,

hydrocracking etc. does not yield a satisfactory product
distribution. The amounts of fuel oil are too high.

Ch. 4 - 140
Conversion of Heavy Residue
For heavy oil the situation is even worse with ~ 50% fuel
oil being produced even in a complex refinery.
Fuel oil is worth < original crude. The value of the
products decreases in the order: gasoline> kerosene/gas
oil > crude oil > fuel oil.

Ch. 4 - 141
Conversion of Heavy Residue

There are several reasons for an increased incentive to

convert fuel oil into lighter products:

1. The demand for light products such as gasoline and automotive

diesel fuels continues to increase while market for heavy fuel oil is
declining

2. Environmental restrictions become more important. Fuel oil

contains high amounts of S, N, and metals, so measures must be
taken to lower emissions

3. With the exception of Western Europe, the quality of crude oil

shows a worsening trend. It becomes heavier with higher amounts
of hetero-atoms, so more extensive processing is required to obtain
the same amount and quality of products.

Ch. 4 - 142
Conversion of Heavy Residue

In principle there are two solutions for upgrading

residual oils and for obtaining a better product
distribution. These are carbon out and hydrogen in
processes

1. Examples of carbon rejection processes are the Flexicoking

process (Exxon) and the FCC process discussed earlier

2. Examples of hydrogen addition processes are the LC-fining

process (Lummus) and the HYCON process (Shell).

Ch. 4 - 143
Fluid Coking and Flexicoking

Both FLUID COKINGTM and FLEXICOKINGTM use fluid bed

technology to thermally convert heavy oils such as vacuum
residue, atmospheric residue, tar sands bitumen, heavy whole
crudes, deasphalter bottoms or cat plant bottoms

FLEXICOKING goes one step further than FLUID COKING: in

addition to generating clean liquids, FLEXICOKING also
produces a low-BTU gas in one integrated processing step that
can virtually eliminate petroleum coke production

The advantages are: flexibility to handle a variety of feed

types; high reliability with the average service factor between
90 -95%; large single train capacity provides an economy of
scale that lowers investment cost; able to process 65 kB/SD of
20 wt% Conradson Carbon resid in a single reactor; time
between turnarounds routinely approaches two years; able to
process very heavy feed stocks such as deasphalter bottoms
at high feed rates

Additional FLEXICOKING benefit: Integrated gasification of up

to 97% of gross coke production

Ch. 4 - 144
The Fluid Coking Process

The fluid coking residuum conversion process uses non-

catalytic, thermal chemistry to achieve high conversion
levels with even the heaviest refinery feedstocks

Since most of the sulfur, nitrogen, metals, and Conradson

Carbon Residue feed contaminants are rejected with the
coke, the full-range of lighter products can be feed for an
FCC unit

Use as a single train reduces manpower requirements and

avoids process load swings and frequent thermal cycles
that are typical of batch processes such as delayed coking

The configurations available with fluid coking are:

extinction recycle, once-through, and once-through with
hydroclones.

Ch. 4 - 145
Coker

Ch. 4 - 146
Simplified Fluid Coking Flow Scheme

Ch. 4 - 147
The Flexicoking Process

Flexicoking is a thermal technology for converting heavy feedstocks

to higher margin liquids and producing, a low BTU (i.e. a low
energy content) gas, instead of coke

The conversion of coke to clean fuel gas maximizes refinery yield of

hydrocarbons

The carbon rejection process results in lower hydrogen

consumption than alternative hydrogen-addition systems

The low BTU gas is typically fed to a CO boiler for heat recovery but
can also be used in modified furnaces/boilers; atmospheric or
vacuum pipestill furnaces; reboilers; waste heat boilers; power
plants and steel mills; or as hydrogen plant fuel, which can
significantly reduce or eliminate purchases of expensive natural gas

The small residual coke produced can be sold as boiler fuel for
generating electricity and steam or as burner fuel for cement
plants.

Ch. 4 - 148
Simple Flexicoking Flowscheme

Ch. 4 - 149
The Flexicoking Process

Ch. 4 - 150
Catalytic Hydrogenation of Residues

This is a hydrogen-in route.

It serves two purposes: removal of Sulphur, Nitrogen
and metal compounds, and the production of light
products.
Reactions are similar to those occurring in
hydrotreating and hydrocracking of gas oils, but there
are two important differences.
(1) Residues contain much higher amounts of sulphur,
nitrogen and polycyclic aromatic compounds; and
(2) removal of metals, which are concentrated in the
residual fraction of the crude, means that operating
conditions are more severe and hydrogen consumption
greater than for hydroprocessing of gas oils.

Ch. 4 - 151
Catalyst Deactivation

Deposition of metals causes catalyst deactivation.

Basically all metals in the periodic table are present in
crude oil with the major ones being Ni and V.
At the reaction conditions H2S is present, hence metal
sulphides are formed.
The reaction scheme is complex but may be represented
simply as:
Ni-porphyrin + H2 NiS + hydrocarbons and
V-porphyrin + H2 V2S3 + hydrocarbons
The catalyst is poisoned by this process because most of
the deposition occurs on the outer shell of the catalyst
particles, initially poisoning the active sites then causing
pore plugging.

Ch. 4 - 152
 Reactors used for Catalytic Hydrogenation

Three types of reactor are used: (1) fixed-bed reactors; (2)

fluidized-bed reactors (also called ebulliated-bed reactors);
and (3) slurry reactors.

Ch. 4 - 153
The LC-fining Process

Developed by Lummus.
Uses fluidized-bed reactors.

Ch. 4 - 154
Processes with Fixed-bed Reactors

Replacement of deactivated catalyst in a conventional fixed-bed

reactor is not possible during operation.
Depending on the metal content of the feedstock various
combinations can be applied.

Ch. 4 - 155
The HYCON process

Ch. 4 - 156
Catalyst Rejuvenation

Catalyst rejuvenation is achieved by removal of metal sulphides

and carbonaceous deposits (essentially by oxidation), and by
extraction of the metals.

Ch. 4 - 157
Processes with Slurry Reactors

Slurry processes for residue processing are normally

designed with the objective of maximizing residue
conversion.
Downstream reactors are then used to treat the liquid
products for S and N removal.
Examples of the slurry process are the Veba Combi-
Cracking and CANMET process.
Conversion of residual feed takes place in the liquid
phase in a slurry reactor.
After separation the residue from the products they are
further hydro-treated in a fixed-bed reactor containing
an HDS catalyst.
A cheap, once-through catalyst is used which ends up
in the residue.

Ch. 4 - 158
Veba Combi-Cracking process

Ch. 4 - 159
Oil Refinery
Refinery Gas Processes

The World of Energy

Chapter 4

Ch. 4 - 160
Treatment of Refinery Gases
Removal of H2S from gases is usually performed by
absorption in the liquid phase.
The concentrated H2S is frequently converted to elemental
sulphur by the Claus process.
In the Claus process 95-97% of the H2S is converted.
H2S is often removed with solvents that can be
regenerated, usually alkanolamines: e.g. CH2(OH)CH2NH2
MEA (mono-ethanolamine).
These amines are highly water soluble with low volatility
and their reaction with H2S is much faster than with CO2
so that the amount of absorbed CO2 can be limited by
selecting appropriate conditions.

Ch. 4 - 161
H2S Removal by Amine Absorption

Ch. 4 - 162
Typical Claus Process

Ch. 4 - 163