Petroleum Refining and

Processing
CHEG 421

Dr. Ahmed Abdala

Instructor

Dr. Ahmed A. Abdala

 Office: Bu Hasa, Room. 2-214
Phone: 607-5584
e-mail: aabdala@pi.ac.ae
 Class Schedule
 1:00 – 2:00 PM Sunday, Tuesday, and Thursday
 Office Hours:
 2:00 PM – 5:00 PM Tuesday and Thursday
Introduction
Importance of Refining Processes

 Crude oil is a mixture of large number of

compounds composed mainly of C, H, S, N,
and O
 the unprocessed petroleum (crude oil) can
only be used for heating
 Refining processes transform crude oil into
valuable products that can be used in the
marketplace
What Happens During Refining?
 Refining starts with separation of the crude oil
through distillation
 The refinery capacity is reported in terms of its
distillation capacity
 Capacity is reported as BPSD or BPCD
 Distillation produces fractions or cuts
 These cuts have volatilities (Boiling range) close to
those of final products
 These cuts are further converted by changing the
size and/or the structure of the molecules through
cracking, reforming, and other conversion
processes
Crude oil

Petroleum
Cuts

Bases

Products
Refining Processes
1. Distillation
2. Conversion Process
 Decomposition (Cracking)
 Unification (alkylation, polymerization, etc)
 Reforming (catalytic reforming, isomerization)
3. Treatment Processes
 Desalting, hydrotreatment, solvent extraction, dewaxing,
sweetening, etc)
4. Blending
5. Other Operations
 Light end recovery, sour-water treatment, solid waste and
waste-water treatment, cooling, storage, etc
Overall Refinery Flow
C4-
Gas Petrochemical Feedstocks

LPG
C5-180°C
naphtha Motor gasoline
Atmospheric
Distillation

Refining Processes
Crude oil 180-230°C Diesel fuel
kerosene
+
230-350°C Heating oil
gas-oil

350°C Heavy fuel oil

Distillation
vacuum

Vacuum
distillates base oils
550°C

vacuum Residue Bitumen

Atmospheric Residue Coke
 LPG+Gas C1-C4 Refinery fuel
Vapor Recovery
Gas
LSRG C5-C6 LPG
Isomerization

Naphtha C6-C11 Gasoline

Hydrotreatment Reforming
Middle C9-C14 Solvent
Hydrotreatment
Distillates

Treating and Blending

Crude Aviation Fuel

Cracking
Oil
Atmospheric C13-C24

Cat.
Gasoline
Gas Oil Diesel Fuel

Gasoline Heating Oils

Alkylation
Vac. Gas Oil
C20-C40 Lube Oils
Gasoline, naphtha,
Hydrocracking Greases
middle distillates, and fuel oil

Lube C35-C50 Aromatic Asphalt

reduction Dewaxing
base stock
Industrial
Fuels
Deasphalting Asphalt
Refinery
C50+

visbreaking Fuel oil

Gasoline, naphtha,
middle distillates, and fuel oil
coking Coke
Refinery Configuration
 Refining Configuration depends on the demand for gasoline,
diesel, fuel oil, and petrochemicals feed
 The most widely used conversion processes are: catalytic
hydrotreating, catalytic cracking and catalytic reforming
 Catalytic hydrocracking is used more compared to catalytic
cracking, in particular in Europe (high demand for diesel
and jet fuel)
 Refinery complexity is measured by estimating the % of
conversion capacity from the distillation capacity
 Primary growth in processes which aim to reduce sulfur
content (hydrotreating and hydrocracking)
Product Demand

 Demand for gasoline, middle distillates, and

heating oil varies from one region to
another
 Asian demand for gasoline in the last decade
increased over 50%
 US demand for gasoline increased 15%

 European demand dropped due to increasing of

transportation fleet to diesel fuel
Refinery Capacity
 There are about 700 refineries world wide North
America
26%
 Total refinery capacity of 85.1 million BPCD
 Asia capacity: 22.2 MM PBCD Asia West
Europe
 North America: 20.6 MM PBCD 29%
19%

 Western Europe: 15.0 MM PBCD East

Africa Middle
 Eastern Europe: 10.2 MM PBCD 4% East
Europe
13%
 Middle East: 7.0 MM PBCD 9%

 Africa: 3.2 MM PBCD

 In terms of countries
USA China Russia Japan
 Major Companies
 ExxonMobile, Royal Dutch Shell, BP, Chevron, Saudi Aramco, China
National Petroleum, Petroleos de Venzuela, Petroleos Mexicanos, Petroleo
Brasileiro, National Iranian OiI, Total, ConcoPhilips
Industry Characteristics

 Not two crude oils are the same

 Crude oils differs in terms of gravity, sulfur
content, acid content
 Over 150 crude oil grades are traded

 Each refinery is unique

 Refinery configuration, size, sophistication, and
cost are different from refinery to another
depending on location, crude type and products
they produce
Industry Characteristics
 Refinery configuration evolves over time
 After they built, refineries are upgraded to meet current
product specifications and environmental regulations
 Not all refineries are created equally
 Simple refinery consist of a distillation unit and one or
more pretreatment facilities, reforming, and
hydrodesulfurization units
 Complex refinery (cracking) or very complex (coking)
have significant upgrading capacity
 They are able to change the composition of the crude oil input,
converting low value heavy oils and converting them to high
value, light product
Refinery Economics

 Refinery economics are complicated. It

depends on:
 plant configuration, crude oil price, product
prices, strategic decisions, operating cost
 Refinery net margins are about $0.5-4/bbl
 $1/bbl ~ $35 million per year for a 100,000
BPSD
 Decision to upgrade, enhance, or modify
existing configuration
Cost Estimation
 Source for cost data are published annually in the October
issue of the Hydrocarbon Processing and the Oil and Gas
Journal or other commercial databases
 Process Technology
 Simple
 Cracking
 Coking
 Cost versus size
 The cost of a refining unit of capacity Q can be approximated
from a similar plant of capacity Q1 as follow:
x
 Q 
C (u i ,Q ) = C (u i ,Q 1 )  
Q 1 
 Where x vary between 0.5-0.7
Cost Estimation

 Utility Requirement
 Utilities include steam, electricity, cooling water,
process water, boiler feed water, chilled water,
natural gas, fuel oil
 The cost data for utilities are normalized with
respect to construction requirement, process
specifications, location, and time of installation
Cost Estimation: Nelson-Farrar factor

 The cost of a plant at time

t2, C(t2), can be obtained by
multiplying the original cost
price at time t1, C(t1) by the
ratio of cost indices:
 I (t 2 ) 
C (t 2 ) = C (t 1 )  
 I (t )
1 

 The Nelson-Farrar (NF)

cost index are published in
the first issue of each month
of the Oil and Gas Journal
Refinery Complexity: Unit Complexity

 The Nelson complexity factor quantify the relative

cost of components that makes up a refinery
 Atmospheric distillation has a factor of 1
 The cost of each other unit are expressed relative
to atmospheric distillation
 The complexity factor of unit ui of capacity Qi is
the ratio of the construction cost of that unit C(ui,
Qi) to the cost of a distillation unit, u0, of capacity
Q0 C (u i ,Q 1 )
γ (u i ) =
C (u0 ,Q 0 )
Refinery Complexity, γ(R)

 The complexity factor of a refinery is determined

by the complexity of each individual unit weight by
its percentage of distillation capacity
 Simple refinery has γ(R) < 5
 Complex refinery 5 < γ(R) < 15
 Very complex refinery γ(R) > 15
Example: Refinery Complexity
Capacity Complexity
 Estimate the Process
BPSD Index
complexity factor Atmospheric Distillation 501000 1
of ExxonMobile’s Vacuum distillation 227000 2
Louisiana refinery Coking 112500 5.5

that has the Cat. Cracking 229000 6

following units and Cat. Reforming 75500 5

capacity: Cat. Hydrocracking 24000 6

Cat. Hydrotreating 333500 1.7
Alkylation 140000 11
Polymerization 9500 9
Lubes 16000 60
Oxygenates 7000 10
Hydrogen (MCFD) 12000 1
Complexity Index
Capacity % of Complexity Complexity
Process
BPSD Distillation Index Factor
Atmospheric Distillation 501000 100.0 1 1.00
Vacuum distillation 227000 45.3 2 0.91
Coking 112500 22.5 5.5 1.24
Cat. Cracking 229000 45.7 6 2.74
Cat. Reformin 75500 15.1 5 0.75
Cat. Hydrocracking 24000 4.8 6 0.29
Cat. hydrotreating 333500 66.6 1.7 1.13
Alkylation 140000 27.9 11 3.07
Polymerization 9500 1.9 9 0.17
Lubes 16000 3.2 60 1.92
Oxygenates 7000 1.4 10 0.14
Hydrogen (MSCF) 12000 2.4 1 0.02

Refinery Complexity index Sum 13.38

Petroleum Refining and
Processing
CHEG 421

Chapter 2:
Petroleum Products
Refinery Products
 There are few numbers of products that dictate
the refinery design
 However, many other products are produced
 To avoid storage and waste disposal costs, some
items are sold for prices less than the cost of fuel
oil
 Further processing of some fractions to produce
products with greater value may be more
economical
Classification of Petroleum Products

 Based on their specific gravity (volatility),

refinery products can be classified as:
1. Low boiling point products
2. Gasoline
3. Distillate fuels
4. Residue fuel Oil
Low boiling

Gasoline

Middle
Distillates

Residue
Petroleum Products:
low Boiling Point Products
 Gases (C1, C2, C3 and their olefins)
 Methane is used as refinery fuel or feedstock for
synthesis gas
 Ethane is used as fuel or feedstock for production of
ethylene or hydrogen
 Propane is mainly used as LPG
 LPG specifications:
 Maximum VP at 37.8°C of 210 psig
 95% BP of -38.3° C at 1 atm
 Propylene and ethylene are used for production of
polymers
Low Boiling Point Products: n-C4

 Butanes is used as LPG or as additive to

gasoline
 C4 is cheaper than gasoline
 C4 has high ON (90s)
 n-C4 has lower RVP than i-C4
 The amount added is limited by the RVP of
gasoline (environmental and mechanical)
Low Boiling Point Products: i-C4

 Produced mainly via FCC and HC

 i-C4 is used for alkylation process
 Converted to i-C4= which is used for
production of Oxygenates via reaction
with alcohol
 MTBE, ETBE
Refinery Products: Gasoline
 Mixture of hydrocarbons having BP ranges from 38
to 205° C
 Mainly used as automobile fuel
 Different grades in the market based on their
antiknock performance (ON)
 Gasoline is blend of gasoline bases produced by
different units in the refinery
 LSR gasoline, isomerate, reformate, cat. cracked
gasoline, hydrocracked gasoline, polymer gasoline,
alkylate gasoline, n-butane, additives (oxygenates)
Characteristics of Gasoline

 Antiknock quality
 Ease of starting
 Quick warm-up
 Low tendency to vapor lock
 Low engine deposits
1. Antiknock Characteristics
 Knocking is caused by the instantaneous ignition of
the fuel at certain points of the combustion
chamber
 Knocking leads to:
 Overloading of the cooling system
 Temperature elevation in cylinder and head gaskets
 Mechanical damage due to the erosion of the cylinder
head and the piston and deterioration of the spark
ignition and valves
 The antiknocking properties of gasoline is
quantified by Octane number (ON)
Why does knocking occur?

 4-stroke engines was developed by Beau de

Rochas in 1862
 In such engines
the combustion
of air/fuel mixture
is triggered by a
spark plug
Knocking
Octane number
 Octane number characterizes the anti-knock
characteristics of gasoline
 It represent the ratio of i-octane in its mixture with n-
heptane which produces knock similar to the tested fuel
 RON is the octane number measured under mild
conditions (city driving) of 600 rpm
 MON is the octane number measured under tough
conditions (highway) of 900 rpm
 PON, Posted (pump) octane number, is the average of
the RON and the MON
 The difference between Mon and RON represents the
sensitivity of the fuel to the engine conditions
Octane number of different HCs

Paraffins Naphthenes Aromatics Olefins

Normal iso

Liquid
Low Low Medium High low
density

RON Very low High Medium Very high High

Sensitivity
Very low Very low low high Very high
(RON-MON)
2. RVP
 Reid Vapor Pressure (RVP) is the pressure built by
the vapors of a gasoline contained in a standardized
bomb at 37.8 °C
 It characterize the vaporization capacity of the fuel
 RVP affects engine starting, rate of acceleration, and
tendency towards vapor lock
 RVP should not exceed the max Ambient Max.
Temperature Allowable,
allowable limit to avoid vapor lock ,°C RVP, kPa

37.8° C
16 88
21 76
27 65
32 55
3. Boiling Range

 Engine warm up is related to the % distillate at 70°

C and the 90% ASTM distillation temperature as
follow:
Ambient
27 16 4 -7 -18 -29
Temperature,° C

% dist. At 70° C 3 11 19 28 38 53

90% ASTM dist. 188 177 171 163 154 149

 Colder weather needs more volatile gasoline

Components of the Gasoline Pool
 The gasoline product is produced by blending
gasoline fractions from different processes plus
n-butane and ON boosting additives.
 The following component constitute the final
gasoline:
 LSR Gasoline
 Isomerate
 Reformate
 Cat. Cracked gasoline
 Hydrocracked gasoline
 Polymer gasoline
 Alkylate gasoline
 n-butane
 Oxygenates
Light Straight Run Gasoline

 Fraction of naphtha C5 - 88° C

 Mainly C5 and C6
 Cannot be upgraded by reforming
 Can be upgraded by isomerization
 Can be added directly to the gasoline pool
 Has low octane number (70-80) and high
vapor pressure
Reformate Gasoline
 Gasoline produced by catalytic reforming of:
 Heavy straight run gasoline
 Coker gasoline
 Heavy FCC and HC gasoline (sometimes)
 Octane number ~ 90-104
 Contains high ratio of aromatics
 Aromatics has higher ON compared to paraffins but
may form visual pollutants in the air and could be
carcinogenic
 This may impact the severity of reforming and limit the
use of catalytic reforming processes in the future
Other Gasoline Fractions
 FCC and HC gasoline
 Light fraction is added to the gasoline pool
 Heavy fraction is reformed
 Polymer gasoline
 Polymerization of C2, C3, and C4 olefins
 Mainly olefins
 Photoreactive and causes visual air pollution
 Alkylate gasoline
 Produced via reaction of C3, C4, and C5 olefins with isobutane
 Isoparaffinic
 Produces larger quantity from available light olefins compared to
polymerization
Non-gasoline Components
 n-butane
 Blended with gasoline to adjust the vapor pressure
 Photoreactive and causes visual air pollution
 Oxygenates
 Oxygen containing compounds (ethers or alcohols)
 Methyl tertiary butyl ether (MTBE)
 Ethyl tertiary butyl ether (ETBE)
 Tertiary Amyl methyl ether (MTBE)
 Methanol
 Ethanol
 Blended with gasoline to increase the ON
Properties of Oxygenates
Prem.
MTBE ETBE TAME Methanol Ethanol
Gasoline
BP, ° C 30-190 55 73 86 65 78
RVP, kPa 35-90* 55 40 10 524 154
Calorific Value, kJ/g 32 26 27 27 16 21
Heat of vaporization
289 337 321 310 1100 854
(kJ/kg)
RON 95 118 118 115 126 120
MON 85 101 101 100 95 99
Sensitivity 10 17 17 15 31 21
Maximum Allowed incorporation,
15 15 15 3 1
% vol.
Typical Composition of Gasoline Pool
% in Olefins Aromatics
Component
pool % %  Reformate gasoline has
LSR Gasoline 3 0 10 high aromatic content
Reformate 27 1 63  FCC gasoline has high
Isomerate 4 0 1 aromatic, olefin, and sulfur
FCC 38 30 30 content
HC 2 3 3  heavy FCC gasoline
Coker 1 5 5 responsible for about
Alkylate 12 0.5 0.5 85% of the sulfur content
Polymer 0.5 96 0.5 of gasoline
n-butane 3 2.6 0
 Polymer gasoline has very
high olefin content
Distillate fuels
 Jet (turbine) fuel
 Diesel fuels
 Aviation
 Railroad
 Heating oils
 Heating fuels production is decreasing due to increase in
the production of transportation fuels and the use of
natural gas in heating
 Environmental regulation on fuel emissions has led to
replacing heating oils with natural gas and LPG
Jet and Turbine Fuel
 Used for aviation and military aircrafts and jets
 The base fraction is the SR kerosene
 Military Jet fuel are based on naphtha
 Naphtha based jet fuel is more volatile (less safe to
handle)
 More profitable to produce jet fuel by blending SR
kerosene and HC gasoline
 More expensive than diesel fuel and heating oil
 Less cracked stocks can be used due to limit of
aromatics and double ring aromatics content
imposed by the clean burning act
Jet and Turbine Fuel Characteristics
 Smoke point:
 Characterize the content of aromatics and naphthalenes
 Hydrocracking reduce aromatic content
 Freeze point (-40 to -50º C)
 Boiling point range
 177-288º C
 Flash point
 43-66º C
 Components of jet fuel pool
 Low sulfur or desulfurized kerosene
 hydrotreated light coker gas oil
 hydrocracked kerosene
Automotive Diesel Fuels
 Volatility, ignition quality (cetane number), viscosity, sulfur
content, percent aromatics and cloud point are the
important properties for diesel fuel
 BP 180 – 320° C
 Flash point limit 52° C
 Cetane Number (CN)
 The % of n-cetane (high quality ignition) in its mixture with α-
methyl naphthalene (low quality ignition)
 It measures the fuel’s ignition delay
 Can be calculated based on the API gravity and ASTM 50% distilled
temperature
 Diesel fuel have CN between 40-55
Calculation of Cetane number
ASTM 50%
Specific gravity 15 °C distilled temperature
Cetane Number
Cetane Number versus Structure
Paraffin
Naphthene Aromatic Olefin
Normal Iso

Liquid
Low Low Medium High low
density

Cetane
Very high Low Medium Low Low
number

Octane
Very low Very High low High Very high
Number

Trends of CN and ON as function of structure are

opposite
Railroad Diesel Fuel and Heating Fuels

 Railroad diesel fuel

 Similar to automotive diesel fuel but heavier
 BP up to 400° C
 Lower Cetane number (< 40)
 Heating (fuel) oil
 Consumption vary from one location to another
 LPG is more widely used
 Similar to kerosene but higher pour point and end point
 Blended from naphtha, kerosene, diesel, and cracked gas
oil
Residue fuel oil

 Residue of the vacuum distillation tower

 Viscosity and sulfur content are important
properties
 Used for heating
Petroleum Refining and
Processing
CHEG 421

Chapter 3:
Refinery Raw Materials
Crude Oil
 Crude oil and natural gas condensates are the
refinery raw materials
 Crude oil is the term for "unprocessed" oil, the
stuff that comes out of the ground. It is also known
as petroleum.
 Crude oil is a fossil fuel
 It was made naturally from decaying plants and animals
living in ancient seas millions of years ago
 Anywhere you find crude oil was once a sea bed.
 Crude oils vary in color, from clear to tar-black,
and in viscosity, from water to almost solid
Composition of Crude Oil

 Crude oil is a very complex mixture of

compounds composed of (mainly) carbon,
hydrogen, oxygen, and sulfur
 Carbon and Hydrogen are by the major
components (Hydrocarbons)
 Gases
 Liquids

 Solids
Crude Oil Composition
 On average, crude oils are made of the following elements
or compounds:
 Carbon - 84%
 Hydrogen - 14%
 Sulfur - 1 to 3% (
 hydrogen sulfide, sulfides, disulfides, elemental sulfur
 Nitrogen - less than 1%
 (basic compounds with amine groups)
 Oxygen - less than 1%
 carbon dioxide, phenols, ketones, carboxylic acids
 Metals - less than 1%
 nickel, iron, vanadium, copper, arsenic
 Salts - less than 1%
 sodium chloride, magnesium chloride, calcium chloride
1. Hydrocarbons

 Paraffins (alkanes) have the molecular form

of CnH2n+2
 Naphthenes (cycloalkanes) are cycloparaffins
with the molecular form CnH2n
 Aromatics are cyclic compounds that
contain the benzene ring
 Olefins are not present in crude oil but
introduced during refining processes
2. Heterotomic HC

 HC compounds contains atoms other than

C and H such as S, N, O and metals
 S as H2S, Thiophene, mercaptane, sulfides, and
disulfides
 N as Pyridine and Payroll

 O as Carboxylic, phenols, furan, CO2

 Metals as organometallic compounds

(porphyrins)
Organic Sulfur Compounds
Organic Nitrogen Compounds

Nonbasic Basic
Pyroll C4H5N
Pyridine C5H5N
Indole C8H7N Quinoline C9H7N

Indoline C8H9N
Carbzole C12H7N

Benzo(a)carbazole Benzo(f)quinoline
C12H7N C13H9N
Organic Oxygen Compounds
Porphyrins
 Cyclic organometallic compounds
3. Others

 Traces of elements and metals Cu, Ca, Mg

 Salts
Properties of Crude Oil: °API
 141.5
API − 131.5
Specific Gravity
 Water has API of 10
 Crude oil have API between 10 and 50º
 The higher the API the better the lighter is the oil
 API gravities are not linear and therefore cannot
be averaged
 Reference temperature for specific gravity and
°API is 60° F (15.6° C)
Sulfur Content

 Has great influence on the value of crude oil

 It varies from less than 0.1% to greater than
5%
 Sour crude has sulfur content > 0.5%
 Sweet crude has sulfur content < 0.5%
Metal Content, ppm

 Vary from few ppm to more than 1000 ppm

 Ni, Va, Cu severely affect catalyst activity
 Concentrated on the heavy fractions and
residue
 Some appear in higher-boiling distillates
 May be reduced by solvent extraction
Salt Content

 Mostly chlorides
 Expressed as lb NaCl/1000 bbl
 Salts cause corrosion problems
 Crude with salt content higher than 10
lb/1000 lb must be desalted to about 0.5
lb/1000 lb before distillation
Nitrogen Content

 Organic nitrogen compounds cause severe

poisoning of catalyst and cause corrosion
problems
 High nitrogen content is highly undesirable
 Crude with nitrogen content above 0.25%
requires nitrogen removal
Carbon Residue
 Related to asphalt content of the crude oil and the
quality of the lube oil fraction
 Indication of C/H Ratio of crude oil
 The lower the carbon residue, the higher the
value of the crude
 Measure by different standard methods
 Ramsbottom (RCR)
 Conradson Carbon (CCR)
 ASTM methods (D-524, D-189)
 Reported as weight%
Pour Point

 Pour point is the lowest temperature after

which the oil ceases to flow
 Indication of the paraffinic and aromatic
content of crude oil
 High pour point means high paraffin content
 Critical property for transportation of oil in
pipelines
Total Acid Number (TAN)

 TAN is the number of mg of potassium

hydroxide required to neutralize 1 g of oil
 Also used to monitor acidity of crude oil
and lube oils
 Crude oils with high acid content causes
rapid corrosion in particular for
fractionation columns
Other Properties

 Kinematics Viscosity
 RVP
 Flash point
 Cloud Point
 Ash Content
 Characteristics Units

Crude Characteristics
Specific Gravity at 60/60°F

API Gravity at 60°F

0.8261

39.8

Kinematic Viscosity at 70°F Cst 3.79

100°F Cst 2.94

 Murban Field 122°F

Pour Point
Cst

°F
2.37

-20

Flash Point °F Below 0

Reid Vapour Pressure at 100°F PSI 4.1

Water Content Vol. % <0.05

Water Sediment Vol. % <0.05

Salt Content as NaCl lbs/100 bbl 1

Salt Content as NaCl weight % 0.00081

Total Acid Number mg KOH/gm 0.052

Strong Acid Number mg KOH/gm Nil

Sulphur Content weight % 0.82

Ashaltenes weight % 0.12

Wax Content weight % 5.72

Conradson Carbon Residue weight % 1.55

Ash content weight % 0.0038

Hydrogen Sulphide ppm wt Nil

Mercaptane Sulphur ppm wt 3.2

Basic Nitrogen weight % 0.026

Characterization Factor weight % 12.0

Distillation Range

 Boiling range of crude gives indication of the

quantity of various products present
 The boiling range is determined by
distillation curves
 True Boiling Point (TBP) distillation method
 ASTM distillation methods

 Equilibrium Flash Vaporization

Crude Distillation Curves
 True Boiling point (TBP)
 USBM Hempel method
 ASTM D-285
 15: 5 distillation
 ASTM: Standard Tests
1. D-86 for light fractions at atmospheric
pressure
2. D-1160 for heavier fractions (> 500°F)
carried out in vacuum
 Equilibrium Flash Vaporization (EFV)
Crude Distillation Curves

 Degree of separation by distillation

decreases in going From TBP to ASTM to
EFV
No High Degree of
Fractionation Fractionation

Flash ASTM TBP

TBP Distillation
TBP
 Constructed by fractionation at atmospheric (up
to 275 °C) and vacuum pressure (300 °C)
 USBM Hempel Distillation
 Lacks information about low BP
 Distillation temperature at vacuum must be
corrected to atmospheric pressure
 Low BP can be obtained via chromatography
Vacuum to Atmospheric
1100

1000
Boiling Point at 760 mm Hg, °F

900

800

700

600

500

400

300
100 200 300 400 500 600 700 800
Boiling point at 40 mm Hg, °F
ASTM to TBP

-40
-30
-20
TBP cut point - ASTM EBP

-10
0
10
20
30
40
50
60
70
100 200 300 400 500
EBP - IBP (ASTM)
TBP and API Graph
Crude Assay
 Source, Identification, and
General Characteristics
 Distillation Data
 Atmospheric (up to 275° C)
 Vacuum (up to 300° C)
 Summary
 Cuts
Boiling Range of Crude Oil

 TBP distillation curve constructed using only

atmospheric and vacuum distillation data does not
contain any information about the low boiling
point components (light ends)
 Low boiling point components include
 Gaseous HCs (C1 to C5)
 Inert gases (N2)
 Acid gases (H2S and CO2)
 Water
Chromatographic Assay Data
 Relative amounts of low boiling point materials
in crude oil can be obtained using
chromatographic and mass spectrometric
techniques
 crude oil can be characterized based on
chromatographic information about the relative
amounts of:
 Light ends
 Paraffinic materials
 Aromatic materials
 Naphthenic materials
 Chromtographic crude Assay
Light-ends:
Component Mole

Chromatographic Assay Methane

Ethane
%
41.83
8.84
Propane 7.11
i-Butane 1.47
n-Butane 3.75
i-pentane 1.25
n-pentane 1.63
N2 0.48
H2S 0.00
CO2 0.87
H2O 0.00
Paraffins:
Cut Mole
Fraction
Hexane (C6) 0.0268
Heptane (C7) 0.0371
Octane (C8) 0.0348
Nonane (C9) 0.0231 Aromatics:
Decane (C10) 0.0240 Component Mole
Undecane (C11) 0.0183 fraction
Dodecane (C12) 0.0142 Benzene 0.0004
Tridecane (C13) 0.0141 Toluene 0.0001
Tetradecane (C14) 0.0113 Ethyl benzene, p+ m- 0.0070
Pentadecane (C15) 0.0099 xylene
Hexadecane (C16) 0.0074 o-xylene 0.0028
Heptadecane (C17) 0.0082 1,2,4, tri-Methyl 0.0028
Octadecane (C18) 0.0060 Benzene
Nonadecane (C19) 0.0049
Eicosane (C20) 0.0046
Heneicosane (C21) 0.0039 Naphthenic
Docosane (C22) 0.0036 Component Mole
Tricosane (C23) 0.0032 fraction
Tetracosane (C24) 0.0027 Cyclopentane 0.0002
Pentacosane (C25) 0.0024 Methyl CycloPentane 0.0125
Hexacosane(C26) 0.0021 cyclohexane 0.0050
Heptacosane (C27) 0.0020 Methylcyclohexane 0.0156
Octacosane(C28) 0.0018
Noncosane (C29) 0.0016
Tricosane + (C30+) 0.0133
Cutting Crude Oil

 After constructing the TBP distillation curve,

the amount of different cuts that can be
produced from atmospheric distillation of
crude oil can be calculated based on their
initial and end boiling point
 These data are usually represented in a
distribution plot
Crude Oil Fractions
Fraction Vol.%
 Typical initial and end Boiling, °F

boiling points for Gas <50 -

LT. Naphtha 50-200 8
atmospheric distillation
HV. naphtha 200-400 20
cuts are as follow:
Kerosene 400-500 10
Gas oil 600-1100 15
residuum >1100 45
Heavy Naphtha Fraction (200-400 °F)

4% 22%
Heavy Naphtha Fraction (200-400 °F)

 Heavy naphthaha vol.% = 22-4

=18 %
 Mid Point
at 13% (4 +18/2)
 Mid Boiling Point 315°F
 API 46°
 Specific gravity, G= 0.8
 Kw=11.5 315° F

 CI=34.4
13%
Gas Oil Fraction (500-650 °F)

36% 60%
Gas Oil Fraction (500-560 °F)
 Heavy naphtha vol.% = 60-36
= 22 %
 Mid Point
 at 37% (36 +22/2)
 Mid Boiling Point 485°F
 API = 35°
 Specific gravity, G=0.85 485° F

 Kw =11.5
 CI =39
37%
Characterization Factor, Kw
 Indication of the paraffinicity of crude oil
 UOP or Watson Characterization factor
1
TB
3

KW =
G
TB=mean average BP =(T20+T50+T80)/3
G=specific gravity at 60° F
 Varies from ~10 to 15
 Highly aromatics/naphthenic compounds have low Kw (KW~10)
 Highly paraffinic compounds have high KW (KW ~15)
 Crude oils have KW between 10.5 (highly naphthenic) to
12.9
Correlation Index, CI
 Indication of the aromaticity of the crude oil or
fraction
 Useful for individual fractions from crude oil
87552
CI = + 473.7 G − 456.8
TB
 Straight-chain paraffins have CI of 0
 Benzene has CI of 100
 High CI means high content of aromatics and
naphthenes
 Low CI means high content of paraffins
Crude oil Suitable for Asphalt

 Crude oil suitability for asphaltene production

can be predicted from the values of KW and API
by estimating KW and API of the residue cut
 If crude oil follows the following 2 criteria, it
could be suitable for producing asphalt
1. KW of the residue (400° C average boiling point) is
less than 11.8 and API is below 35
2. The difference between KW of the 400° and the 290°
C is less than 0.15
Classification of Crude Based on API
 Conventional Crude Oil, API >20
 Heavy Crude Oil, API <20
 Bitumen, API < 10

Conventional Heavy
Bitumen
Crude crude

API 35 20 15 10
Classification of Crude Oil

 Paraffinic base, naphthenic base, asphalt base, or

mixed
 Based on the API of 250-275 atmospheric and
275-300 vacuum cuts (US Bureau of Mines)

Cut 1 40 33
paraffin Intermediate naphthene

Cut 2 30 20
Classification of Crude Oil: USBM
Cut 1 40 33
paraffin Intermediate naphthene

Cut 2 30 20

API
Cut 1 Cut 2
Paraffin 40 30
Paraffin/Intermediate 40 20-30
Intermediate 33-40 30
Intermediate/Paraffin 33-40 20-30
Intermediate/Naphthene 33-40 20
Naphthene/Intermediate 33 20-30
Naphthene <33 <20
Condensates
 The natural gas condensate is also referred to as simply
condensate, or gas condensate, or sometimes natural
gasoline because it contains hydrocarbons within the
gasoline boiling range
 Condensates are ultra-light crudes having up to 98%
distillates (boiling below 360° C).
 It is a low-density mixture of hydrocarbon liquids that are
present as gaseous components in the raw natural gas
produced from many natural gas fields
 It condenses out of the raw gas if the temperature is
reduced to below the hydrocarbon dew point temperature
of the raw gas
 It is ideal for a new topping refinery which wishes to feed a
Petrochemical Cracker nearby
Condensates
 Raw natural gas may come from any one of three
types of gas wells:
 Crude oil wells
 Raw natural gas that comes from crude oil wells is called
associated gas
 This gas can exist separate from the crude oil in the
underground formation, or dissolved in the crude oil
 Dry gas wells
 Typically produce only raw natural gas that does not contain any
hydrocarbon liquids
 Such gas is called non-associated gas
 Condensate wells
 These wells produce raw natural gas along with natural gas
liquid
 Such gas is also non-associated gas and often referred to as wet
Processing of Condensates
 Condensate Splitters produce the following low sulfur fractions
 LPG 3 to 8 %
 Naphtha ranging 25% to 75%
 Kerosene 20 to 40%
 Gas Oil 10 to 30%
 Condensate splitters produce Naphtha for a petrochemical Plant
by processing a small amount of feed compared to a Crude
Distillation column
 The Naphtha from condensates can be highly paraffinic for olefin
crackers
 It can be Naphthenic/Aromatic (ideal for Aromatic Petrochemical
complex)
 Kerosene and Diesel streams are conveniently processed in a
refinery before dispatched as finished products
Crude Distillation

 First major processing units in the refinery

 Crude oil is separated by distillation into
fractions according to their boiling range
 These fractions are the feedstock to the
following processing units
 Typical
crude
distillation
unit

Animation
Typical Crude Distillation unit

 Crude distillation unit consists of few sections

 Crude desalting
 Atmospheric distillation column
 Vacuum distillation column
 Auxiliary equipment
 Preflash tank
 Stabilizer to remove C3 and C4 from LSR gasoline
 Storage tanks
 Pumps
 Heat exchangers
What happens in Crude Distillation Units

 Crude oil from storage tanks is pumped to

desalting unit
 Before it reaching the desalting drum it is
heated via heat exchangers
 In desalting unit, salt is washed with water
and water is then removed with the aid of
chemicals (demulsifiers) or electric field or
both
What happens in Crude Distillation Units

 As crude oil leaves the desalting drums, it is heated in

furnace
 Sometimes it goes through preflash tank where light components
are separated and only the liquid portion of crude oil is heated in
the pipestill furnace
 Hot crude oil is fed into atmospheric distillation column
 The vapor portion of the feed is separated into fractions
 The heavy portion is collected from the bottom of the atmospheric
distillation column as residue
 Residue of the atmospheric distillation unit is fed to vacuum
distillation column
 Separated into gas oil fraction and the heavy vacuum residue
Desalting Crude Oils

 Crude with Salt content >10 lb/1000 bbl

must be desalted. Now all crude oils are
desalted to:
 Minimize fouling (scaling) and corrosion
 Remove metals in inorganic compounds
dissolved in water emulsified with crude
 Removing of suspended soils (sand, clay, iron
oxide and sulfide)
 60 - 80% removed
Desalting Process
1. Mixing crude oil with “wash” water
 3-10% water
 100-159 °C
 Water to oil ratio and temperature depend on the density
of the crude oil
 pH adjusted to between 6 and 8
2. Separation of wash water and oil
 Demulsifiers
 Electric field ( AC or AC and DC) 12-35 kV
 Single stage or two stage
 Ac or Dual field
 Salt content is estimated by either titration or
conductivity measurement
Animation
Single Stage

Demulsifier
2-Stage Desalting Unit
Determination of salt content

 Titration
 HACH with Mercuric nitrate
 Potentiometric

 Mohr titration

 Potentiometric in mixed solvent

 Conductivity
Cost of typical desalting unit

 For a typical 100 MBPSD

 Capital Cost ~ 5.5 MM$
 Other costs
 Power
 10-20 kWh/1000bbl
 Water
 4-12 m3/1000 bbl
 Demulsifier
 2-5 kg/1000 bbl ($3/kg)
 Caustic
 5-14 kg/1000 bbl ($0.5/kg)
Atmospheric Distillation

 After Desalting Crude Oil is pumped

through a series of heat exchangers and
heated to about 280-300 ° C
 After heated in heat exchangers, crude oil
may be subjected to preflashing process
where light ends are removed as vapors
 Liquid from the bottom of the preflash
column is heated in a gas-fired pipestill
(furnace)
Flow Diagram of Distillation unit

 Distillation Unit with no preflash column

Flow Diagram of Distillation unit

 Distillation Unit with preflash column

 Light Ends are recovered
Flow Diagram of Distillation unit
 Distillation Unit with preflash Tank
 Light Ends are mixed with the topped crude
leaving the furnace
Furnace

 Furnace is used to heat the crude oil to the

temperature required for the atmospheric
column feed
 This temperature (350-400 °C) should allow
vaporization of all the side streams plus 20%
of the bottom residue stream
Atmospheric Distillation Tower
 Atmospheric Distillation
tank is a tall vertical
vessel
 The upper portion of the
column (above the feed
point) is called rectifying
section
 The lower portion is
called stripping section
Inside the Distillation Column
 Trays are used to provide contact Trays
between the liquid (condensed
vapor) and the vapor
 Atmospheric distillation column

downcomers
usually contains 30-50 trays
 4-8 trays per side stream plus
similar number above and below
the feed point
 Vapors flow upward through the
tray (perforation, bubble caps, …)
while liquids flows downward
through downcomers
What happen inside the column: trays
 Lighter components of the liquid is
vaporized and flow upward to the
next upper try
 Heaver components of the vapors
are cooled, condensed and flow
down to the lower tray (through
downcomers)
 Accordingly, heavier components
are concentrated on the bottom
stream (residue) and lighter
components are concentrated in
the overhead stream
 Mid size components are
concentrated in the side streams

Molecules
Reflux and Pump-around

 Reflux is provided by condensing the tower

overhead vapors and returning a portion of
the liquid to the top of the column
 Reflux is used to remove the heat from the top
of the tower and increase the fractionation
 Reflux can also be provided at lower point
in the column, pump-around reflux
Side Stream Strippers

 Side streams contains light ends that are in

equilibrium with heavier components
 These light compounds increase the flash
point of the side stream product
 A separate small stripping tower (4-10 trays)
is used to strip the light components and
vent them back to the tower along with
stripping steam
Condenser

 The overhead condenser on

the atmospheric tower
condenses C5 and heavier
fraction of the vapor
 This condensed liquid is the
light gasoline which contains
C3 and C4
 Reflux

LSR Naphtha

Kerose
ne

Kerosene

Pump around 1 Diesel

Diesel

Gas Oil
Steam

Pump around 2
Gas Oil

Crude Oil

Steam

Residue
Cost of Atmospheric Distillation Tower

 For 100,000 bbl/day unit

 Capital Cost 82 MM$
 Utilities Costs
 Water150 tons/1000 bbl
 Steam 450 tons/day

 Power 900 kWh/1000 bbl

 Fuel 52.7 x 106 kJ/1000 bbl

Vacuum Distillation

 Distillation of the residue from the

atmospheric distillation (topped crude)
tower at low pressure (25-40 mmHg)
 Topped crude is heated to 390-450°C in a
furnace
 Steam addition minimize coke formation and
furnace outlet temperature
PFD of Vacuum Distillation
 Distillation of the residue from the atmospheric distillation
(topped crude) tower at low pressure (25-40 mmHg)
 Topped crude is heated to 390-450°C in a furnace
 Steam addition minimize coke formation and furnace outlet
temperature
 Products of Vacuum Distillation
 Gases
 Vacuum Gas oil
 Light
 Heavy
 Lube Oil base
 Vacuum Residue
(Asphalt)
Vacuum Distillation Operation
 Dry Operation
 No steam is added to the topped crude before the
furnace inlet nor to the vacuum column
 Requires highest furnace outlet temperature
 Damp Operation
 Steam is added to the topped crude at the furnace inlet
 Requires intermediate furnace outlet temperature
 Wet Operation
 Steam is added to both the topped crude at the furnace
inlet and the bottom of the vacuum column
 Requires lowest furnace outlet temperature
Operation of Vacuum Column

 The effective pressure of the hydrocarbons

at the flash zone determines the fraction of
feed vaporized at a given furnace outlet
=
Effective pressure Absolute total pressure − partial pressure of steam

 Steam is essential to minimize the pressure

drop between the vacuum inducing device
and the flash zone
Pressure Maintaining Devices
 Steam Ejectors and Barometric Condenser are
used to create vacuum pressure at the top of the
column
1. High velocity steam enters a zone containing low
velocity vapors
2. Steam mix with these vapor and propel them towards
Venturi-shaped diffuser
3. Inside the diffuser, the kinetic energy is converted to
pressure energy carrying
the steam and vapors to

higher pressure zone
.
Cost of Vacuum Distillation Unit

 For 100,000 bbl/day unit

 Capital Cost 60 MM$
 Cooling water and Steam costs

 Sour water treatment

 Utility
 Power 300 kWh/1000 bbl
 Cooling water 150 tons/1000 bbl

 Fuel 31.65 x 106 kJ/1000 bbl

Sulfur Distribution in Fractions

 The sulfur content of different fractions can

be determined based on:
 Type of crude oil
 Sulfur content
 Fraction boiling
range
Nitrogen Distribution in Fractions

 Nitrogen content of
each fraction can be
estimated based on:
 The crude oil nitrogen
content
 The boiling range of
each fraction
Material Balance Around Distillation Unit
Fraction End
Point, ° F
Gases 90
 The following are TBP and gravity mid-percent LSR 180
curves for a 34.2° API Middle East Crude oil Gasoline
with 1.45% Sulfur and 0.29% Nitrogen. H. Naphtha 330

Assume a 100,000 BPCD crude oil feed rate Kerosene 500

to the atmospheric crude unit L. Gas Oil 610

H. Gas Oil 800

1. Make a complete material balance around an
atmospheric crude distillation y = -7E-08x 6 + 2E-05x 5 - 0.0016x 4 + 0.0745x 3 -
TBP
2. Make complete sulfur and 1.6631x 2 + 23.878x + 77.494
R² = 0.9992

nitrogen weight balance for

the feed and products

T, ° F

API
.
API

y = -2E-05x 4 + 0.0032x 3 - 0.2085x 2 + 4.1735x +

41.008
R² = 0.5138
Vol%
 Fraction End
Point, ° F
TBP
y = -7E-08x 6 + 2E-05x 5 - 0.0016x 4 + 0.0745x 3 - 1.6631x 2 + 23.878x + 77.494
Gases 90
R² = 0.9992
LSR 180
Gasoline
H. Naphtha 330

Kerosene 500

L. Gas Oil 610

H. Gas Oil 800

T, ° F

API
API

y = -2E-05x 4 + 0.0032x 3 - 0.2085x 2 + 4.1735x + 41.008

Vol% R² = 0.5138
 Material Balance
End
vol% API BPCD Lb/BPD Lb/h wt.% wt.% S S, Lb/h wt.% N N, Lb/h
Point, °F
Feed
Gases 90
LSR Gasoline 180
H. Naphtha 330
Kerosene 500
L. Gas Oil 610
H. Gas Oil 800
Atmospheric
Residue
Design of Crude Oil Preheat Train
 Crude oil is heated in heat exchanger
 Light ends are separated in preflash column
 Liquid from preflash are heated in a furnace
 Light ends are mixed with hot liquids and fed to
atmospheric tower
Conversion Processes
 Processes which involve chemical reactions
 Objectives of Conversion Processes:
1. Convert low value materials to high value/high demand
products
 Cracking
 Alkylation
 Polymerization
2. Improve product characteristics
 Reforming
 Isomerization
3. Remove impurities and undesired compounds
 Hydrotreatment
Cracking Processes
 Convert low-value heavy fractions into lighter
products by cracking long chains in shorter chains
 Cracking requires energy
 Can be done thermally at high temperature (thermal
cracking or coking processes)
 Involve free radical mechanisms yielding variety of by-
products
 Alternative route to reduce the amount of energy
and increase selectivity is using catalyst
 Catalytic Cracking
 Catalytic Hydrocracking
Thermal Processes-Coking
 Coking is sever cracking process
 Used to convert the “bottom of barrel” into
valuable products (naphtha and gas oil)
 Coking Processes is needed to:
 Keep pace with the growing demand for transportation
fuels
 More stringent legislation
 The opportunity for significant improvement in

Gases
refinery profit margins

Distillates
Feed

Coke
Coking-Chemistry
 Thermal cracking processes proceeds via
free radical-mechanism which involves the
following steps

• Session of C-C bond

Initiation

• Cracking, Addition, Chain Transfer,

Propagation Condensation, and Polymerization

• Radical Recombination
Termination
Coking-Mechanism
 Initiation
↓ • •
R − CH2 − CH2 − R' 
→ R − C H2 + C H2 − R

 Propagation
 Chain transfer
• •
R − C H2 + R − CH2 − CH2 − R' 
→ R − CH2 − CH2 − R + R' − C H2
 β-Session • •
R − CH2 − C H2 
→ R + CH2 = CH2

 Hydrogen Substitution
• •
R' − CH2 − CH2 − CH3 + R 
→ R − H + CH3 − C H − CH2 − CH2 − R'

 Termination • •
R + R' 
→ R − R'
 Radical Recombination •
R + H 
•
→ R−H
• •
H + H 
→ H2
Thermal Cracking-Secondary Reactions
 Hydrogen Transfer
Naphthenes +Olefins → Aromatics + Paraffins
 Condensation/Polymerization
Ar − Ar + 2nArH 
→ 2 Arn +1 + 2H2

=
CH CH2 + R −=
CH CH − R' 
→

R’
R

 These reactions lead to coke

formation
Coking Process: Feed
 The following fractions can be used as feed for
coking process
 Residue (Atmospheric or Vacuum)
 Tar from thermal crackers
 Catalytic cracking “decant oil”
 Coal tar pitch
 Hydrogen to carbon ratio is the main characteristic
for feedstocks. It can be quantified by:
 Ramsbottom Method test
 Conradson Carbon Test
 Microcarbon Resid Test
Characteristic of Petroleum Products
4 CH4

Hydrogenation
Hydrogen/Carbon Atomic Ratio

3
LPG
naphthaKerosene
Jet
Diesel Gas
2 oil
Crude
oil
Atm
Vacuum
Residue
Residue
1
Cracking
Coke
0
0 10 20 30 40 50
Average Carbon Number (atoms/molecule)
Typical Products from a Barrel of
Coker Feedstock

Source: Foster Wheeler, SYDECSM delayed coking

Coking Process: Products
 Coke
Goke weight% = 1.6 (wt .% Conradson Carbon )

 Gasoline
= 1.29 + 0.343 (wt .% Conradson Carbon )
Gasoline weight%

 186.5 
Gasoline Vol% =   ( Gasoline weight% )
 131.5 + ° API 
 Gases
( ) = 7.8 + 0.144 ( wt.% Conradson Carbon )
Gases C 4− weight%

 Gas oil
100 − (Coke weight% + Gasoline weight% + Gases weight% )
Gas Oil weight% =

 155.5 
Gas Oil Vol% =   ( Gas oil weight% )
 131.5 + ° API 
Gas Composition
 Typical gas composition, sulfur- Component Mole %
free basis is as follow: Methane 51.4
Ethene 1.5
Ethane 15.9
Propene 3.1
Propane 8.2
Butenes 2.4
1-Butane 1.0
n-Butane 2.6
H2 13.7
CO2 0.2
Total 100
Delayed Coking Products
 Naphtha is split into two fractions
 Light naphtha (35% with 65°API)
 Hydrotreated and either isomerized or blended with gasoline
components
 Heavy naphtha (65% with 50°API)
 Hydrotreated and reformed
 Gas oil is split into two fractions
 Light gas oil (67% with 30°API)
 Hydrotreated and catalytically cracked
 Heavy gas oil (33% with 13°API)
 Used as fuel oil or sent to vacuum unit
Sulfur and Nitrogen Distribution
 Sulfur Distribution  Nitrogen Distribution H. Naphtha
1%
LCGO
2% HCGO
Gas, 30
22%
L Naphtha, 2
H Naphtha, 3

LCGO, 15

HCGO, 20
Coke
75%

Coke, 30
Comparison of Predicted and Observed Yield

 Compare predicted and observed Feedstock I II

coke and gasoline yield for the °API 15.7 10
following feedstocks? Conradson
10.8 21.6
Carbon, wt. %
Observed
20.4 23.8
Gasoline (vol%)
Wt.% coke=1.6 (wt% Conradson carbon)
Observed Coke
coke (feed I) = 17.28 wt.% (Fair agreement) 22.3 33.4
(wt%)
coke (feed II) = 34.6 wt.% (good agreement)

wt.% gasoline=11.29+0.343(wt% Con carb) vol.% Gasoline = 186.5/(131.5+API)+wt.%

Gasoline (feed I) = 14.9 wt.% Gasoline (feed I) = 18.4 vol% (good agreement)

Gasoline (feed II) = 18.7 wt.% Gasoline (feed II) = 24.6 vol% (good agreement)
Products of Coking: Petroleum Coke

 Type of coke depend on the process, the

operating condition and the feedstock
 Coke produced from coking is called
“Green Coke”
 It contain high molecular weight hydrocarbons
(volatile materials)
 Green Coke can be used for:
 Fuel grade coke
 Anodes or electrodes for Al and steel
production
 Requires calcination at 1000-1300°C
Sponge Coke
 Hard porous, irregular shaped lumps with
size from 20˝ to fine dust
 Have high surface area
Needle Coke
 Produced from highly aromatic feedstocks
and operating at high pressure and high
recycle ratio
 Has microscopic elongated crystalline
structure
 Ideal for electrode production
Shot Coke
 Produced unintentionally
 Produced during upsets or from very heavy
crude oil or high sulfur content residues
 Clusters of shot-sized pellets
 Operation conditions are adjusted to avoid
shot coke formation
 No market
 Sign of operational troubles
Uses of Petroleum Coke
 Fuel, “Fuel Grade Coke”
 85% Carbon, 5% hydrogen, 10% S, N, O, V, and Ni
 Manufacture of anodes for aluminum production,
“Anode coke”
 Direct use as carbon source for manufacture of
elemental P, CaC, and SiC
 Manufacture of electrodes for use in electric
furnace production of elemental P, CaC, and SiC
 Manufacture of Graphite
Coking Processes
Coking Processes: 1. Delayed Coking
 Developed to minimize the yield of residue fuel oil
 Feed can be vacuum residue, aromatic gas oils, and
thermal Tars
 The furnace temperature exceeds the coking
temperature without significant coke formation by
using very high velocity (very low space time in the
heater)
 Using isolated drums, the heater effluent is
allowed sufficient time for coking to take place
Delayed Coking Process
 The feed (after heat exchangers) enters the bottom of fractionator
where it mixes with the condensed recycle
 The mixture is heated to the coking temperature in a furnace heater
 Coking is prevented by using short space time and injection of steam or
boiler feedwater
 The mixture is sent to one of the two coking drums
 The overhead vapor stream is sent to the fractionator to rejoin the feed
and the coke is formed in the drum
 When the drum is filled, the hot
stream from the furnace is directed
to the other drum and the coke
is removed from the first drum
by mechanical or hydraulic means
 The overhead stream from the
fractionator is sent to a vapor
recovery unit where gases and
naphtha are separated
Delayed Coking Process
Delayed Coking Unit
Delayed Coking Operation
 Furnace temperature ~ 500° C
 Higher temperature produces more shot coke
 Requires furnace tubes decoking at shorter intervals (few months)
 Pressure
 15-90 psig
 Hot fresh liquid feed is charged to the fractionator two to
four trays above the bottom of the vapor zone
 The hot vapors from the coke drum are quenched by the cooler
feed liquid
 Materials lighter than the desired coke drum feed is stripped from
the fresh feed
 The fresh feed liquid is preheated (energy saving)
Coke Removal
 When the coke drum is filled to a safe margin the
heater effluent is switched off to the empty coke
drum
 The drum is isolated, steamed, cooled by filling
with water, opened and drained, the coke is
removed
 Coke removal can be done by mechanical means or
by hydraulic means
 Drill or reamer
 High pressure water jets
 Coke is collected and transported
Delayed Coking Cycle
 Typical cycle time is about 24 hours
 Shorter cycle time increase capacity
 Shorter cycle time results in lower liquid
yield and shorter drum life
Operating Conditions
 Main operating conditions:
 Heater outlet temperature
 Fractionator pressure
 Temperature of the vapors raising to the gas oil withdraw tray
 Increasing the heater temperature or the fractionator
pressure:
 increases the cracking reaction
 increase yield of gas, naphtha, and coke
 reduces the yield of gas oil
 Fractionator pressure has the same effect as the heater
temperature
 More recycle is condensed and sent to the furnace
Coking Processes: Fluid Coking
 Continuous Fluidized-Bed Process
 Enough coke is burned to satisfy the heat
requirement of the reactor and the feed preheat
 20-25% of the coke produced in the reactor
 The rest of the coke is withdrawn from the burner
 Advantages
 Operates at once through (no recycle)
 No external heat fuel supply required
 Disadvantage
 Coke cannot be used as heating element if have high
sulfur content
Coking Processes: Fluid Coking

scrubber

Burner
Reactor
Coking Processes: Flexicoking
 The feed is preheated to 370°C in a furnace and sprayed
into the reactor
 The sprayed feed contacts a fluidized bed of hot coke
 This hot coke is recycled to the reactor from the heater at
sufficient rate to provide enough heat to maintain the
reactor at 520° C
 Provide both sensible and latent heat of vaporization
 The cracked vapors pass through cyclone separators in the
top of the reactor to separate the entrained coke particles
 The vapors are quenched where some of the high boiling
point cracked vapors are condensed and recycled to the
reactor
Coking Processes: Flexicoking
 Coke is deposited as thin film on the surface of existing
coke particles in the reactor fluidized bed which is stripped
by steam
 Coke flows from the reactor to the heater
 Heated to 600°C
 Coke flows from the heater to the gasifier
 Reacts with air and steam to produce flue gas which flow to the
bottom of the heater to provide heat
 About 60-97% of the coke is gasified
 Coke gas leaves at the top
of the heater
 Entrained coke is removed and
the gas used as fuel gas (CO, H2,
CO2, and N2)
Coking Processes: Flexicoking

scrubber

Gasifier
Heater
Reactor
Coking Processes: Flexicoking
Yield from Coking Processes

Yield, Wt.%

Delayed Coking Fluid Coking Flexicoking

Gas 9.3 11.8 11.8

Light Naphtha 2.0 1.9 1.9

Heavy Naphtha 8.0 7.8 7.7

Gas Oil 46.7 50.4 50.4

Coke 34.0 28.1 28.1

Net Coke 34.0 22.4 2.1

Capital Costs and utilities for coking
processes
 Capital cost of delayed coking and fluid
coking is about the same
 Flexicoking is about 30% more
 Utility requirements for flexi and fluid coking
is higher than those of delayed coking
 Fluidized bed
 More power is required for flexicoking
process for air blower
Visbreaking
 Relatively mild thermal cracking process
 Used to reduce the viscosity and pour point of
the residue to meet the fuel oil specifications
 Or to reduce the amount of light heating oil
that is required to blend with the residue to
meet the fuel oil specifications
 Produce gasoline and gas oil that is catalytically
cracked
Visbreaking
 Long paraffinic side chains attached to
aromatic rings are the primary cause of high
pour point and viscosity for paraffinic base
residue
 Operating condition favors breaking of the
side chains and subsequent cracking of these
chains
 Limited cracking reaction to avoid formation
of polymerization products
Visbreaking
 The degree of viscosity and pour point
reduction is function of the composition of
the residue feed
 Waxy feedstocks achieve pour point
reduction from 15-35°F and final viscosities
from 25-75% of the feed
 High asphaltene content in the feed reduces
conversion and therefore yield smaller
change in the properties
What Happens during Visbreaking?
 Cracking of the side chains attached to
cycloparaffins and aromatic rings
 The cracking takes place at or near the ring
 Cracking of resins to light hydrocarbons
(olefins) and other compounds that converts
to asphaltenes
 Some cracking of naphthene ring
 At T > 480°C
Severity of Visbreaking
 The severity of the process can be
expressed in terms of:
 Yield of materials boiling below 166°C
 Vol.% Gasoline (US)
 Vol.% (Gas + gasoline) (Europe)

 The reduction of the viscosity

 The amount of standard cutter stock needed to
blend the visbreaker tar to No. 6 fuel oil
Visbreaking Processes
 The reaction is time-temperature dependent
 There are two modes of operation
1. Coil Cracker
 Higher furnace outlet temperature (500°C)
 Short reaction time (1-3 min)
2. Soaker Cracker
1. Lower furnace outlet temperature (440°C)
2. Long reaction time
 Soaker cracker requires less energy and less
shut downs to remove coke
Soaker Visbreaker
Soaker Visbreaker
Coil Visbreaker
Visbreaking Operation
 The feed is introduced to the desired temperature
 500° C for coil cracking process
 440° C for soaker cracking
 In soaker cracking process, as the feed leaves the heater it
enters a soaking drums which provide additional cracking
time
 Visbreaking process operates at
 High pressure for liquid phase process
 Low pressure for 20-40% vaporization at the furnace outlet
 Fuel consumption accounts for 80% of the operating cost
(soaker visbreaking requires less energy)
 Soaker visbreaking requires less capital costs
Yield of Visbreaking Process
 Visbreaking process produces Gas, Naphtha,
Gas Oil, and Tar
 Gas ~2.5 wt.%
 Naphtha ~ 6 wt.%

 Gas oil ~ 15 wt.%

 Tar ~ 80 wt.%
Petroleum Refining and
Processing
CHEG 421

Dr. Ahmed Abdala

c
Catalytic Cracking
 Most important and most widely used refinery
process
 Convert heavy oil into more valuable gasoline and
lighter products
 Over 10 MMBPD of oil is processed via catalytic
cracking
 Catalytic Cracking is
Thermal versus Catalytic Cracking
Compared to Thermal
Wt.%
Cracking:
Product Thermal Catalytic
Cracking Cracking
• Catalytic Cracking Gas 6.6 4.5
produces more gasoline Propane 2.1 1.3
with higher octane number Propylene 1.0 2.0
i-butane 0.8 2.6
• Catalytic Cracking n-butane 1.9 0.9
produces gases with higher Butylene 1.8 2.6
olefins content C5+ gasoline 26.9 40.2
Light Cycle Oil 1.9 33.2
Decant Oil 7.7
Residual Oil 57.0 -
Coke - 5.0
Catalyst Deactivation and Regeneration

 Due to the cracking reaction, coke is produced

and deposited on the catalyst reducing its activity
 Regeneration of the catalyst by burning the coke is
necessary
 Catalyst continuously moved from reactor to
regenerator and back to reactor (moving/fluidized
bed)
 The cracking reaction is endothermic and heat can
be supplied by the regeneration heat
 Reactor temperature ~500°C
 Feed temperature 260-425°C
 Regeneration exit temperature 650-815°C
Catalytic Cracking Unit Layout

Animation
Classification of Cat Cracking Processes

 Moving-bed
 Thermafor Catalytic Cracking (TCC)
 Fluidized-bed (much more popular)
 Fluid Catalytic Cracking (FCC)
 Riser cracking unit
 Rise is a pipe that transport the catalyst from the
regenerator to the reactor
 Bed cracking unit
Location of the Cracking Reactions

 Bed-type FCC
 Dense phase fluidized-catalyst
 Most of the cracking occurs in the reactor bed

 Reaction is controlled by the depth of the bed

and temperature
Location of the Cracking Reactions

 Rise-type FCC
 Most of the reaction occur on the riser where
the catalyst activity and the temperature are at
their highest
 Minimum bed level in the reactor
 Control of the temperature and reaction by
varying the rate of circulation of the catalyst
 Higher conversion and better selectivity
 Shorter and better controlled reaction time
Side by Side Unit

Reactor
Riser
termination

S
Reactor
Side Regenerator
Regenerator

valve stripper

Riser
Riser
Feed Air/Catalyst
Feed
Injection Injection Distribution
S
Side Side valve
S valve
Side valve
Side
Side by Side Unit
Orthoflow/Stacked Type Unit
Inside the Riser
 For the riser process, the hot feed contact the
catalyst at the base of the feed riser line
 The feed is vaporized by the heat from the hot
regenerated catalyst and heated to the required
temperature
 Mixture of HC and the catalyst travels up through
the riser into the reactor
 The reaction starts once the feed contacts the hot
catalyst and continues until the vapors are
separated from the catalyst
Inside the Reactor

 Mixture of HC and the catalyst travels up

through the riser into the reactor
 The reaction starts once the feed contacts
the hot catalyst and continues until the
vapors are separated from the catalyst
 The HC vapors are sent to fractionator
 The catalyst are circulated back to the
regenerator
FCC Regenerator
Before and in the Regenerator
 Catalyst leaving the reactor contains HC
adsorbed on the surface and deposited coke
 Removed by steam before the regeneration
 Coke is burned in the regenerator using hot air
 Catalyst temperature rises to 600-850°C
 Air flow rate controls the regeneration
temperature
 Coke is either burned to CO or CO2
 If Coke is burned to CO, the flue gas must be burned to
CO2 to recover the available fuel energy
 The regenerated catalyst contains from 0.01 to 0.4
wt.% residual coke
FCC Catalyst

 Amorphous Silica Alumina Catalyst (old catalyst)

 Natural
 Synthetic
 Crystalline Silica alumina Catalyst (new catalyst)
 Zeolite
Zeolite

 Compounds of aluminum, silicon, and oxygen

containing strongly acid sites.
 have an extremely high surface area, which provides
many sites where reactions can occur
Cracking Reactions

 Primary Reactions
 Paraffin → Paraffin and Olefin
 Alkyl Naphthene → Naphthene + Olefin

 Alkyl Aromatic → Aromatic + Olefin

Catalytic Cracking Mechanism

 Mild thermal Cracking

n-C 8 H 18 
→ CH 4 + C 5 H 11 -CH=CH 2
 Proton Shifting
o
C 6 H 13 - C H 2 -CH 3 +H 2O + [ Al -O-Si]
o
+
→ C 6 H 13 - C H-CH 3 + [HO-Al-O-Si] -

Catalytic Cracking Mechanism

 Beta Session
C 5 H 11 -CH-CH 3 
→CH 3CH=CH 2 + CH 2CH 2CH 2CH 3

 Rearrangement
+ +

C H 2CH 2CH 2CH 3  CH 3 C H-CH 2CH 3
CH CH
3 3
+
CH 3 − CH − C H 2 
 CH 3 − C − CH 3
 C+ Stability:
+

Tertiary > Secondary > primary

 Hydrogen Ion transfer
CH 3
+
CH 3 C -CH3 + C 8 H 18 
→CH 3 CH -CH 3 + C 5 H 11 - C H-CH 2 -CH 3
+ CH 3
Cracking of Paraffins

 Produces gases with high content of C3 and C4

 Reaction rates and products depend on:
 Size and structure of paraffins
 Tertiary carbon are easily cracked
 Quaternary carbon are very resistant
 Isomerization to branched structures
 Aromatics formation through secondary reactions that
involve olefins
 The catalyst effect on the reaction rate is more
pronounced as the chain length increases
Olefin Cracking

 Olefins (originally present or produced

through the thermal cracking step) undergo
the following reactions:
 Carbon- Carbon bond session
 Isomerization
 Polymerization
 Saturation, aromatization and carbon formation

Aromatization
 Olefin → Isomerization
Saturation
Olefin Cracking

 Hydrogen transfer reaction for branched

olefins produces high iso-to normal paraffins
higher than the iso-to normal ratio of the
parent olefin
 Naphthenes act as hydrogen donor in
transfer reactions with olefin to yield
isoparaffins and aromatics
Cracking of Naphthenes

 Dehydrogenation
 Catalytic and produces aromatics
 Extensive for C9 naphthenes

 Carbon-carbon bond session on the side

chain
 Carbon-carbon bond session on the ring at
temperature above 540°C
 Produces more saturated gases than those from
cracking of paraffins
Cracking of Aromatics

 Aromatics with side chain with less than 3

carbon atoms
 Not very reactive
 Aromatics with longer side chain
 Clean split of the side chain
 Produces benzene
Advantages of Zeolite Catalysts

 Compared to amorphous silica alumina catalysts,

Zeolites provides
 Higher gasoline yield at given conversion
 Gasoline with higher content of paraffinic and
aromatic HCs
Amorphous
Zeolites
 Lower coke yield catalyst
Conversion 55 65
 Higher i-C4 production
 Higher overall conversion per Coke, wt.% 4 4
C5+ Gasoline,
pass without overcraking vol%
38 51

C3-, wt.% 7 6
C4’s, vol% 17 16
Zeolite Activity

 Due to high activity of zeolite, the catalytic

effect can be achieved with only 10-25% of
the circulating catalyst
 Amorphous silica alumina type catalyst is
used as the reminder
 Higher attrition resistance
 Much cheaper
Effect of Contaminants on catalyst Activity

 Basic Nitrogen, Fe, Ni, V, and Cu acts as

poisons for the catalyst
 Basic nitrogen neutralize the acid sites
 Metals deposit and accumulate on the
catalyst
 Increase the amount of coke and gas
 Reduce the coke burn up on the regenerator
and increase required air
 Nickel effect is 4 times as great as V
Effect of Ni and V on Catalyst Activity

 Effect of Nickel can be offset by adding

passivators to the feed catalyst
 Effect of Vanadium can be offset by adding metal
traps compounds
such as Tin, Barium and
Strontium Titanates
 Metal removal process
can be also used
 Sodium also affect the
catalyst activity
FCC Pretreating
 Producing gasoline and gas oil with accepted sulfur and
nitrogen content requires either the feed or the products
to be hydrotreated
 Hydrotreating the feed increases the yield of naphtha and
lighter components while maintaining the % olefin and ON
of the naphtha
 Hydrotreating units are either:
 HDS
 Mild hydrocracking (MHC)
 Partial conversion hydrocracking unit (aromatic hydrogenation)
 Sulfur content in the final product has to be less than 85
ppm
FCC Pretreating

 Partial conversion hydrocracking units

requires higher operating conditions than
HDS and MHC units
 HDS and MHC (800-1000 psig)
 Partial conversion HC (1400-1600 psig)

 Partial conversion HC produces diesel with

higher cetane number compared to MHC
units
 More aromatics with MHC than with partial
conversion units
Important Definitions
 Activity
Ability to crack gas oil to lower boiling fractions
 Catalyst/Oil ratio
Lb catalyst/lb feed
 Cycle stock
Portion of the products not converted to naphtha and
lighter products
 Conversion
Volume of feed -Volume of Cycle stock
Converion= x100
Volume of Feed
Important Definitions
 Efficiency
% Gasoline x Conversion
 Recycle Ratio
= Volume Recycle / Volume of fresh feed
 Selectivity
The ratio of the yield of desirable products to the yield of
undesirable products (coke and gas)
 Space velocity: WHSV (LHSV)
weight/hr (volume/hr) of feed per weight (volume) of
catalyst
Process Variables

 Feedstock
 Temperature
 Catalyst/oil ratio
 Space velocity
 Catalyst type and activity
Conversion
 Conversion increases with the increase of
 Reaction temperature
 Catalyst/oil ratio
 Catalyst activity
 Contact time (decrease of space velocity)
 Space time Increasing conversion not necessarily
mean increasing % gasoline
 Increasing temperature increases conversion but
may increase gas and coke yield as well as gasoline
octane number
Conversion

 Increasing conversion not necessarily mean

increasing % gasoline
 Increasing temperature increases conversion but may
increase gas and coke yield as well as gasoline octane
number
 The conversion is limited by the coke burning
ability of the regenerator
 Air compression limitations (oxygen may be added to
air)
 After burning temperature limitations
FCC operating condition

 Generally FCC units are operated at

 Maximum regeneration temperature 1200-
1500°F (650-820° C)
 Reactor temperature 850-950° F (450-510° C)
to minimize coke formation and gas production
 Reactor Pressure 15-20 psig
 Higher pressure would increase coke formation
and degree of saturation
FCC Heat Recovery
 Sensible heat form hot flue gases (1200-1500°F) from the
regeneration section is recovered through waste heat
boilers
 Heat of combustion of CO to CO2 is also recovered by
installing CO-burning waste heat boilers
 Power recovery turbines can also be used to recover more
energy hp kW
Waste heat boiler only 45 34
Power recovery only 78 58
Waste heat boiler only + Power recovery 106 79
Co burning waste heat boiler 145 108
. Co burning waste heat boiler + power recovery 206 154
Energy recovered per lb/s flue gas
FCC Yield Estimation

 Yield of FCC units can be estimated based

on
 The catalyst type
 The feed type
 Coke burning ability
 We will discuss example of yield Estimation
based on zeolite catalyst
 Different set of charts should be used for
amorphous silica alumina catalyst
Conversion versus Coke%
 Conversion can be
estimated based on the
coke burning ability of
the regenerator and
the feed characteristics
 The regenerator ability
will determine the coke
wt.%
 The design conversion is
estimated based on the
max allowed coke%
Fuel Gas Yield

 Based on the
conversion and
feed characteristic
the yield of fuel
gas (C2 and
lighter) is
estimated
LPG Yield

Similarly, the yield of

LPG (C3 and C4) can
be estimated based

LPG, C3 & C4 liquid vol.%

on conversion and
the characterization
factor
C3 Yield

 Yield of C3
paraffin and olefin
can be estimated
based on
conversion and
feed API
C4 Yield

 Yield of C4
paraffins (normal
an iso) and C4
olefin can be
estimated based
on conversion
and feed API
C5+ (gasoline) Yield
 Yield of C4 paraffin
(normal an iso) and C4
olefin can be estimated
based on conversion
and feed
characterization factor
Yield of Light and Heavy Gas Oil

Yield of
C3 + C4
C5+ gasoline
Light Gas Oil
Heavy Gas Oil
be estimated based on
conversion and feed
characterization factor
(figure shown is for
Kw =11.8)
Yield of Light and Heavy Gas Oil

 Yield
 C3 + C4
 C5+ gasoline
 Light Gas Oil
Heavy Gas Oil

Yield, liquid vol%



are estimated based

on conversion and
feed characterization
factor (12.35)
Sulfur Distribution

 % sulfur in product can be estimated based

conversion
Product density
Capital Cost for FCC Units
 The capital cost for a typical 50000 BPD is about
MM$ 150-200
 Other cost includes:
 Feed Fractionation
 Off-gas and product treatment
 Cooling water, steam, and power
supply
 Initial catalyst usage
 Catalyst Replacement
 Utilities
 Steam, Power, Cooling water, Fuel
In class Excersice

 For a 23.0 API catalytic cracker feedstock

with boiling range of 600 to 900° F and
containing 1.5 wt.% sulfur. Make an overall
weight and volume material balance for a
50000 BPCD feed rate when operating at
70% conversion using a zeolite catalyst.
 First calculate the feed Kw;
1

1 600 + 900  3
 460 + 
TB 3
 2 
K= = = 11.63
W
G 141.5
23 + 131.5
Overall Material Balance around the FCC
vol% BPCD API (Lb/h)/BPD Lb/h wt.% wt.% S S, Lb/h

Feed 100 50000 23.0 100 1.5

Coke at 70% conv

C2 and lighter
C3=

C3
C4=
i-C4
n-C4
C5+ Naphtha
TGO
LGO

HGO

Total
Petroleum Refining and
Processing
CHEG 421

Dr. Ahmed Abdala

Catalytic Hydrocracking
 Cracking of heavier feedstock the presence of
hydrogen to produce more desirable products
 Better balance of gasoline and distillates
 Improved gasoline pool octane quality
 Use high pressure, high temperature, a catalyst,
and hydrogen
 Processes feedstocks are difficult to process by
either catalytic cracking or reforming
 High polycyclic aromatic content
 High concentrations of the sulfur and nitrogen
compounds
Advantages of Hydrocracking
 Production of high amount of i-C4 in C4 fraction
 Complementary to FCC
 FCC upgrades atmospheric and vacuum gas oil
 more easily cracked (high amount of paraffins)
 Hydrocracking upgrades cycle oil and coker distillates
 More difficult to crack (more aromatics)
 Growing interest in Catalytic hydrocracaking
 Higher demand for gasoline and jet fuel
 Availability of hydrogen as by-product of reforming
 Environmental concerns that limits sulfur and
aromatic compounds concentration in motor fuel
Hydrocracking Feedstock and Products
Feed Products
 Hydrocracking is a Kerosine Naphtha
versatile process:
SR Diesel Naphtha/Jet Fuel
Atm GO Naphtha, Jet fuel, diesel
 Mode of Operations Vac GO Naphtha, Jet fuel, diesel, lube oil
 Hydroprocessing FCC LCO Naphtha,
 Residual feedstock
FCC HCO Naphtha/distillates
 Hydrocracking
Coker LCGO Naphtha/distillates
 Distilled feed
Coker HCGO Naphtha/distillates
 The two processes use
different catalyst and operates at different operating conditions
Hydrocracking Reactions
 The mechanism of hydrocracking reaction is that of
catalytic cracking reaction with hydrogenation
reaction superimposed
n-C13 → n–C9 + C4= (endothermic cracking step)
C4= + H2→ n–C4 (exothermic hydrogenation)
 Cracking and hydrogenation steps are
complementary
 Cracking provides olefins for hydrogenation
 Hydrogenation provides heat for cracking
Cracking of aromatics

 Initial hydrogenation of condensed aromatics

(Partial saturation)
 This reaction facilitate subsequent cracking of
the rings as will be shown
 Subsequent cracking of the condensed rings
 Ring separation and opening
 Side chain hydrocracking and isomerization
Cracking of Aromatics
H13C6 H13C6
2H2

C2H5 C3H7

Partial saturation

4H2
Ring Cracking

R1 C2H5

+
C3H7
Side Chain Hydrocracking Isomerization

CH3 C2H5

C3H7 C H +

CH3
Isomerization Reactions

 Olefins formed during cracking step is rapidly

hydrogenated maintaining high percent of
isoparaffins in final products
 Prevent reverse reaction to normal paraffins
 Small amount of C3 and lighter gases in product
 Volumetric yield of liquid products is as high as
125% of the feed
 Addition of hydrogenated products which have
higher API than the feed
Hydrocracking Operating Conditions

 Temperature
 Hydrocracking is carried out at catalyst
temperature of 290 to 400° C
 Reactor pressure
 1200-2000 psig
 High hydrogen circulation
 Hydrogen consumption is about 300 scf/bbl feed
Hydrocracking Catalyst
 Catalyst depend on the feed material and desired products
 Crystalline silica-alumina with rare earth metals distributed
to promote hydrogenation
 Rare earth metals such as Pt., W, and Ni
 Higher temperature is used as the catalyst ages to maintain
conversion
 Less naphtha and more gases is produced
 Catalyst regeneration every 2-4 years
 Regeneration by burning of coke and other deposits
 After several regenerations, the catalyst must be replace
Hydrocracking Feed Preparation
 Metallic salts, oxygen, organic nitrogen compounds, and sulfur may
poison the hydrocracking catalyst
 Feed is hydrotreated to:
 Saturate olefins
 Remove S, N, and O compounds
 NH3 does not permanently poison the catalyst as organic nitro-
compounds do
 Low concentration of H2S catalytically inhibit saturation of aromatic
rings
 Hydrogenation reactions are highly exothermic
 Saturation reactions
 Denitrogenation and desulfurization
 Water content of the feed must also be reduced to less
than 25 ppm
 At the high hydrocracking temperature, steam causes collapse of
catalyst and agglomeration of the rare earth atoms
Hydrocracking Process

 Fixed bed catalytic process

 Liquid down flow
 One or two stages depending on:
 The size of the unit
 Desired products
 Single-stage permit complete conversion to gasoline
and lighter product through recycling of the heavier
material
GOFining Process (Exxon Mobile)

 Fixed bed regenerative process

 Molecular sieve catalyst
 Impregnated with a rare earth metals
 Single or two stage process

 Operating Conditions
 350-420°C
 200-2000 psig
 Depends on age of the catalyst, desired
product, and feed type
Process Variables and Severity

 Severity is measured by the degree of

conversion of the feed to lighter products
 Variables:
 Temperature
 Pressure
 Space velocity
 Hydrogen consumption
 Nitrogen content of the feed
 H2S content of the gases
Process Variables
 Temperature
 Primary variable (Reaction rate double by increasing the
temperature by 10° C)
 Less effect on conversion
 Temperature has to be increased to compensate for loss of the
catalyst activity
 Pressure
 Affect the PH2 and PNH3
 Conversion increases with increasing PH2 and decreases with PNH2
(H2 effect dominates)
 LHSV = liquid flow rate (BPD)/catalyst volume (bbl)
 As the feed rate increases, the conversion is lowered
 This can be compensated by increasing the temperature
Effect of Impurities
 Nitrogen:
 N2 greatly affects the catalyst activity due to contact with organic nitrogen
compounds which in turn deactivate the catalyst and therefore reduces the
conversion
 H2S
 H2S has a catalytic effect which reduce the saturation of aromatics which
leads to:
 High ON naphtha
 Very low smoke point jet fuel
 Corrosion problems
 Decrease Catalyst activity
 Heavy polynuclear aromatics
 Formed due to the hydrocracking reactions
 Can build up if the bottom of the fractionator is recycled
 High concentration causes fouling in heat exchangers
Hydrocracking Yield
1. Estimate light naphtha (C5-180°F) yield
 Figure 7.3 based on API and Kw of the feed
2. Estimate Heavy naphtha (180-400°F) yield
 Figure 7.4 using the yield of light naphtha and Kw of the feed
3. Calculate the yield of butanes
 LV% i-C4=0.377*(LV% of Light Naphtha)
 LV% n-C4=0.186*(LV% of Light Naphtha)
4. Calculate the wt.% of propane and lighter
 Wt.% C3 and lighter =1.0+0.09*(LV% of Light Naphtha)
 Composition: 20% C1, 15 C2, 65% C3, by mole
 Composition: 8.8% C1, 12.4 C2, 78.8% C3, by weight
5. API of the product is estimated by estimating the KW of each stream
(Figure 7.5)
6. Convert the flow rates to mass flow rate
7. Estimate the flow rate of 400+ fraction by difference
Yield of Hydrocracking: Naphtha Yield
Products Kw and API

 Based on mid boiling point of the product and Kw

of the feed
 G can be calculated from KW:
3
TB
G =
KW
 Calculate API from G
Hydrogen Balance

 Hydrogen Consumption: from figure 7.4

based on feed KW
 Add hydrogen consumption for sulfur removal
 Hydrogen on the feed and product is
estimated from figure 7.6 based on the KW
and TB of each fraction
 Hydrogen content for heavy naphtha is about
13.9 wt.% (do not use figure)
 Hydrogen in solution = 1 lb/bbl feed
H2 in Feed and Product
Example

 A hydrocracker feedstock has a boiling

range of 650 to 920°F and API of 23.7° and a
sulfur content of 1.7 wt.%. If the
hydrocracking hydrogen consumption is
1500 scf/bbl of feed and the feed rate is
7500 BPD, determine:
 Total hydrogen consumption
 Barrels of gasoline and Barrel of jet fuel
produced per day
Overall Material Balance
lb/hr
Component vol.% wt.% BPD API lb/h wt.% S lb/h S Kw
from BPD
Feed 100 100
H2, SCF/bbl
H2S
C3-
Products

N-C4
C5-180° F
180-400° F
400-520° F
Total
H2 Balance
Component wt.% lb/h lb/h H2
H2S
C3-
n-C4
OUT

C5-180° F
180-400° F
400-520° F
H2 in solution, 1 lb/bbl
Total
Feed
Hydrogen
In

Total
Added H2
Total
Cost
 Capital Cost depend on
the severity of the process
(hydrogen consumption)
 Other costs include
 Initial catalyst
($150/BPD)
 H2 generation and supply
 Spare H2 recycle
compressors
 Recovery of gases
 Feed fractionation
 Sulfur recovery
 Cooling water, steam,
and power supply
Petroleum Refining and
Processing
CHEG 421

Dr. Ahmed Abdala

Hydrotreating

 Catalytic Processes
 Objectives
 Stabilize products
 Reduce olefin and aromatic content
 Remove objectionable heteroatoms elements
from products or feedstock
 Remove S (HydroDeSulfurization or HDS)
 Remove N (HydroDeNitrogenation or HDS)

 Remove O (HydroDeOxygenation or HDO)

 Remove Metals
Product Stabilization

 Olefins and aromatic are very active

compounds
 Diolefins are gum-forming materials
 Stabilization converts olefins and diolefins to
paraffins and aromatics to naphthenics
H2

3H2
Heteroatoms Removal

 Removal of S, N, O compounds
 Removal of metals
 Necessary for:
 Product specifications (low sulfur diesel fuel)
 Protect downstream catalyst
Hydrotreating Catalyst
 Tungsten and molybdenum sulfides on alumina
 Cobalt and Molybdenum oxide on Alumina
 Highly selective for sulfur
 Easy to regenerate
 Resistant to poisons
 Must be activated by converting them to sulfides
 Nickel oxide, Tungsten oxide, Nickel sulfides, and vanadium
oxide
 Ni-Co-Mo or Ni-Mo system for denitrogenation and
aromatic reduction
 Presulfided with CS2, RSH, or RSSR to activate
 Sulfiding agents can be injected in the feed stream
 Catalyst Consumption from 0.001-0.007 lb/bbl feed
Hydrotreatment Reactions
 Most hydrotreatment reactions are highly
exothermic
 Reactions includes
 Saturation
 H-desulfurization
 H-denitrogenation
 H-deoxygenation
 Hydrogenation
 H-dealkylation
 Side reactions
 Hydrocracking and Coke formation
Aromatic Reduction

 Controlled by the hydrogen partial pressure

 Depend on the feedstock
 Equilibrium yield is favored at low temperature
(exothermic reaction)
 Reaction rate increases with temperature
 High pressure single stage process at 200-300° C
reduces hydrogen consumption required to
achieve certain aromatic reduction
Hydrotreating Reactions: Desulfurization

 Mercaptans
RSH + H2 → R-H + H2S
 Sulfides
R-S-R + 2 H2 → 2 R-H + H2S
 Disulfides
R-S-S-R + 3 H2 → 2 R-H + 2 H2S
 Thiophenes
+ 4 H2 → C4H10 + H2S
S
Hydrotreating Reactions: Desulfurization

 The ease of desulfurization is dependent upon the type of

sulfur compounds.
 Lower boiling compounds are desulfurized more easily.
 The difficulty of desulfurization increases in the following
order:
Paraffins < Naphthenes < Aromatics
 Complete saturation of the ring takes place before sulfur is
removed
 Hydrogen consumption increase in the following order:
Mercaptans< Sulfides< disulfides<Thiophenes
 Hydrogen consumptions is about 70 scf/bbl of feed per
percent sulfur
Hydrotreating Reactions: Denitrogenation

 Pyrrole
NH
+ 4 H2 → C4H10 + NH3
 Pyridine
+ 5 H2 → C5H12 + NH3
N
 Amine
RNH2 + H2 → RH + NH3
 Nitrogen removal requires more sever
operating conditions than does desulfurization
 Hydrogen consumptions is about 320 scf/bbl of feed
per percent nitrogen
Hydrotreating Reactions: Deoxidation and
Dehalogenation
 Phenol
OH

+ H2 → + H2O

 Peroxides
C7H13OOH + 3 H2 → C7H16 + 2H2O
 Hydrogen consumptions is about 180 scf/bbl of feed per
percent oxygen
 Chlorides
RCl + H2 → RH + HCl
Hydrotreating Reactions: Hydrogenation

 Olefins
CH3-CH2-CH2-CH=CH2 + H2 → CH3-CH2-CH2-CH2-CH3
 Diolefins
CH2=CH-CH2-CH=CH2 + 2 H2 → CH3-CH2-CH2-CH2-CH3
 Aromatics
+ 3 H2 →

 Hydrogen consumption are calculated based on

stoichiometric amounts
Hydrotreating Reactions: Hydrocracking

 Appreciable under sever conditions

C10H22 + H2 → C4H10 + C6H14

 Increases hydrogen consumption rapidly

Hydrotreating Operating Conditions

 Feed to hydrogen ratio

 Recycle = 360 m3/m3 feed
 Consumed =36-140 m3/m3 feed
 Temperature
 ~ 250-400°C
 High temperature increases desulfurization and denitrogenation but
also increase hydrocracking
 Pressure
 690-20700 kPa (Hydrogen Partial Pressure)
 Space velocity
 LHSV= Volume of feed @60°F/volume of catalyst bed
 LHSV =1.5 – 8
Hydrotreating Severity

Reaction conditions Reaction

Mild
Olefin Saturation
low T, short τ, low P
Aromatic
Moderate
saturation
Severe
HDS
High T and long τ
Very severe HDN
Ease of dehydrogenation Reaction

 Desulfurization ease depend on the type of

compound to be treated
 In order of increasing difficuilty
Paraffins < naphthenes < aromatics
 The heavier the feed the more difficult the
desufulrization process
 Denitrogenation is more difficult than
desulfurization
Hydrogen Consumption

 Hydrogen required for the hydrotreatment

reactions, chemical hydrogen
 Hydrogen losses
 Lost in equilibrium with light gases (significant
and comparable to chemical hydrogen)
 Absorbed in liquid products (small amount)
 1 lb/bbl feed
 Removed with purge gas
Hydrogen Requirement for a Refinery

 The typical refinery runs at a hydrogen deficit

 As hydroprocessing becoming more prevalent, this deficit will
increase
 As hydroprocessing progresses in severity, the hydrogen demands
increase dramatically
 Trend in more hydroprocessing is driven by several factors:
 Heavier & higher sulfur content crudes
 Reduction in demand for heavy fuel oil
 Increased use of hydrodesulfurization for low sulfur fuels
 More complete protection of FCCU catalysts
 Demand for high quality coke
Hydrogen Sources

 Steam reforming of natural gas is the main source

of hydrogen
 CH4 + H2 O 
→ CO + 3 H2 Reforming

 CO + H2 O → CO2 + H2 Shift

 Absorption of CO2
 Catalytic reforming
 Dehydrogenation and cyclization of paraffins
 Dehydrogenation of naphthenes
 Isomerization of paraffins
Hydrotreating Catalyst

 Cobalt and Molybdenum oxides on Alumina

 Highly selective for sulfur
 Easy to regenerate
 Resistant to poisons
 Must be activated by converting them to sulfides
 Ni-Co-Mo or Ni-Mo system
 Selective for Nitrogen and aromatic saturation
 Presulfided with CS2, RSH, or RSSR to activate
 Sulfiding agents can be injected in the feed stream
Hydrotreating Catalyst

 Catalyst pore size has great impact on the process

at start-of-run (SOR) and as the catalyst ages
 Pore size must be large to reduce diffusion limitation
 Surface area decreases with increasing pore size
 Catalyst consumption is about 0.001-0.007 lb/bbl
feed depending on the severity of the process and
the gravity and metal content of the feed
Hydrotreating Processes
1000
Hydrogen Consumption, SCF/bbl feed

Gas
oil
750

Heavy
Distillates

500
Light
Distillate

250

naphtha

0
0 300 600 900 1200 1500
Pressure, psig
Hydrotreating Process Variables

Temperature 520-645° F

Pressure 100-3000 psig

Hydrogen
2000 scf/bbl feed
Recycle
Hydrogen 200-800 scf/bbl
Consumption feed
Space velocity
1.5-8.0
(LHSV)
Hydrotreatment Processes
 Naphtha Desulfurization
 Hydrogen consumption 50 to 250 scf/bbl (70-100 scf/bbl for each 1
wt% S)
 Vapor outlet about 700° F
 Distillates Hydrotreating
 Produce Ultra Low Sulfur Diesel
 Saturation of olefin to increase cetane number
 Higher hydrogen consumption than naphtha Desulfurization
 Naphtha is produced
 Gas Oil Hydrotreating
 Higher temperature (650° F)
 More expensive unit because it require more intensive
hydrogenation
 More complex strippers
Hydrotreating Processes
Desulfurization Unit

H2S, NH3, water,

C3 and lighter gases
700-800°F

Fractionator
Reactor
100° F

100° F
Separator
Hydrotreatment of Middle Distillates
Cost of Hydrotreating Plant

 Capital cost of 10 MBPD unit is about 12-25 MM$

 The cost increases with the feed density
 Other costs
 Hydrogen generation
 Sulfur recovery
 Catalyst replacement
 $.05/bbl
 Utilities
 Steam, power, cooling water
 CHEG 421
Petroleum Refining and Processing

Chapter 10:
Catalytic Reforming and
Isomerization
Catalytic Reforming
 Objectives of the process:
 Improve the octane number of naphtha (SR, hydrocracker and
coker)
 Increase the aromatic content of naphtha (feed to aromatics
complex)
 Currently provides 30-40% of the gasoline requirement
 Produces hydrogen as by-product, utilized for
hydroreatment
 Second most important unit after catalytic cracking
 Expected to decrease due to restrictions on aromatic
content of gasoline
Catalytic Reforming: Feedstock
 Feedstocks of the catalytic reforming unit are:
 Heavy SR gasoline/naphtha
 Heavy hydrocracking naphtha
 Heavy coker naphtha
 The reforming process leads to:
 Minimum change in the boiling range of the stock passed through
the unit
 Increase on the ON of gasoline
 Slightly decrease the naphtha yield
Catalytic Reforming: Product
 Reforming is the second highest contributor to the gasoline
pool after catalytic cracking
 The Gasoline Produced from reforming has:
 High ON
 Low vapor pressure
 Very low sulfur content
 Low olefin content
 High aromatic content
Catalytic Reforming: Feed vs. Products

 The reforming process increases the aromatic

content of the feed while it reduces the naphthenic
content and the paraffinic content

Component Feed Products

Paraffins 30-70 30-50
Olefins 0-2 0-2
Naphthenes 20-60 0-3
Aromatics 7-20 45-60
Catalytic Reforming Reactions
 Paraffins and Naphthenes undergo
 Cyclization
 Dehydrogenation
 Isomerization
 Ease of these reactions increases with increasing the
number of carbon atoms
 Lighter feedstock (LSR Gasoline) is mainly composed of
paraffinic compounds that tend to crack to butane and light
fraction and therefore not economical to be processed via
reforming
 Heavier fractions (boiling above 200°C) are easily
hydrocracked causing excessive carbon laydown on the
catalyst
Catalytic Reforming Reactions
 Many side reaction takes place yielding undesired
products
 Reaction conditions must be adjusted to minimize
side reactions
 Paraffins are converted to aromatic via the
following sequence of reactions
 Paraffins ⇒Naphthenes ⇒Aromatics
 Undesirable reactions includes dealkylation of side
chains on naphthenes and cracking of paraffins and
naphthenes
Catalytic Reforming Reactions
 There are four major reactions that take place during
reforming process
 Dehydrogenation
 Dehydrocyclization
 Isomerization
 Hydrocracking
 Desirable reactions leads to formation of aromatics and
isoparaffins as follow:
 Paraffins are isomerized to isoparaffins and to some extent
converted to naphthenes
 Olefins are saturated to paraffins
 Naphthenes are converted to aromatics
 Aromatics are essentially unchanged
Dehydrogenation Reactions
1. Dehydrogenation of alkylcyclohexanes to aromatics (fastest)
CH3 CH3 + 3 H2

2. Dehydroisomerization of alkylcyclopentanes to aromatics

CH3 + 3 H2

3. Dehydrocyclization of paraffins to aromatics

n-C7H16 + 3 H2

 Highly endothermic
 Highest reaction rate of the reforming reactions
 Interheaters have to used between catalyst beds to keep mixture at
sufficiently high enough temperature for the reactions to proceed at
practical rates
Dehydrogenation Reactions
 Dehydrogenation reactions produces aromatics
which improves the octane number
 Aromatics have higher density compared to
paraffins and naphthenes with the same number
of carbon atoms
 The reformatted gasoline end point is higher
than that of the feed naphtha because aromatics
have higher boiling points than paraffins
 The yield of aromatics increases by high
temperature, low pressure, low space velocity,
and low hydrogen to carbon mole ratio
Effect of Reforming on the TBP

Feed

Reformate
Isomerization reactions
 Converts paraffins and cyclopentanes to isoparaffins
 Yield products with octane number lower than that if
converted to aromatics
 Rapid reaction
 Increased by high temperature, low space velocity, and low
pressure
 Isomerization of n-paraffins
CH3
CH3-CH2-CH2-CH2-CH2-CH3 → CH3-CH- CH2-CH2-CH3
 Isomerization of alkylcyclopentanes

 CH3 + 3 H2

91 RON 83 RON 100 RON

Hydrocracking Reactions
 Exothermic
 Produces lighter liquid and gas products
 Slow reactions
 Occur in the last section of the reactor
 Involve cracking and saturation of paraffins
 Extent of the hydrocracking reaction is determined by the
concentration of paraffins in the feedstock. However, the
relative fraction of isomers produced in any molecular
weight is independent of feedstock
 Yield of hydrocracking is increased by high temperature,
high pressure and low space velocity
Yield

 Hydrocracking and aromtization reactions

must be controlled carefully in order to
obtain high product yield
 Operating conditions must be monitored
 Temperature
 Pressure

 Hydrogen ratio

 Space velocity
Reforming Reactions Yield

 Naphthenes → Aromatics (98% yield)

 Methyl cyclopentane → Benzene
 Cyclohexane → Benzene
 Methyl Cyclohexane → Toluene
 Dimethyl cyclopentane → Toluene
 Dimethyl cycloheaxane → xylene
 Cycloheptane → Toulene
 Methyl cycloheptane → xylene
Reforming Reactions Yield

 Paraffins → Aromatics (low yield)

 1 mole n-C6 → 0.05 moles Benzene
 1 mole n-C7 → 0.01 moles Toluene
 1 mole n-C8 → 0.28 moles C8 aromatics
 1 mole n-C9 → 0.45 moles C9 aromatics
Feed Preparation

 Because the process is catalytic, the

presence of certain sulfur and nitrogen
compounds in the feed are undesirable
 Feed must be pre-hydrotreated to remove
these materials
 Hydrotreatment utilize hydrogen from the
reforming process
 Some feed may need to be distilled to adjust
the boiling range of the products
Catalytic Reforming Processes

 Platforming Process (UOP)

 Powerforming Process (Exxon)
 Ultraforming Process (Amoco)
 Catalytic Reforming (Englhard)
 Magnaforming (ARCO)
 Reforming (IFP)
 Rheniforming (Chevron)
Catalytic Reforming Processes

 Based on the frequency of catalyst

regeneration the process is classified to:
 Continuous
 Cyclic

 Semiregenerative
Continuous Reforming Processes

 Catalyst is removed and replaced during

normal operation
 Catalyst is maintained at high activity
 High capital cost
 Lower operating cost
 Low pressure
 Lower hydrogen recycle rates
Continuous Reforming
Semi-regenerative Reforming Processes

 The unit has to be taken off stream for

regeneration
 Regeneration every 3-24 months based on
severity of the process
 Use of high pressure and high hydrogen recycle
rate to minimize coke laydown
 Minimum capital cost
Cyclic Reforming Processes

 A swing reactor is used for catalyst regeneration

 No need for unit shut down for regeneration
 When the catalyst activity drops down a certain
level, the reactor is isolated from the stream and
replaced by the swing reactor
 After regeneration, the reactor is used as the
swing reactor
 Intermediate capital cost
SemiRegenerative Reforming Process
Chemical Changes During the Reaction
Reforming Catalyst

 The catalytic reforming is bi-function

catalyst
1. Hydrogenation, dehydrogenation function
 Provided by metals such as platinum or Rhenium
supported on alumina
 Pellets ~ 1-2 mm with active surface area of 180-
200 m2/g and 0.6 cm3/g pore volume
 Metal content 0.5-0.6%
 Metal dispersion on the alumina surface and
agglomeration are crucial factors
Reforming Catalyst

2. Structural modification function

(isomerization)
 Requires acid type catalyst
 Provided by alumina after fixation of chlorine
(0.8-1.4%) on its surface
 Presence of water may eliminate chlorine
 Rechlorination by injection of chlorinated
products OH OH
+ H2O + HCl
Cl OH
Catalyst Deactivation vs. Yield
Catalyst Aging and Regeneration
1st Cycle 2nd Cycle 3rd Cycle

C1-C4 and coke yield C1-C4 and coke

yield increase

C5+ and H2 yield

C5+-H2
yield decrease

Temperature

Feed Temperature
must be increased
Catalyst Poisoning and Regeneration

 Permanent Poisons
 Pb, Hg, Cu, Na, Fe, Ni, Cl2, Si
 Semi-permanent poisons
 Coke
 Temporary poisons
 Sulfur (Pt + S → PtS reduced reforming activity/high
cracking activity)
 Sulfur must be removed from reforming feed (S <1 ppm)
 Organic Nitrogen
 NH3 leads to neutralize the acid sites of the catalyst
 Water and Chlorine
Reactor Design
Reforming Reactors
Reforming Reactors

 For cyclic and regenerative processes, fixed bed

reactor are used
 The reactors have internal lining for insulation
 Reactor walls are composed of steel containing 5%
Cr and 0.5 Mo to resist H2 embitterment
 Vapor distribution is important to provide
maximum contact with catalyst
 Temperature monitoring to determine catalyst
activity and coke burn off operations
Yield Calculation for Reforming Process

 Based on the amount

of naphthenes and
aromatics on the feed

C5+ , Yield, vol.%

stream or the
characterization factor
(KW), the reformate
yield and research
octane number can be
estimated
Yield Calculations, Dry Gas

 The yield of the

dry gas C1+ C2
and C3 can be
estimated based
on the volume %
of reformate
Yield Calculations, Wet Gas

 The yield of wet

gas, n-C4 and i-C4,
can also be
estimated based on
the yield of
reformate
Yield Calculations, Hydrogen

 The net hydrogen

production of
reforming process
can be estimated
based on the yield
of reformate
Cost of a Reforming Unit

 The capital cost of the

continuous process is
greater than fixed bed
processes
 Other Costs:
 Initial catalyst
($280/BPD)
 Operating costs ($50-
100/BPD + $0.07/bbl)
 Utilities
Material Balance around the
reformer
 A 180-380° F virgin naphtha stream with a
mean average boiling point of 275° F a 50.2°
API is reformed to a 96 RON clear gasoline
blending stock. The naphtha feed contains
0.01 weight% sulfur.
 Make an overall material balance around the
reformer for a 10000 BPD feed rate.
Material Balance around the Reformer
vol% BPCD API Lb/BPD Lb/h wt.% wt.% S S, Lb/h

Feed

H2

C1+C2

C3

i-C4

n-C4

C5+ Reformate

H2S

H2 Net
Isomerization Process

 Converts normal paraffins to isoparaffins

 Improves the octane number of light
gasoline
 Feed
 n-butane
 Light straight run naphtha

 Light coker naphtha

Isomerization Process by Feed
 n-butane → Iso-butane
 Used as feed for alkylation Process
i-C4 + Olefin → Alkylate gasoline
 Production of isobutene which is used for Production of
Oxygenates
i-C4 → i-C4= + H2
i-C4= + Alcohol→ Oxygenates
 n-C5 and n-C6 → i-C5 and i-C6 (isomerate
gasoline)
 Added to the gasoline pool
 Accounts for 5-10% of the gasoline pool
 Improve the octane number by 12-20 numbers
Octane Number of Pentane and Heaxne Isomers

C6 Isomers C5 Isomers
Isomer MON RON Isomer MON RON

24.8 26
61.7 61.9

73.4 73.5

92.3 90.3
74.5 74.3

100.5 94.3

85.5 80.2
91.8 93.4
Mechanism of Isomerization
Isomerization Process

 Reaction is preferred at low temperature

(200-400° F) due to the higher equilibrium
conversion at low temperature
 Atmosphere of hydrogen is used to
minimize carbon deposition
 A very active catalyst is required to increase
the reaction rate
Isomerization Catalyst
1. Platinum with organic chlorides
 The organic chlorides are converted to HCl in the
reactor
 Water and other oxygen source must be eliminated
from the feed to avoid catalyst deactivation and
corrosion problem
2. Molecular Sieve base catalyst
 Tolerate feed saturated with water
3. Platinum supported on metal oxides
 Higher activity than zeolitic isomerization catalysts
 Can be regenerated
 3 years or more catalyst life
Isomerization Catalysts

Generation Type T, ° C Advantages Disadvantages

Difficult to implement
Friedel 80-100
1st Very active Sensitive to impurities
Crafts
corrosive
Not very sensitive to poisons
Reforming 350-500 Not very active
2nd non corrosive
Pt/Al2O3 Low conversion per run
Easy to implement
Continuous chlorination in feed
Halogenate 100-150
3rd Very Active Corrosive
d Pt/Al2O3
Sensitive to poisons (H2O)
Relatively active
250-260 Not very sensitive to poisons
4th Pt/zeolite More Expensive
Easy to implement
Isomerization Yield
 The actual product distribution
Feed Product
is dependent on: LSR component
Wt.% Wt.%
RON

 Type and age of the catalyst n-pentane 33 13 62

Isopentane 22 42 92
 Space velocity Normal Hexane 20 3 26

 Temperature 2,2 dimethyl butane 1 15 96

2,3 dimethyl butane 2 5 84
 The pentane fraction is 75- 2-methyl pentane 12 15 74

80wt.% iso-pentane 3-methyl pentane 10 7 74

 The hexane fraction is 86-90

wt.% hexane isomers
Isomerization Processes

 Once through process

 Recycle
 n-pentane is separated from the reactor products
and recycled
 Increases RON by 3 numbers
 n-pentane and n-hexane are separated and recycled
 Increases RON by 5-7 numbers
 n-paraffin can be separated from i-paraffin by
fractionation or by vapor phase adsorption of the normal
paraffin on molecular sieve bed
Isomerization Process: Recycle
n-C5

1. i-C5 separation
2. Reactor
3. Iso/n separation

i-C5

C5

Temperature 95-205°C
n-C5, nC6
Pressure 1725-3450 kPa
Hydrogen to HC 0.05 to 1
mole ratio
Single pass LHSV 1-2 h-1
Liquid Product yield >98 wt.%
Isomerization Process: Once Through
n-Butane Isomerization
Effect of Process Temperature on ON
Effect of Cracking Reaction on Yield

 Hydrocracking occurs during

isomerization reactions and leads LSR
component
vol% on
feed
to formation of light gases (1-4%) C1-C2 2

 The gas composed mainly of 0.5

C3
i-C4 1
methane (95%) and 5% ethane by n-C4 1
weight C5-C7 102
Capital Cost of Isomerization Units

 Capital cost for a typical 10,000 BPD unit is

about MM$ 32
 Other costs
 Hydrogen source
 Feed desulfurization

 Initial catalyst charge ($90-$160 /BPD)

 Utilities
 Cooling water, steam, power supply
Petroleum Refining and
Processing
CHEG 421

Dr. Ahmed Abdala

Alkylation Process
 Important refinery process for production of high
octane number gasoline component (alkylate
gasoline)
 Alkylate produced via reaction of low molecular weight
olefin with isobutane or higher isoparaffins
 The reaction is reverse of the cracking reaction
 Alkylate gasoline is a mixture of branched HC of
gasoline boiling range
 Alkylate has MON of 90-95 and RON of 93-98
 It has low vapor pressure
 An excellent blending component for gasoline
Alkylation Feedstock
 Olefins
 C3=, C4=, or C5=
 From FCC
 From dehydrogenation of paraffins
 Iso-butane
 From isomerization, hydrocracking, catalytic cracking,
and reforming
 Iso-pentane
 Not as commonly used as i-C4 because it has high ON
and low vapor pressure and, therefore, can be used as a
gasoline blend
Alkylation Process Catalyst

 Non Catalytic
 High pressure, high temperature
 Not commercially viable

 Catalytic (Sulfuric Acid or Hydrofluoric acid)

 Low temperature
 5-21° C (for sulfuric acid)
 < 38° C (or hydrofluoric acids)
Alkylation Reactions

Iso-paraffin + Olefin →

acid
iso-paraffin

CH CH CH CH
3 3 3 3
CH 3 - C - CH 3 + CH 2 = C - CH 3 
H 2 SO4 / HF
→ CH 3 - C -CH 2 - CH -CH 3
H CH
 3 
2,2,4 trimethyl pentane (iso-octane)

CH CH
3 3
CH 3 - C - CH 3 + CH 2 =CH-CH 3 
H 2 SO4 / HF
→ CH 3 - C -CH 2 - CH 2 -CH 3
H CH
 3 
2,2 dimethyl pentane (iso-heptane)
Alkylation Process Variables
 Olefin Type
 The ratio of C4= to C3= affects both the quality of
alkylate and the acid consumption
 Using propylene reduces the alkylate ON by 5 numbers
and increases the acid consumption two times
compared to using butylene
 Isobutane concentration
 Olefin has higher solubility in the acid than iso-butane
 Isobutane/olefin ratio (5/1 to 15/1, 100/1 to 1000/1
internal ratio)
 High ratio reduces polymerization reactions
Alkylation Process Variables
 Reaction temperature
 Low temperature to reduce oxidation reduction reactions (Tar and
SO2) and to reduce polymerization of olefins
 Mixing
 Vigorous mixing is essential at low temperature as the acid viscosity
is very high
 To disperse the isoparaffin in the acid continuous phase
 Acid Strength and Composition
 93-95% for H2SO4(1-2% water, the reminder is HC diluents)
 86-90% for HF ( <1 % water, the reminder is HC diluents)
 Olefin Space Velocity
 Volume of olefin/hr divided by the volume of acid in the reactor
 Contact time 5-25 min for HF and 5-40 min for H2SO4
Alkylation Process Variables
 Alkylate quality can be predicted using F
correlating factor
I E ( I / O )F
F =
100( SV )o
 IE = isobutane in reactor effluent, liquid volume%
 (I/O)F = volumetric isobutane/olefin ratio in feed
 (SV)O= Olefin Space velocity, (v/h)/v
 The alkylate quality increases with F value
 F value range from 10-40
Alkylation Products

 LPG grade propane liquid (if propylene is

used)
 Normal Butane
 C5+ alkylate (160-190%)
 Tar (1-3%)
Hydrofluoric Acid Process (UOP)

Acid Settler

i-C4
Acid
Philips HF Process
 Dry Olefin and isobutane feedstock
are mixed with cooled acid
 Reaction takes place in the reactor
pipe
 The acid is separated in the acid
settler
 The acid layer at the bottom of the
settler is accumulated in the acid
acumulator
 The acid is cooled and recycled
 The hydrocarbon products are sent
to set of fractionation columns to
remove gaseous products (C3 and
C4, i-C4) and alkylate
 i-C4 is recycled
H2SO4 Processes
 Dried olefin is mixed with dried i-C4 and introduced into
the autorefrigerated reactor (1)
 HC products are compressed (2) and returned to the
reactor (to absorb heat of reaction)
 HC products are separated from the acid in the acid
settler (4)
 C3 is separated in depropanizer (3)
 i-C4 is separated from the
HC products in column 5
 Alkylate is removed from
n-C4 in column 6
HF Process versus H2SO4 Process

 HF has less capital and operating costs due to:

 Smaller and simpler reactor design
 Can use cooling water instead of refrigerant
 Smaller settling devices for emulsion
 Complete regeneration of the acid
 More flexible in terms of temperature and i-paraffin to
olefin ratio
 Less need for agitation for mixing of the acid and HC
Disadvantages of HF Systems
 HF process has the following added cost over
H2SO4 system
 HF requires more equipment to recover and neutralize
HF in various streams
 Dry the HF to greater extent
 Safety
 Cost for HF mitigation
 Polymerization is more pronounced in HF processes
 ON of alkylate from HF process is not as high as that of
H2SO4 Process
 HF usage is limited in highly populated areas
Polymerization
 C3= and C4= can be polymerized to form a high-octane
olefin product boiling in the gasoline range
 RON ~ 97, MON~ 83
 Alkylation is a better alternative to convert low olefins into
gasoline
 Alkylation produces highly isoparaffin products while
polymerization produces mainly olefinic
 Each one mole of olefin produces one mole of gasoline product in
alkylation while every two or three moles of olefins produce one
mole of gasoline product
 However, capital and operating costs for polymerization
process is lower than alkylation process
Polymerization Reactions

 Butene produces mainly dimers (diisobutene)

 Propylene produces dimers and trimers with low
conversion ~10%
CH 3 CH 3 CH 3 CH 3
=
CH 2 CH − CH 3 +=
CH 2 CH − CH 3 
→ CH 2 − C −=
CH C − CH 3
CH 3
CH 3 CH 3
3 CH 2 = CH − CH 3 
→CH 3 − CH 2 − CH = C − CH = CH − CH 3

CH 3
2=
CH 2 CH − CH 3 
→ CH 3 − CH 2 −=
CH C − CH 3
Polymerization Catalyst
 Acid catalyst
 Phosphoric acid mixed with natural clay
 Film of liquid phosphoric acid supported on quartz
 Sulfur poisons the catalyst
 Basic materials neutralize the catalyst
 Oxygen dissolved in the feed must be removed
 Catalyst consumption 0.5-1 lb/100 gal polymer
 Sulfur, basic materials and oxygen increases
catalyst consumption
Polymerization Process
 Feed
 Mixture of C3, C4, C3=, and C4=
 C3 and C4 act as diluents and a heat sink
 Pretreatment
 Contacted with amine solution to remove H2S
 Caustic washed to remove mercaptans
 Scrubbed with water to remove amines and caustic
 Dried through silica gel or molecular sieve
 350-400 ppm water is added to promote ionization of the
acid
 Reaction temperature is about 400°F
 Reactor pressure is about 500 psig
Polymerization Process

 Olefin is heated to 400°F and passed over

the catalyst bed
 The heat of reaction is removed by injecting
cold propane quench or by generating steam
 Reactor product is fractionated to separate
C4 and lighter materials
 Gasoline yield is 90-97% of the olefin feed
by weight (0.7 bbl/bbl olefin)
UOP Polymerization Unit
IFP polymerization Process (DIMERSOL)

 .2 =
CH2 CH − CH 3 
→ CH 3 − CH 2 −=
CH C − CH 3
CH 3

 Only dimerized C3= Olefin to produce isohexene

 Catalyst:
 Homogenous aluminum alkyl
 Requires high purity of C3 + C3= (>99%)
 C2s and C4s poison the catalyst
 Dienes and acetylenes should be removed
 Has low capital cost and operate at low pressure
IFP polymerization Process (DIMERSOL)
Yield of Alkylation Unit
Propylene Butylene Amylene
Component
Vol% Wt.% Vol% Wt.% Vol% Wt.%
Olefin 100 100 100 100 100 100
Feed iC4 160 171.3 120 112.6 140 145.06
Total 260 271.3 220 222.6 240 245.1
C3= 29.8 29.05 0 0 0 0
nC4 0 0 12.71 12.4 0 0
C5 7.17 8.53 6.8 7.08 45.2 43.5
Products C 5
+
159.4 212.56 151.1 176.56 145.6 156.2
alkylate
Alkylate
12.6 18.2 11.9 15.0 14.4 17.6
Bottoms
Tar 1.7 3.0 1.0 1.5 2.1 3
Feed/Products 1.23 1.0 1.199 1.0 1.158 1.0
Polymerization Yield

Yield, bbl/bbl olefin feed

Alkylate Polymer Dimate

C5+ gasoline 1.55 0.68 0.68

RON 94 97 97

MON 91 83 82
Alkylation Process Cost

 Capital cost for a 10 MBPD alkylation unit is

about $50 MM
 The operating cost
 Royalty ($0.03-0.04 /bbl alkylate)
 Utilities
 Steam 200 lb/bbl alkylate
 Cooling water circulation (3500 gal/bbl alkylate)

 Acid (0.3 lb HF/bbl alkylate or 30 lb H2SO4/bbl

alkylate)
 Caustic (0.2 lb/bbl alkylate)
Polymerization Process Cost

 Capital cost
 $ 1.75 MM for a 500 BPD unit
 $ 5.0 MM for a 2000 BPD unit

 The operating cost

 Utilities
 Fuel (36 MBtu/bbl Polymer)
 Cooling water circulation (290 gal/bbl polymer)
Material Balance of Alkylation Unit

 Make an overall Component BPD API Lb/hr

iC4 9510 119.8
volume and weight
C4 = 3520 104
Balance around an

Feed
C 3= 1550 148
alkylation unit with C 5= 1800
feed rates of 1550 Total 16380
BPD of propylene, C 3= , C 4= , C 5=
3520 BPD of
nC4
butylenes, 1800 BPD
Products

C5+ alkylate 47.9

of amylene, and 9510 Alkylate
BPD isobutane Bottoms
Tar
Total
Material Balance
Component Propylene Butylene Amylene Overall
BPD Vol% BPD Vol% BPD Vol% PBD
Olefin 3520 100 1550 100 1800 100 6870
Feed

iC4 5632 160 1860 120 2520 140 10012

Total 9152 260 3410 220 4320 240 16882
C3 1049 29.8 0 0 0 0 1049
nC4 0 0 197 12.71 0 0 197
Products

C5 252 7.17 105 6.8 814 45.2 1171

C5+ alkylate 5611 159.4 2342 151.1 2621 145.6 10574
Alkylate Bottoms 444 12.6 184 11.9 259 14.4 887
Tar 60 1.7 16 1 38 2.1 113
Feed/Products 7416 1.23 2844 1.199 3731 1.158 13991

Note: available iC4 is less than required!!

Material Balance of Polymerization Unit

Component BPD API Lb/hr

C3=
Feed C4=
Total

Product C5+ Polymer

Petroleum Refining and
Processing
CHEG 421

Dr. Ahmed Abdala

Importance of Refining Processes

 Basic intermediates produced from

different refinery operations are blended to
produce final products
 Objectives of Blending
 Allocate available blending components
 Economically meet market demand and
specifications
Physical Properties of a Blend
 Physical properties of a blend can be estimated from
the physical properties of blending stocks
 Some properties blend linearly
 Properties that do not blend linearly are substituted
with another “property” which blend linearly
 RVP is substituted with Vapor Pressure Blending Index
(VPBI)
 Viscosity is substituted with Viscosity Factor (VF)
 Flash Point is substituted with Flash Point Blending
Index(FPBI)
 Pour point is substituted with Pour Point Blending Index
(PPBI)
Reid Vapor Pressure

 RVP of gasoline is adjusted by adding n-butane with

other gasoline components
 The RVP is blended linearly on a molar basis
 The amount of n-butane required to give required
blend RVP can be calculated by:
n
M t ( RVP )t = ∑ M i ( R V P )i
i =1

or
n
( RVP )t = ∑ ( mol fraction )i ( RVP )i
i =1
Vapor Pressure Blending Index

 RVP of gasoline blend can also be calculated on

volumetric basic using the VP blending index
(VPBI) n
RVP = ∑ v (VPBI )
 i
i = 1 volume fraction
i

or
n
BPDt * RVP = ∑ BPDi (VPBI )i
i =1

 VPBI can be obtained from table 12.2 based on the

RVP
VPBI
RVP Calculations

 Calculate the amount of n-butane required to

produce 10 psi gasoline by blending LSR Gasoline,
Reformate, Alkylate, and FCC gasoline with the
following flow rates
Base BPD lb/h mol/h
LSR Gasoline 4000 39320 457
Reformate 6000 69900 617
Alkylate 3000 30690 295
FCC 8000 87520 810
n
M t ( RVP )t = ∑ M i ( RVP )i
i =1
Blending Properties of Gasoline Components
RVP Calculations
Base BPD lb/h mol/h RVP, psi Mi*RVPi
LSR Gasoline 4000 39320 457 11.1 5073
Reformate 6000 69900 617 2.8 1728
Alkylate 3000 30690 295 4.6 1357
FCC 8000 87520 810 4.4 3564
n-C4 W mC4 MC4 52 52MC4
∑ 21000+W 227430+ mC4 2179+MC4 11721+52M

 M C 4 + 2179  x10 = 111721 + 52 M C 4

M C4 = 240 mol / h
= 240*
= 58 13920 lb / h
WC4 = 13920
= / 8.49 1640 BPD
RVP Calculations using VPBI
Base BPD lb/h mol/h RVP, psi VPBI, psi BPDi*VPBIi
LSR Gasoline 4000 39320 457 11.1 18 5073
Reformate 6000 69900 617 2.8 3.62 1728
Alkylate 3000 30690 295 4.6 6.55 1357
FCC 8000 87520 810 4.4 6.37 3564
n-C4 W mC4 MC4 52 138 138W
∑ 21000 +W 227430+ m
C4
2179+ MC4 164330+138W

n
BPDt *VPBI t = ∑ BPD i (VPBI )i
i =1
[W + 21000 ] x17.8 =
164330 + 138W
W = 1740 BPD
mC 4 = 1740
= * 8.49 14800 lb / h
M C 4 = 14800
= / 58 250 mol / h
Blend Octane Number

 Octane number is blended on volumetric basis

 True Octane numbers do not blend linearly and a
blending octane number is used
 The Octane Number of a Blend Can be calculated
as follow:
 n   
Desired ON Blending ON of component i

Bt ON t = ∑  B
 ON i 
 i =1  bbl of component i
i

total gasoline ,bbl  

 n   
Desired ON Blending ON of component i

ON t = ∑  vi ON i 

i = 1  volume fractionof component i 
 
ON Calculations

 Calculate the octane Base BPD Lb/h MON RON

number of the gasoline LSR
4000 39320 67 78
blend with 10 psi RVP Gasoline

and the following Reformate 6000 69900 84 94

components:
Alkylate 3000 30690 96 97

FCC 8000 87520 77 92

n-C4 1640 13920 92 93

∑ 22640
ON Calculations
MO BPD* BPD*
Base BPD Lb/h RON
This image cannot currently be displayed.

N MON RON
MON blend =
∑ BPD * MON
i i

∑ BPD
LSR
4000 39320 67 78 286000 312000
i Gasoline

RON blend =
∑ BPD * RON
i i
Reformate 6000 69900 84 94 504000 564000
∑ BPD i
Alkylate 3000 30690 96 97 288000 291000
1826880
=
MON blend = 80.7
22640 FCC 8000 87520 77 92 616000 736000

205520 n-C4 1640 13920 92 93 150880 152520

=
RON blend = 90.8
22640
∑ 22640 1826880 2055520

RON blend + MON blend

PON blend = 85.7
2
Adjustment of ON
 If the PON is not Compound RVP, RON MON
psi
acceptable, this can be
Methanol 40 135 105
corrected by:
Ethanol 11 132 106
1. Increasing the ON of
the reformate by t-Butanol 6 106 89
increasing the severity MTBE 9 118 101
of the process
ETBE 4 118 102
2. Using octane blending
TAME 1.5 111 98
agent such as MTBE,
TEL - 10000 13000
ETBE, TAME,
methanol, ethanol, t-
butanol
Adjustment of ON

 For the previous Base BPD Lb/h RVP MON RON

example
LSR
4000 39320 11.1 61.6 66.4
 We can calculate Gasoline

both the BPD of n- Reformate 6000 69900 2.8 84 94

C4 and MTBE Alkylate 3000 30690 4.6 96 97

required to FCC 8000 87520 4.1 77 92

n-C4 X 52 92 93
produce gasoline
ΜΤΒΕ Y 9 118 101
blend with RVP of
10 and PON of 91
Adjustment of ON

MON*BP
Base BPD Lb/h RVP MON RON VPBI VPBI*BPD RON*BPD
D

LSR
4000 39320 11.1 61.6 66.4 20.3 81200 246400 265600
Gasoline

Reformate 6000 69900 2.8 84 94 3.62 21720 504000 564000

Alkylate 3000 30690 4.6 96 97 6.55 19650 288000 291000

FCC 8000 87520 1.4 77.1 92.1 1.52 12160 616000 736000

n-C4 X 52 92 93 138 138 X 92X 93X

ΜΤΒΕ Y 9 101 118 15.6 15.6 Y 101Y 118Y
21000 164330 1676000 1903000
∑ +X +138X +92X +93X
+Y +15.6Y 100Y +118Y
ON Calculations
n
BPDt *VPBI t = ∑ BPD i (VPBI )i
i =1
[ 21000 + X + Y ] x17.8
= 134730 + 138 X + 15.6Y (1)

MON blend =
∑ BPD * MON
i i
∑ BPD * RON
RON blend =
i i

∑ BPD i
∑ BPD i

1655200 + 92 X + 101Y 1857400 + 93 X + 118Y

MON blend = RON blend =
21000 + X + Y 21000 + X + Y
MON blend + RON blend
PON blend =
2
( 1655200 + 92 X + 101Y ) + ( 1857400 + 93 X + 118Y )
91 = (2)
2 * ( 21000 + X + Y )
Solution, continued

 Rearranging equations 1 and 2 yield

=Y 54.64 X − 108668 (3)
=
3 X 309400 − 37Y (4 )
 Solving Equation 3 and 4 you get X and Y (BPD of
n-C4 and MTBE)
 X=2134 BPD
 Y=8190 BPD
 RON=96.5
 MON=85.5