Chapter 3:

Refinery Feedstocks
 Chapter 3- Refinery Feedstocks

➢Basic raw material is petroleum or oil. Other raw materials: synthetic crude
oils (Gilsonite, tar sand, shale oil, etc.) and natural gas liquids.

➢Chemical compositions are uniform. Physical characteristics vary widely.

➢Crude oils bases: paraffin, naphthene, asphalt, aromatic, or mixed base.

➢Paraffinic and asphaltic are based on the properties of the residuum left
from nondestructive distillation.

➢Paraffinic and asphaltic are more descriptive to the refiner; they convey the
nature of the products to be expected and the processing necessary.
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
 Crude Oil Composition :Elemental 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

Principal groups or series of HC’s that occur naturally in crude

oil are Paraffins, Aromatics, and Naphthenes.

❑ 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
 Crude Classifications According to types of hydrocarbons
( Parafffins , Naphthenes, Aromatics)
This rating is important to the refinery since the value of the crude oil decreases from
classification 1 to 6 : Crude Classifications (in order of decreasing value):

1) Paraffinic Crudes 4) Aromatic – Naphthenic Crudes

• paraffins + naphthenes > 50% aromatics > 50%
• paraffins > naphthenes 5) Aromatic - Intermediate Crudes
• paraffins > 40% • aromatics > 50%
2) Naphthenic Crudes • paraffins >10%
• paraffins + naphthenes >50% 6) Aromatic – Asphaltic Crudes
• naphthenes > paraffins • naphthenes > 25%
• naphthenes >40% • paraffins < 10%
3) Paraffinic – Naphthinic Crudes
• aromatics < 50%
• paraffins < 40%
• naphthenes < 40%
2. Heterotomic
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)
 Sulfur Compounds
• Difficulties with sulfur-containing oils arise in
• Corrosion in low boiling products such as gasoline. Can be treated
by sweetening.
• Odor is most obnoxious in gases containing sulfur.
• Poor explosion characteristics of gasoline fuels.

• H2S is a light gas, it tends to concentrate in the top section of certain

distillation columns, overhead piping, and condensers. As a result,
sulfide corrosion is more likely to occur in these sections.

• Mercaptans and sulfides are highest in heavy oil streams from

distillation and coker units. Sulfur is more corrosive at high
temperatures.
Organic Sulfur Compounds
 Nitrogen compounds
• N2 is present as organic nitrogen (i.e., in combination with HC (e.g., Pyrole
C4H5N).

• High N content (> 0.25 wt% N) is undesirable in crude oils because

• cause severe poisoning or deactivation of cracking catalysts in processing.

• corrosion problems such as hydrogen blistering.

• Nitrogen compounds are more stable than sulphur compounds and therefore
are harder to remove.
• Nitrogen compounds contribute to gum formation in finished products
• The hydrotreater unit is used to remove N2 from feed streams to reformer and
hydrocracker units to protect the catalyst in these units.
Organic Nitrogen Compounds
Oxygen compounds

• The oxygen content of crude oil is usually less than 2 wt%.

• high oxygen content indicates that the oil has suffered prolonged
exposure to the atmosphere.
• Oxygen in crude oil can occur in a variety of forms include alcohols,
ethers, carboxylic acids, phenolic compounds,.
• The presence of oxygen compounds causes the crude to be acidic with
consequent processing problems such as corrosion.
Organic Oxygen Compounds
Metal Content, ppm

❑ Vary from few ppm to more than 1000 ppm

❑ Ni, Va, Cu, Fe severely affect catalyst activity

❑ Concentrated on the heavy fractions and residue

❑ V concentration > 2 ppm in fuel oil can lead to severe

corrosion to turbine blades and deterioration of refractory
furnace linings and stacks

❑ Some appear in higher-boiling distillates

❑ May be reduced by solvent extraction

3. Others

❑ Traces of elements and metals Cu, Ca, Mg

❑ Salts
Crude Oil Properties
• There is no way to analyze each crude for each pure
component.
• To evaluate any crude, several properties are examined,
and the crude is given a certain value.

• Crudes: Arab light, Arab Heavy, Dubai crude, Oman light,

Brent crude, …

• Main Properties: API Gravity, Sulfur Content, Pour Point,

Carbon Residue, Salt Content, Characterization Factors
Kw, Nitrogen Content, Distillation Range, and Metals
Content.
Crude Oil Properties:
Color

• Color indicates the degree of refining the crude oil has

gone through.

• Discoloration of distilled products is an indication of

• Thermal decomposition
• Entertainment of dark-colored tarry materials that are
inherently dark in color
Crude Oil Properties:
°API

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 while
Specific gravities can be averaged.
Reference temperature for specific gravity and °API is 60° F (15.6° C)
Classification of crude oil according to gravity

• The API of crude oils varies typically between 10 and 50,

• Most crude oils falling in the range of 20-45.
• Using API gravity, the conventional crude oils can be
generally considered as Light (°API>30), Medium
(30>°API>22), and Heavy (°API<22).
Crude Oil Properties:
Sulfur Content

❑ Has great influence on the value of crude oil

❑ It varies from less than 0.05% to greater than 5%
( up to 10 %)
❑ Sour crude has sulfur content > 0.5%
❑ Sweet crude has sulfur content < 0.5%
Now You Classify The Crude Oil
 Why crude oil classification is important
Classification helps in:
i) determine the price of a specific barrel of crude,
ii) how much demand there is for that particular oil.

Comments
• Sweet crude is easier to refine and safer to extract and transport than sour crude
• light crude causes less damage to refineries and thus results in lower maintenance
costs over time.
• light Sweet crude oil is more preferred by refineries as it contains valuable chemicals
which is needed to produce the light distillates and high quality feedstocks
• So , sweet crude commands up to a $15 dollar premium per barrel over sour.
•
Crude Oil Properties:
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
Crude Oil Properties:
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%
 Crude Oil Properties:
Pour Point
❑ Pour point is the lowest temperature after which the oil stops to flow
❑ Indication of the paraffinic and aromatic content of crude oil
❑ High pour point means high paraffin content
❑ The lower the pour point the lower the paraffin content, and
the greater the content of aromatics.
❑ Critical property for transportation of oil in pipelines
❑ It is a critical specification for middle distillates used in cold
countries or at high elevations.
Crude Oil Properties:
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
Crude Oil Properties:
Characterization Factors
• Watson Characterization Factor, KW
KW = (TB)1/3/SG
TB = mean average B.P. of crude, oR
SG = specific gravity at 60oF/60oF.
Depending on the value of the Watson characterization factor,
crude oils are classified as
(Kw = 11-12.9), paraffinic(
Kw =10-11), naphthenic
KW < 10 for highly aromatic materials
KW ~ 15 for highly paraffinic compounds.

• Correlation Index, cetane

• indexCI
CI = 87,552/TB + 473.7 SG - 456.8
CI = 0 for straight-chain paraffins
CI = 100 for Benzene.
• Lower CI: more paraffins
• Higher CI: more naphthenes and aromatics.
Characterization Factors: cont.

Paraffins Naphthenes

KW 12.15 - 12.9 10.5 - 11.45

CI 9.5 - 33.7 43.7 - 83

VI 79 - 151 -60 + 40
Tests on Petroleum Fractions
Viscosity: It is usually measured in centi Stokes or Saybolt seconds
at 37.8 and 99 ºC. These two points are used to find viscosity index
of the fraction.
Aniline point: It is an indication of the amount of the aromatic
content in a given fraction.
Cetane number: It measures the ability for autoingnition in diesel
(compression ignition) engines. It is the percentage of pure cetane
(n-hexadecane) in a blend of cetane and alpha methyl naphthalene
which corresponds to the ignition characterstics of a given diesel
sample
Sediments: These are solid materials that are not soluble in the
hydrocarbon or water and can be comprised of sand, drilling mud,
rock or minerals, particles from
 Tests on Petroleum Fractions: cont.

• Smoke point: It is a measure of the burning qualities of kerosene and jet fuels.
It is measured in terms of the maximum height in mm of a smokeless flame of
fuel.
• Cloud point is the temperature at which solidifiable compounds present in the
sample begin to crystallize or separate from the solution under a method of
prescribed chilling.
• Cloud point is a typical specification of middle distillate fuels; ASTM D-2500.
• Flash point: Flash point is the temperature to which a product must be heated,
under prescribed conditions, to release sufficient vapor to form a mixture with air
that can be readily ignited (in the presence of a flame).
• It is used as an indication of the fire and explosion potential.
• It is important for gasoline and naphtha.
Tests on Petroleum Fractions: cont.

Freezing point: It is the temperature at which the hydrocarbon liquid

solidifies at atmospheric pressure. It is one of the important property
specifications for kerosene and jet fuels due to the low temperatures
encountered at high altitudes in jet planes.
Reid Vapor Pressure (RVP): Pressure of fluid within a closed
container.
❑ Used for volatile non-viscous products: gasoline, kerosene, etc.

❑ It is important for HC’s with low b.p. which can not be distilled at

atmospheric pressure without a loss.

❑ It is important with respect to

• Safety in transporting products

• Vapor lock in gasoline feed systems
• Starting characteristics of motor fuels
.
Crude Characteristic
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

Petroleum
products with
carbon numbers &
boiling ranges
 Crude Distillation Curves
❑ True Boiling point (TBP)
o USBM Hempel method
USBM- U.S. Bureau of Mines.
using 15 theoretical stages at a reflux ratio of 5:1
o ASTM D-285
ASTM - American Society for Testing and Materials
❑ ASTM: Standard Tests
1. D-86 for light fractions
at atmospheric Pressure
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
ASTM to TBP
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 CO 2 )
Water
 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
Each fraction has an IBP and EP on ASTM curve (Cut Point)
because of un efficient fractionation the IBP of heavier fraction is
interrelated with the EP of lighter fraction.
Cut points and mid bp
 Crude Oil Fractions
• Typical initial and end boiling points for atmospheric distillation cuts are as
follow:

Fraction Boiling, °F Vol.%

Gas <50 -

LT. Naphtha 50-200 8

HV. naphtha 200-400 20

Kerosene 400-500 10

Gas oil 6000-11105

residuum >1100 45
 Heavy Naphtha Fraction (200-400 °F)
HV. Naphtha cut 200-400 °F

2
 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 46°
315°F

Kw=11.5
CI=34.4
Gas Oil Fraction (500-650 °F)

36% 60%
 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
 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 refineryhwich wishes to feed a PetrochemicalrCacker
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