Refining Processes

Crude Distillation
Crude oils are first desalted and then introduced with steam to an atmospheric
distillation column. The atmospheric residue is then introduced to a vacuum
distillation tower
Solvent Deasphalting
This is the only physical process where carbon is rejected from heavy petroleum
fraction such as vacuum residue. Propane in liquid form (at moderate pressure) is
usually used to dissolve the whole oil, leaving asphaltene to precipitate. The
deasphalted oil (DAO) has low sulphur and metal contents since these are removed
with asphaltene.

Solvent Extraction
In this process, lube oil stock is treated by a solvent, such as N-methyl pyrrolidone
(NMP), which can dissolve the aromatic components in one phase (extract) and the
rest of the oil in another phase (raffinate). The solvent is removed from both phases
and the raffinate is dewaxed.
Solvent Dewaxing
The raffinate is dissolved in a solvent (methyl ethyl ketone, MEK) and the solution
is gradually chilled, during which high molecular weight paraffin (wax) is
crystallized, and the remaining solution is filtered. The extracted and dewaxed
resulting oil is called ‘‘lube oil’’. In some modern refineries removal of aromatics
and waxes is carried out by catalytic processes in ‘‘all hydrogenation process’’.
Chemical Catalytic Conversion Processes
Catalytic Reforming
In this process a special catalyst (platinum metal supported on silica or silica base
alumina) is used to restructure naphtha fraction (C6–C10) into aromatics and
isoparaffins.
Hydrotreating
This is one of the major processes for the cleaning of petroleum fractions from
impurities such as sulphur, nitrogen, oxy-compounds, chlorocompounds,
aromatics, waxes and metals using hydrogen.
Catalytic Hydrocracking
For higher molecular weight fractions such as atmospheric residues (AR) and
vacuum gas oils (VGOs), cracking in the presence of hydrogen is required to get light
products. In this case a dual function catalyst is used. It is composed of a zeolite catalyst
for the cracking function and rare earth metals supported on alumina for the
hydrogenation function. The main products are kerosene, jet fuel, diesel and fuel oil.
Catalytic Cracking
Fluid catalytic cracking (FCC) is the main player for the production of gasoline. The
catalyst in this case is a zeolite base for the cracking function. The main feed to FCC is
VGO and the product is gasoline, but some gas oil and refinery gases are also
Produced.
Thermal Chemical Conversion Processes
These processes are considered as upgrading processes for vacuum residue.
Delayed Coking
This process is based on the thermal cracking of vacuum residue by carbon rejection
forming coke and lighter products such as gases, gasoline and gas oils. Three types of
coke can be produced: sponge, shot and needle. The vacuum residue is heated in a
furnace and flashed into large drums where coke is deposited on the walls of these
drums, and the rest of the products are separated by distillation.
Flexicoking
In this thermal process, most of the coke is gasified into fuel gas using steam and air.
The burning of coke by air will provide the heat required for thermal cracking. The
products are gases, gasoline and gas oils with very little coke.
Visbreaking
This is a mild thermal cracking process used to break the high viscosity and pour
points of vacuum residue to the level which can be used in further downstream
processes. In this case, the residue is either broken in the furnace coil (coil
visbreaking) or soaked in a reactor for a few minutes (soaker visbreaker). The
products are gases, gasoline, gas oil and the unconverted residue.
Refinery Property Estimation

The following list summarizes the refinery process and product properties required
for process design calculations:

1. True boiling point curve (always given) of crude and intermediate/product streams
2. Volume (Mean) average boiling point (VABP)
3. Mean average boiling point (MEABP)
4. Weight average boiling point (WABP)
5. Molal average boiling point (MABP)
6. Characterization factor (K)
7. Vapor pressure (VP) at any temperature
8. Viscosity at any temperature
9. Average sulfur content (wt %)
10. Degree API
11. Enthalpy (Btu/lb)
12. ASTM conversion to TBP and vice‐versa
13. Viscosity of a mixture using viscosity index
14. Flash point of a mixture using flash point index
15. Pour point of a mixture using pour point index
16. Equilibrium flash vaporization curve
 Physical properties of feedstocks and products

API
API = (141.5/SG 15oF) – 131.5 The purpose of this equation was to extend the range
of the specific gravity scale. Crude oil SG changes, although small, may be
Important.
Crude Oils oAPI = 10 – 50
Higher oAPI, more paraffinic crude, higher yields of gasoline.
Lower oAPI, more aromatic crude, lower yields of gasoline.

Salt Content
Measured by ASTM – 3230 (lb NaCl/1000 bbl)
Desalting is necessary because NaCl content > 10 lbs/1000 bbl leads to corrosion
Metals
Measured by EPA Method 3040. These include Ni, V, Ag, Hg, Na, and Ca. Metals
can cause catalyst deactivation and corrosion.
Sediment and Water
Measured by ASTM D – 96 These inorganic particles can lead to operational
problems.
Acidity
Measured by ASTM – 664
Pour Point
Measured by ASTM D-97 – temperature at which oil ceases to flow. Diesel may
contain waxes, smaller than candle wax, which could solidify in cold weather.
Flash Point
Temperatures above which the oil will spontaneously combust. Fractions in vacuum
tower are the least combustible. They are the heaviest.
Vapor Pressure
Measured by ASTM D-323 Also know as Reid vapor pressure (RVP). True vapor
pressure is usually 5-9% > RVP
Carbon Residue
The solid residue (%wt) remaining after heating to coking temperatures (700-800oC)
ASTM D-524 Ramsbottom Carbon
ASTM D-189 Conradson Carbon
CCR incr. then Asphaltene incr.
 Base of crude oil

1. (Mallison classification according to residuum) a material left behind after

distillation of fractions.

Residue > 50% paraffins Paraffinc base

Residue < 20% paraffins Asphaltic base
Residue 20-50% paraffins Mixed base

2. The U .S. Bureau of Mines designated base of crude oil.

 Refinery Products
4. Characterization Factor

The most widely used index is characterization factor (Watson, Nelson and Murphy).
It was originally defined as:
In which:

TB is the average molal / Mean boiling point (R)

S is the specific gravity at 60 F
It has since related to viscosity, aniline, temperature, molecular weight, critical
temperature, percentage of hydrocarbon etc.
K ≥ 12.15 (Paraffinic Base)
K< 11.5 (Aromatic Base)
K between 11.5-12.15 (Napthenic Base)
5. Correlation Index (C .I)
Like (C.F) related to boiling point and gravity
C.I for Parafine =0 C.I for Benzene =100
C.I =0-15 Parafine C.I =15-50 either Naphtenes or mix (Parafine Naphtenes)
C.I = above 50 Aromatic
 Refinery Products
6. Viscosity Index: (V. I)

A series of numbers ranging from 0-100 which indicate the rate of change of
viscosity with temperature.
Paraffinic base V.I =100
Naphthenic base V.I = 40
 Refinery Products
Simulated Distillation by Gas Chromatography
The boiling point distribution of the whole crude oil can be determined by an injection of
the sample in a gas chromatograph which separates the hydrocarbons in boiling point
order. The retention time is related to then boiling point through a calibration curve. The
results of this test are comparable to the true boiling point tests. In addition, the boiling
point distribution of light and heavy petroleum cuts can also be done by gas
chromatography. One of the standards methods of measurements is ASTM D5307.

API Gravity
The gravity of crude oil determines its price commercially. It is generally expressed as API
gravity defined as:
API = 141.5/SG- 131.5
where SG is the specific gravity defined as the density of the crude oil relative to the
density of water both at 15.6 C (60F). The API gravity can range from 8.5 for very heavy
crudes to 44 for light crudes. Crude oils can generally be classified according to gravity.
Crude Category Gravity
1. Light crudes API > 38
2. Medium crudes 38 > API > 29
3. Heavy crudes 29 > API > 8.5
4. Very heavy crudes API < 8.5
The API gravity is also measured for various petroleum fractions. One of the standard tests is ASTM D1298.
 Refinery Products
Pour Point
The pour point is defined as the lowest temperature at which the sample will
flow. It indicates how easy or difficult it is to pump the oil, especially in cold
weather. It also indicates the aromaticity or the paraffinity of the crude oil or the
fraction. A lower pour point means that the paraffin content is low.
Pour points for the whole crude and fractions boiling above 232C(450F) are
determined by standard tests like ASTM D97.
Refinery Products
 The Petroleum Refinery
Refinery Products

Gas from petroleum is classified under several names

a) Natural gas : It is readily available in nature, in almost as a finished product. It contains mainly
methane It may be accompanied by other dry fractions like ethane and propane to a small extent. In
addition to these combustibles some inert like CO2 ,N2 , noble gases are also present. The proportion
of methane ranges from 85% to 98%.

b) Associted gas : This is obtained from oil reservoirs and this exists as a separate gas cap over liquid
phase. The proportion of CH4, C2H4 , C3H8 vary depending on reservoir conditions. When the gas phase
is taken out, it may still contain some liquid , hyrocarbons mainly of volatile range like butane and
pentane which when condensed are treated as (Natural Gasoline ).

c) Disolved gas : Gas may be present in liquid HC mainly in the dissolved state depending upon the
formation pressure. When the pressure dercreased, this dissolved gas comes out of the oil. This gas is
separated before transportation in pipe lines or tankers . The remaining is first to come out of the
distillation column because of higher temperature.
 The Petroleum Refinery
d) Refining off gas : In refinery , gas is formed in cracking and reforming operations due to the thermal
degradation of liquid hydrocarbons. During stabilization of wild gasoline or processed gasoline, the
gases are vented. This forms a major source of heat energy for refinery, as wall as feed stock for
petrochemicals. All the gases contain impurities like CO2 ,N2 , mercaptans, H2S, water vapor, suspended
impurities. First three paraffins are gases at room temperature. The mixture of methane and ethane is
called dry gas , propane and butane mixture is called wet gas.

e) Liquefied Petroleum Gas (LPG) : Propane is frequently used as LPG after being mixed with butane.
The most important property of this fuel is the vapor pressure. For factility leak detection, the gas is
mixed with small amount of odorous mercaptans.
 The Petroleum Refinery
Gasoline
Most refiners produce gasoline in two grades, regular and premium and in addition supply a low-lead
or non-lead gasoline to comply with antipollution requirements.

The principal difference between regular and premium fuels is the antiknock performance.

Gasoline is a complex mixture of hydrocarbons C4-C12 having a boiling range from 100 to 400 oF as
determined by ASTM method. Components are blended to promote :

1) high antiknock property.

2) ease of starting.
3) quick warm-up.
4) low tendency to vapor lock.
5) low engine deposits.
Normal butane is blended into gasoline to give the desired vapor pressure which is a compromise
between high RVP to improve starting characteristics and a low RVP to prevent vapor lock and reduce
evaporation losses. As butane has a high blending octane number as much as vapor pressure
limitation permits.
The addition of 10% ethanol to gasoline increases the RVP of the blend by about 1 psi.
 The Petroleum Refinery
Reid Vapor Pressure
Reid vapor pressure (RVP) is a way to measure how quickly fuels evaporate; it's often used in determining
gasoline and other petroleum product blends. The higher a fuel's RVP, the more quickly it evaporates. The
more quickly a fuel evaporates, the more it contributes to the ozone layer. RVP represents the fuel's
evaporation at 100 degrees Fahrenheit (37.8 degrees Celsius), and is measured in pounds per square inch, or
PSIs. The property that RVP measures often is referred to as the gasoline's volatility. To obtain the RVP, a
chilled sample is placed in a special vapor chamber that is heated to 100 degrees Fahrenheit (37.8 degrees
Celsius). The reading records the observed constant pressure in the chamber. There are national industry
standards for the bath, the thermometer and the pressure monitoring device so that consistency can be
maintained among RVPs.

The RVP for gasoline should always be below 14.7 PSI, which is normal atmospheric pressure. If the RVP is
higher than 14.7 PSI, excess pressure will build up, and the fuel might boil and evaporate while in the car's
gas tank. The Environmental Protection Agency (EPA) regulates RVP for gasoline that you buy at retail gas
stations during the summer months to help reduce emissions [source: Environmental Protection Agency].
The summer generally includes the dates June 1 through September 15, except in certain areas with
extended summer seasons. The summer fuel volatility regulations exclude Alaska, Hawaii and U.S. territories,
but otherwise are outlined by state and country. During summer months, RVPs typically can go no higher
than 9.0 PSI and usually are between 7.0 and 7.8 PSI in metropolitan areas. The precise regulations and
amounts on county borders are managed by regional EPA offices.

Measuring vapor pressure of gasoline also reveals the fuel's tendency to vapor lock in high operating
temperatures or at high altitudes. Vapor pressure affects starting and warm-up of car and plane engines. For
crude oils, understanding vapor pressure can help oil companies more safely gather, refine, store and
transport their products .
 The Petroleum Refinery
Gasoline specifications
The most important properties are :

1) Boiling Range :
This governs ease of starting, rate of acceleration, loss by crankcase dillution. and tendency towards
vapor lock.

Engine warm-up time is affected by the % distilled at 158 oF and the 90% ASTM distillation
temperature.

Warm up is expressed in terms of the miles of operation required to develop full power without
excessive use of the choke.
 The Petroleum Refinery
Crankcase dilution is controlled by the 90% ASTM distillation temperature and is also a function of
outside temperature.

Tendency to vapor lock is directly proportional to the RVP of the gasoline.

RVP is approximately the vapor pressure of the gasoline at 100 oF in Lb/in2 absolute.

2) Antiknock Properties :
There are two types of octane numbers for gasoline engines : those determined by
- the motor method (MON)
- the research method (RON)

both methods use the same basic test engine but operate under different conditions.

The RON (ASTM D-908) represents the performance during low-speed driving when acceleration is
relatively frequent, and the MON (ASTM D-357) is a guide to engine performance and high speeds or
under heavy load conditions.

The difference between the RON & MON of gasoline is an indication of the change of performance
under both city and highway driving and is known as the "sensivity" of the fuel.
 The Petroleum Refinery
Obviously, the driver would like for the fuel to perform equally well both in the city and on the
highway, therefore low sensitivity fuels are better.

Since the posting of octane numbers on the service station pump has been required in the United
States, the posted octane number (PON) is the one most well-known by the typical driver. This is the
arithmetic average of the research and motor octane numbers [(RON + MON)/2].

In the mountain and high altitude regions, altitude affects several properties of gasoline, the most
important of which are losses by evaporation and octane requirement.

Octane number requirement is greatly affected by altitude and, for a constant spark advance, is about
three units lower for each 1000 ft (305 m) of elevation.

Octane requirements for the same model of engine will vary by 7 to 12 RON because of differences in
tune-up, engine deposits, and clearances.
 The Petroleum Refinery
Distillate Fuels
1)Jet Fuels: Commercial jet fuel is a material in the kerosene boiling range and must be clean burning.

One of the critical specification of jet fuels is its smoke point and this limits the % of cracked products high in
aromatic that can be incorporated. Specification limit the aromatic conc. to 20%. Hydrocracking saturates the
aromatics in the cracked products and raise the smoke point.

The freeze point specification is very low (-40 oF to -58 oF) max. and hydrocracking is also used to isomerizes
paraffin and lower the freeze point. In addition the other limiting specification is flash point (110 to 150 oF).

Naphtha jet fuel is produced for military and is a wide- boiling- range stock which extends through the
gasoline and kerosene boiling range.

2) Diesel Fuels: The major performance characteristics of diesel fuels, some what in the order of importance
are : (cleanliness, ignition quality, volatility, viscosity)

No.1 diesel fuel: is generally made from virgin stocks having cetane No. above 50 . It has a boiling range from
360 to 600 oF (250 to 320 oC) and is used in high- speed engines in trucks and buses, it is called some time
super diesel.
No.2 diesel fuel : is similar to No.2 fuel oil, and has a wider boiling range (350 to 650 oF) than No.1. It is
usually contains some cracked stocks and may be blended from naphtha, kerosene , and light cracked cycle
oils.
 The Petroleum Refinery
Limiting specifications are:

Flash point ( 120 to 125 oF min.)

Dist. Range
Cetane No. (52 min.)
Pour point (-10 to +10 max.)

The ignition properties of diesel fuels are expressed in terms of cetane number which expressed the
volume % of cetane (C16H34 , high ignition quality) in a mixture with alpha-methl-naphthalene (C11H10 ,
low ignition quality).

3) Heating Oils

No.1 fuel oil is very similar to kerosene but has a higher pour point and end point.

Limiting specification are

Distillation, pour point, flash point and sulfur content.
No.2 fuel oil is very similar to No. 2 diesel fuel, contains cracked stock, and is blended from naphtha,
kerosene, diesel and cracked- cycle oils.
 The Petroleum Refinery
Limiting specification are:

Sulfur content ( 0.25 to 0.5% max. )

Pour point ( -10 to +5 max. )
Distillation
Flash point ( 120 oF min.)
Aviation Turbine Fuels , ( ATF) , Jet Fuels
Modern jet engines use fuel similar to kerosene. It is a most flexible fuel in its boiling range ( upto 300
oC )

Important properties
Pour point not higher than -30 oC
Smoke point high
Volatility
Water content
 The Petroleum Refinery
Naphtha:

These fractions are highly volatile and fall in the boiling range of motor spirits.

These are mostly used as solvents in paints, perfumery and other industries. Solvent grades are
produced by distilling wide cut naphthas into small boiling range cuts.

Naphthas are not suitable for combustion because of the rapid flame propagation, resulting in
explosions.
Cuts boiling below 80 oC donot have any aromatics, hence their solvent power is also less, such
fractions are sent for cracking operations.
80-120 oC fraction is reformed to produce an improved octane No. and this goes as a blend into SRG.

Kerosene
Approx. boiling point range 150-250 oC
Low viscosity
Good degree of refinement to be fairly stable.
Light in colour
Free from smoke
Used as illuminating oil and converted into aviation fuels.
 The Petroleum Refinery
Diesel Fuels

Boiling point range 250-320 oC

Mainly two types : classification of diesel oils is done according to speed and load of the engine as
1) high speed diesels
2) low speed diesels

Lube Oils

The principal source of lubricating oil is the fraction that is left after components, namely gasoline,
kerosene, diesel oil during crude distillation.
Boiling point >350 oC obtained from vacuum distillation units.

Residuum after precipitation of asphaltenes are known as bright stocks and form good source for lube
oils.