Recovering oil usually requires two to three stages,

which are briefly described as follows:

 
Stage 1: Primary Recovery
12% to 15% of the oil in the well is recovered without the
need to introduce other substances into the well.
 
Stage 2: Secondary Recovery
The oil well is flooded with water or other substances to drive
out an additional 15% to 20% more oil from the well.
 
Stage 3: Tertiary Recovery
This stage may be accomplished through several different
methods, including MEOR, to additionally recover up to 11%
more oil from the well.
 
 Enhanced Oil Recovery
Enhanced oil recovery (EOR) refers to the recovery of oil that is left behind
after primary and secondary recovery methods have either been exhausted or
no longer economical.

There are different modes of Enhanced Oil Recovery (EOR) methods

• Chemical Methods
• Gas Flooding
• Microbial Processes
• Thermal Processes
• Novel Methods
• Computer Simulation
 Chemical Methods

Chemical methods focus mainly on alkaline–surfactant–polymer (ASP)

processes that involve the injection of micellar–polymers into the
reservoir.

Chemical flooding reduces the interfacial tension between the in place

crude oil and the injected water, allowing the oil to be produced.

Micellar fluids are composed largely of surfactants mixed with water. (The
slug is a solution usually containing a mixture of a surfactant, co-
surfactant, alcohol, brine, and oil that acts to release oil from the pores of
the reservoir rock)
 Gas Flooding
Gas Flooding technologies primarily use carbon dioxide flooding as a
method to produce more oil from the reservoir by channeling gas into
previously-bypassed areas.

Carbon dioxide flooding technologies, experiment with a number of

foams, gels, and thickening agents to improve sweep efficiency.
 
 Microbial Processes

Microbial enhanced oil recovery refers to the use of microorganisms to

retrieve additional oil from existing wells, thereby enhancing the petroleum
production of an oil reservoir.
In this technique, microorganisms are introduced into oil wells to produce
harmless by-products, such as slippery natural substances or gases, all of
which help propel oil out of the well.

MEOR is used in the third phase of oil recovery from a well, known as
tertiary oil recovery.
 Thermal Processes

Heavy oil is recovered by introducing heat into the reservoir through

thermally controlled processes.

Steam flooding or air injection are the most frequently-used thermal

recovery methods.

Steam flooding is conducted by injecting steam into reservoirs that are

relatively shallow, permeable, and thick, and contain moderately viscous
oil.

The dominant mechanism in thermal recovery by steam is the reduction

in the viscosity of the oil, allowing flow to the well bore.
 Novel Methods
 
Novel methods include down hole electric heating,
microwave heating, seismic wave stimulation, and
wetting ability reversal.

Of these, seismic stimulation has met with success

in Russia and is currently being tested in the U.S.
 Computer Simulation

Reservoir simulation is advancing rapidly with improved computing

capabilities.

Reservoir simulators are useful in the design and prediction of

performance in EOR projects.

Improved hardware and software programs are becoming available that

include EOR applications.

Reservoir simulation should be considered as a tool in any enhanced oil

recovery project.
 
 
 Geographical Locations
North Sea Crudes - Brent, Osberg, Forties, North Sea
basket. "North Sea" often includes areas such as the
Norwegian Sea and the area known as "West of Shetland",

Brent Sweet Light crude is light but not as light as the West Texas
Intermediate (WTI). Brent crude is suitable for the production of
gasoline.

The sulfur level is 0.36% whereas the API gravity is around 38.5
degrees for the North Sea crudes.
 Geographical Locations

United State Crudes – West Texas Intermediate (WTI),

West Texas Sour (WTS), Light Louisiana Sweet (LLS).

The sulfur content is 0.24% and the API gravity is 39.6

degrees.
The WTI is ideal for the production of gasoline due to its
low sulfur content and it is lighter than Brent crude.
OPEC Reference Basket or West African Crudes - Bonny light,
Escravos, Forcados

The OPEC Basket, including a mix of light and heavy crudes, is heavier
than both Brent crude oil, and West Texas Intermediate crude oil.

API gravity around 35 degrees and sulfur level of 0.2%.

 
The new OPEC Reference Basket of Crudes (ORB) is made up
of the following: Saharan Blend (Algeria), Girassol
(Angola), Oriente (Ecuador), Iran Heavy (Islamic Republic
of Iran), Basra Light (Iraq), Kuwait Export (Kuwait), Es
Sider (Libya), Bonny Light (Nigeria), Qatar Marine
(Qatar), Arab Light (Saudi Arabia), Murban (UAE) and
Merey (Venezuela).

Persian Gulf Crudes – Dubai, Arab and Qatar

API gravity around 37 degrees and 1.08% of sulfur level are the
measures.
 Composition of Hydrocarbons

Fluids found in petroleum reservoirs consist of petroleum and brine

Petroleum maybe gaseous, liquid or solid

Chemical composition of petroleum

1. Molecules contain C and H
2. Alkane series form basis CnH2n+2

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% (found in organic compounds such as
carbon dioxide, phenols, ketones, carboxylic acids)
• Metals - less than 1% (nickel, iron, vanadium, copper, arsenic
Salts- Leass than 1% (NaCl, mgcl2, CaCl2).
 Major Classes of
hydrocarbons in crude oils
 The major classes of hydrocarbons in
crude oils
 
Paraffins (Aliphatic) general formula: CnH2n+2 (n is a whole
number, usually from 1 to 20) straight- or branched-chain
molecules can be gasses or liquids at room temperature
depending upon the molecule examples: methane, ethane,
propane, butane, isobutane, pentane, hexane.
 
Aromatics general formula: C6H5 - Y (Y is a longer, straight
molecule that connects to the benzene ring) ringed
structures with one or more rings rings contain six carbon
atoms, with alternating double and single bonds between
the carbons typically liquids examples: benzene,
napthalene.
 
Napthenes or Cycloalkanes general formula: CnH2n (n
is a whole number usually from 1 to 20) ringed
structures with one or more rings rings contain only
single bonds between the carbon atoms typically
liquids at room temperature examples: cyclohexane,
methyl cyclopentane.
 

Other hydrocarbons Alkenes general formula: CnH2n (n

is a whole number, usually from 1 to 20) linear or
branched chain molecules containing one carbon-
carbon double-bond can be liquid or gas examples:
ethylene, butene, isobutene

Dienes and Alkynes general formula: CnH2n-2 (n is a

whole number, usually from 1 to 20) linear or branched
 DISTILLATION
• Simple distillation
• Fractional distillation
• Batch distillation
• Continuous distillation
• Industrial distillation
Distillation is a widely used method for separating
mixtures based on differences in the conditions
required to change the phase of components of the
mixture.
Distillation is the most common separation technique
and it consumes enormous amounts of energy, both
in terms of cooling and heating requirements.
Distillation can contribute to more than 50% of plant
operating costs.
Distillation is used for many commercial processes,
such as production of gasoline, distilled water,
xylene, alcohol, paraffin, kerosene, and many other
liquids.
 Simple Batch Distillation

In simple distillation, all the hot vapors

produced are immediately channeled
into a condenser that cools and
condenses the vapors.

Therefore, the distillate will not be pure -

its composition will be identical to the
composition of the vapors at the given
temperature and pressure, and can be
computed from Raoult's law.

As a result, simple distillation is usually

used only to separate liquids whose
boiling points differ greatly (rule of
thumb is 25 °C), or to separate liquids
from involatile solids or oils.
Characteristics:

- no column; a single equilibrium stage (= the stil pot)

- single charge (F) to stil pot at time = 0
- vapor is withdrawn continuously
- composition of liquid in stil pot (xW) changes continuously
- composition of liquid distil ate (xD) changes continuously
 Fractional Distillation
(Multistage Batch
Distillation)
Fractional distillation must be
used in order to separate the
components well by repeated
vaporization-condensation cycles
within a packed fractionating
column.

This separation, by successive

distillations, is also referred to as
rectification.
Fractional Distillation
(Multistage Batch
Distillation)

As the solution to be purified is

heated, its vapors rise to the
fractionating column.

As it rises, it cools, condensing

on the condenser walls and the
surfaces of the packing
material.

Here, the condensate

continues to be heated by the
rising hot vapors; it vaporizes
once more.
 Distillation Columns are
classified by the manner in
which they are operated:

1.Batch columns process in which the feed to

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

2.Continuous columns process a continuous

feed stream.No interruptions occur unless there
is a problem with the column or surrounding
process units.

They are capable of handling high throughputs

and are the most common of the two types.
• tray column - trays of various
designs used to hold up the liquid to provide
better contact between vapour and liquid;
• packed column - packings are used
to enhance vapour-liquid contact.
Distillation Columns are classified
by the manner in which they are
operated:

•Column internal trays/plates and/or

packings which are used to
enhance component separations.

•A reboiler to provide the necessary

vaporization for the distillation
process.

•A condenser to cool and condense

the vapour leaving the top of the
column.

• A reflux drum to hold the

condensed vapour from the top of
the column so that liquid (reflux)
can be recycled back to the column.
Atmospheric Distillation
Atmospheric Distillation
To separate crude into different
products by boiling point differences.
Prepare feed for secondary processing
units

Products
• Fuel Gas
• LPG
• Naphtha
• Kerosene
• Light and Heavy Gas Oils
• Reduced Crude Oil
Products Composition
Gasoline C6 – C11
Kerosene C12 – C16
Gas oil C13 – C18
Lubricating oil C16 – C20
Paraffin wax C20 – C30
Residue C30 – C40
 Atmospheric Distillation
In the refining process is the
separation of crude oil into
various fractions or straight-
run cuts by distillation in
atmospheric and vacuum
towers.
The main fractions or "cuts"
obtained have specific boiling-
point ranges and can be
classified in order of
decreasing volatility into
gases, light distillates, middle
distillates, gas oils, and
residuum.
 Process Description
The desalted crude feedstock
is preheated using recovered
process heat.
The feedstock then flows to a
direct-fired crude charge
heater then into the vertical
distillation column just above
the bottom, at pressures
slightly above atmospheric and
at temperatures ranging from
340-370°C (above these
temperatures undesirable
thermal cracking may occur).
All but the heaviest fractions
flash into vapor.
 Process Description
As the hot vapor rises in the
tower, its temperature is
reduced.
Heavy fuel oil or asphalt
residue is taken from the
bottom.
At successively higher points
on the tower, the various major
products including lubricating
oil, heating oil, kerosene,
gasoline, and uncondensed
gases (which condense at
lower temperatures) are drawn
off.
 Crude Oil Desalting

Desalting is an integral part of

refinery crude oil processing
and can be the key to
controlling pipe still corrosion,
heat exchanger fouling,
furnace tube coking, and
process water disposal.

Salts, which normally occur in

the form of brine suspended in
the crude, promote corrosion,
fouling, and coking.
•
 Crude Oil Desalting
The primary function of a desalter is
to remove this salt from the oil.

Other contaminants, such as

sediment, which can promote heat
exchanger fouling and plugging,
erosion, and residual product
contamination, can also be removed
in a desalter.

Electrostatic desalting is used to

remove salts and particulates from crude
oil.

The crude oil brine mixture is contacted

with wash water using a mix valve just
upstream of the desalter vessel.
 Crude Oil Desalting

Salt is extracted from the brine into the

wash water droplets.

The electric field in the desalter

enhances water droplet coalescence so
that water/oil separation requires much
less residence time, and hence a
smaller vessel, than is needed for
unenhanced settling.

Small quantities of desalting aids are

often added to enhance contacting
effectiveness, droplet coalescence, and
water separation.

Desalted oil is removed from the top of

the desalter vessel and the briny water
from the bottom.
Vacuum Distillation Unit
 Vacuum Distillation Unit

To further distill the residuum or

topped crude from the atmospheric
tower without thermal cracking,
reduced pressure is required.

The process takes place in one or

more vacuum distillation towers.

The principles of vacuum distillation

resemble those of fractional
distillation except that larger diameter
columns are used to maintain
comparable vapor velocities at the
reduced pressures.

The internal designs of some

vacuum towers are different from
atmospheric towers in that random
packing and demister pads are used
instead of trays.
 Vacuum Distillation Unit

A typical first-phase vacuum tower

may produce gas oils, lubricating-
oil base stocks, and heavy residual
for propane deasphalting.

A second-phase tower operating at

lower vacuum may distill surplus
residuum from the atmospheric
tower, which is not used for lube-
stock processing, and surplus
residuum from the first vacuum
tower not used for deasphalting.

Vacuum towers are typically used

to separate catalytic cracking
feedstock from surplus residuum.
 Distillation Calculation
SIMPLE (DIFFERENTIAL) DISTILLATION

We will consider a binary mixture of A (more volatile) and B

(less volatile). The set-up is as shown in the Figure.

The condensed vapour is known as the distillate.

The distillate (D) is collected in a condensate receiver.

The liquid remaining in the still is known as the residual.

Material Balance for the still: see the Figure

L1 (F) = initial moles of liquid originally in still

L2 (W) = final moles of liquid remained in still

X1 (xF) = initial liquid composition in still (mole fraction of A)

X2 (xW) = final liquid composition in still (mole fraction A)

At any time t, the amount of liquid in the still is L, with mole fraction
of A in the liquid being x.
 Distillation Calculation
Performing a material balance on A:

Initial amount in still = Amount left in still + Amount vaporized

We have,

xL = (x - dx) (L - dL) + y dL

xL = xL - x dL - L dx + dx dL + y dL

Neglecting the term dx dL, the equation reduces to:

L dx = y dL - x dL

Re-arranging gives the following:

Derivation for Rayleigh equation

Integrating from L1 to L2, and from x1 to x2, we obtain the Rayleigh Equation:

Rayleigh Equation
Distillation Calculation
Using Rayleigh Equation:

Make a graph x vs 1/(y*-x)

What is in the limits of x=0.33 to 0.5

From the calculations above: W = 40.5 (xf=0.5, xw=0.33)

x y* 1/(y*-x)
0.33 0.515
0.36 0.549
0.39 0.580
0.42 0.610
0.45 0.639
0.48 0.666
0.5 0.684
 In Salalah Methanol Company a continuous fractionating column is to be designed
for separating 10,000 kg per hour of a liquid mixture containing 40 mole percent
methanol and 60 mole percent water into an overhead product containing 97 mole
percent methanol and a bottom product having 98 mole percent water. A mole
reflux ratio of 3 is used. Calculate (i) moles of overhead product obtained per hour
and (ii) number of ideal plates and location of the feed plate if the feed is at its
bubble point.
 Equilibrium data:
 x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.9
 y 0.417 0.579 0.669 0.729 0.78 0.825 0.871
0.915 0.959
 Where x = mole fraction of methanol in liquid
 And y = mole fraction of methanol in vapor
 In schlumberger a saturated liquid mixture containing 60 mole %
benzene and 40 mole % toluene is to be distilled continuously into a
distillate product containing 90 mole % benzene and the bottom product
containing 5 mole % benzene. The fractional distillation column will
operate at approximately constant pressure of 1 atm. The reflux ratio is 2.
How many theoretical plates must the column have if the feed is
introduced into the eighth plate? Equilibrium data are:

x 0 0.017 0.075 0.13 0.211 0.288 0.37 0.411 0.581 0.78 1

y 0 0.039 0.161 0.261 0.393 0.496 0.591 0.632 0.777 0.9 1

 100 kmol/h of a feed containing 35 mole%
methanol is to be continuosly distilled in
fractionating column to get 96.5 mole%
methanol as a distillate and 10 mole % as a
bottom product. Find the molal flow rates of
distillate and bottoms, and also draw the
distillation diagram by representing the flows.
 A feed containing 40 mole% benzene and 60
mole% toluene is to be distilled in a
fractionating column to get top product
containing 90 mole % benzene and bottoms
containing not more than 10 mole %
benzene. Find the distillate and bottom
products and represent in a distillation
column diagram?
 A mixture of benzene and toluene containing 60 mole % of
benzene is to be seperated to give a product of 95 mole %
benzene and bottom product containing 10 mole % benzene.
The feed enters a column at its bubble point. It is proposed to
operate the column with reflux ratio of 2.5. It is required to
find the number of theoritical plates needed and position of
feed plate. The vapour- liquid equilibrium data are given as
below:

x 0 0.05 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y 0 0.13 0.2 0.375 0.5 0.6 0.7 0.77 0.83 0.9 0.95 1
1