INTRODUCTION TO CRUDE OIL/ PETROLEUM
Petroleum (also called crude oil) is a mixture of gaseous, liquid, and solid hydrocarbon
compounds.
Petroleum occurs in sedimentary rock deposits throughout the world and also
contains small quantities of nitrogen oxygen and sulfur-containing compounds as well
as trace amounts of metallic constituents.
A complex mixture containing thousands of different organic hydrocarbon molecules
Color: Light brown to dark brown
[Link]: 0.81—0.985
Boiling range: 25 – 400oC Hydrocarbons C1- C70 (4000 compounds)
Fig. 1 Crude Oil
Crude composition
Hydrocarbon Components
C: 84-87%,
H: 11-14%
Hydrocarbon components comprises of Paraffins, Naphthene and Aromatics
Non-Hydrocarbon components
S: 0.05-6%,N: 0.1 -2%,O: 0.05-1.5%.
Metals < 0.1: V, Fe, Ni S-( H2S,Thiols (mercaptans), sulfides, di sulfides, poly sulfides and
thiophenes). Cause corrosion of equipments, bad odour in products,catalyst poisoning, Air
pollution. N –Indols, pyridines and quinolenes (Difficult to remove).
Oxygen compounds: present as naphthenic acids and phenols
Are corrosive in nature and cause odour.
Metal: act as catalyst poisons
The hydrocarbons found in petroleum are classified into the following types
Paraffins(CnH2n+2)saturated hydrocarbons with straight or branched chains, but
without any ring structure.
Cycloparaffins (CnH2n)(naphthenes),saturated hydrocarbons containing one or more
rings, each of which may have one or more paraffin side-chains(also known as
alicyclic hydrocarbons).
Aromatics(CnH2n-6)i.e,hydrocarbons containing one or more aromatic nuclei such as
benzene, naphthalene, and phenanthrene ring systems that may be linked up with
(substituted) naphthalene rings or paraffin side-chains.
Paraffins:
Carbon atoms connected by single bond
Other bonds saturated with hydrogen
Naphthenes:
Ringed Paraffins (Cycloparaffins)
All bonds saturated with hydrogen
Aromatics:
Six Carbon Rings (Multiple Bonding)
All bonds unsaturated
Olefins:
Usually not in crude oil
Formed During Processing
At least two carbon atoms connected by double bond
Only Pennsylvanian oil is exceptional
Fig: 2 A typical example of n-butane, Cyclopentane, Decaline, Benzene, Napthalene, and 1-
butene.
Fig 3: Refinery Products
Pretreatment of Crude Oil
As the Crude oil that comes from drilling operation consists of large amount of impurities.
Crude oil comes from the ground, which contains variety of substances like gases, water, dirt
(minerals) etc.
Pretreatment of the crude oil is important if the crude oil is to be transported effectively and to be
processed without causing fouling and corrosion in the subsequent operation starting from
distillation, catalytic reforming and secondary conversion processes.
IMPURITIES
Impurities in the crude oil are either oleophobic or oleophilic.
OLEOPHOBIC IMPURITIES: Oleophobic impurities include salt, mainly chloride & impurities of Na, K,
Ca& Mg, sediments such as salt, sand, mud, iron oxide, iron sulphide etc. and water present as soluble
emulsified and /or finely dispersed water.
OLEOPHILIC IMPURITIES: Oleophilic impurities are soluble and are sulphur compounds,
organometallic compounds, Ni, V, Fe and As etc, naphthenic acids and nitrogen compounds.
These impurities must be removed to avoid problems in subsequent processing operations. Several
problems which can caused by oleophobic impurities are:
1. Corrosion in the atmospheric distillation overhead system caused by HCl, liberated due to
hydrolysis or dissociation of chloride salts such as calcium chloride and magnesium chloride.
2. Increases consumption of ammonia to neutralize the HCl
3. Erosion of crude oil pumps, pipelines and valves by suspended matter through abrasive action
4. Plugging of equipment and fouling of heat transfer surfaces
5. Product degradation, like high ash content in fuel oil
6. Trace metals in distillates, which act as catalyst poisons.
Pretreatment of the crude oil removes the oleophobic impurities.
PRETREATMENT STEPS ARE
SEDIMENTATION AND DECANTATION
Field separation is the first step to remove the gases, water and dirt that accompany crude oil
coming from the ground and is located in the field near the site of the oil wells. The field separator
is often no more than a large vessel, which gives a quieting zone to permit gravity separation of
three phases: gases, crude oil and water (with entrained dirt).
GAS REMOVAL
When the pressure reduces, the gases escapes out and there is escape of oil along with the gases.
Therefore, these gases are removed and recovered in a group gathering station (GGS) in which
gases are removed in steps, preventing loss of oil.
CRUDE DESALTING
It is a water washing operation performed at the refinery site to get additional crude oil clean up.
Crude Oil Desalting consists of
(a) Purifying process
(b) Remove salts, inorganic particles and residual water from crude oil
(c) Reduces corrosion and fouling
Desalting process is used for removal of the salts, like chlorides of calcium, magnesium and
sodium and other impurities as these are corrosive in nature. The crude oil coming from field
separator will continue to have some water/brine and dirt entrained with it. Water washing
removes much of the water-soluble minerals and entrained solids (impurities).
Commercial crudes, salt contents 10-200 ppb, earlier 10-20 ppb were considered satisfactorily
low. However, many refiners now aim at 5 ppb or less (1-2 ppb) which is not possible through
single stage desalting, hence two stage desalting is required. Desalting process consists of
three main stage: heating, mixing and settling.
Pre Fractionation
It is also a pre-treatment step, a pre-fractionator is installed if the crude to be processes
contains large amount of lighter fractions. A pre=fractionator is a distillation column and
removes light ends. This is required to avoid load on further processing equipmet.
Pre-Heating of Crude Oil
It is a very important step in pre-treatment, before sending the crude oil to atmospheric
distillation unit it is vaporized to a maximum temperature and it requires heating. Crude oil
heating is carried out in a special type of heating furnaces termed as tube still furnaces. The
basic design consists of two sections (a) Radiant Section and (b) Convection Section
The crude oil to be heated enters the convection section and achieve around 70% heating in
this section, the remaining heating is carried out in radiant section where heat is generated
by direct firing. The gases from radiant section moves to convection section where crude oil
is placed in tubes and here heating is done by convection.
Tube Still Furnace
Difference between Conventional Distillation and Crude Oil Distillation
Distillation Fractional Distillation
Distillation is a process used to separate Fractional Distillation is a process used to
liquids with boiling points which separate liquids with closer boiling points
comprises of gaps around 50 degrees at
least.
The process doesn’t have to be repeated The process has to be repeated several
to obtain pure components times to obtain pure component
The experimental set up is simple. Needs The experimental set up is complex. We
a simple apparatus with two simple flasks need a complex apparatus with a
and a condenser fractioning column
This technique can be used to separate a This technique cannot be used to
solvent from solute separate a solvent from solute
Used in the purification of seawater Used in crude oil refining
Conventional Distillation Crude Oil Distillation
Only two key components are obtained Intermediate fractions are recovered
through side stream strippers
Feed enters generally at the middle of the Feed Enters at the Bottom of the Tower
Tower
Reboiler is required at the bottom of the tower No Reboiler is required, heated feed enters the
tower
Relatively lesser number of trays Large number of trays
Only top tray reflux Intermediate refluxes are there
No live steam is injected Live steam is injected at the base of the tower
Tower size small Tower size large