CHEMISTRY AND TECHNOLOGY OF PETROLEUM

Introduction:
The term petroleum comes from the Latin terms petra, "rock," and oleum, "oil." It is used to
describe a broad range of hydrocarbons that are found as gases, liquids, or solids beneath the surface of
the earth. The two most common forms are natural gas and crude oil.
 Natural Gas - is a mixture of lightweight alkanes, accumulates in porous rocks. A typical sample of
natural gas when it is collected at its source contains about 80% methane (CH4), 7% ethane (C2H6),
6% propane (C3H8), 4% butane and isobutane (C4H10), and 3% pentanes (C5H12). The C3, C4, and C5
hydrocarbons are removed before the gas is sold. The commercial natural gas delivered to the
customer is therefore primarily a mixture of methane and ethane. The propane and butanes
removed from natural gas are usually liquefied under pressure and sold as liquefied petroleum gases
(LPG).
 Crude oil - is a composite mixture of hydrocarbons (50-95% by weight) occurring naturally.
Petroleum is found in many parts of the world which include the Middle East, southern United
States, Mexico, Nigeria and the former Soviet Union.
Composition of Crude Oil:
- Crude oil consists mostly of hydrocarbons with small amounts of other organic chemical
compounds that may contain nitrogen, oxygen or sulfur.
- It may also contain trace amounts of metals such as iron, nickel, copper and vanadium.

- Petroleum is a mixture of a very large number of different hydrocarbons. The most common
hydrocarbons found in petroleum crude oil are linear or branched alkanes, (also called
paraffins), cycloalkanes (also called cyclic paraffins or naphthenes), aromatic hydrocarbons
or much more complicated chemicals like asphaltenes which may have a molecular weight
of 800 to 2500.
Formation of Crude Oil:
- According to generally accepted theory, petroleum is derived from ancient biomass. The
theory was initially based on the isolation of molecules from petroleum that closely
resembled known biomolecules.
- More specifically, crude oil and natural gas are products of heating of ancient organic
materials over geological time.
Crude Oil Sources:
Three conditions must be present for oil reservoirs to form, as depicted in the adjacent drawing:
- A reservoir of hydrocarbon material must exist and must have been buried deep enough for
subterranean heat and pressure to have transformed it over a long period of time into crude
oil.
 - A porous, permeable reservoir rock for the crude oil to accumulate in.
- A non-porous, non-permeable cap rock that acts to seal and to prevent the accumulated
crude oil from migrating upward and escaping to the surface.

Enhanced Oil Recovery:

- The initial or primary phase of recovering oil from an underground reservoir takes
advantage of the natural pressure existing in the reservoir, assisted by pumps (if needed) to
lift the oil to the surface.
- Enhanced Oil Recovery (abbreviated EOR) is a generic term for tertiary techniques used to
further increase the recovery of oil from an oil field.

Petroleum Refining
Three Main Steps:
1. Separation
- The oil is separated into its constituents by distillation, and some of these components (such
as the refinery gas) are further separated with chemical reactions and by using solvents.
2. Conversion
- The various hydrocarbons produced are then chemically altered to make them more
suitable for their intended purpose.
- For example, naphthas are "reformed" from paraffins and naphthenes into aromatics.
3. Purification
- The hydrogen sulfide gas which was extracted from the refinery gas in Step 1 is converted to
sulfur, which is sold in liquid form to fertilizer manufacturers.
I. PHYSICAL SEPARATION PROCESS
1. Crude distillation unit (CDU) is at the front-end of the refinery, also known as topping unit, or
atmospheric distillation unit.
- It receives high flow rates hence its size and operating cost are the largest in the refinery.
- This involves the removal of undesirable components like sulphur, nitrogen and metal
compounds, and limiting the aromatic contents.
- 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 operating at
about 50 mmHg, where heavier products are obtained.
A. Crude Oil Desalting
- The crude oil contains salt in the form of dissolved salt in the tiny droplet of water which
forms a water-in oil emulsion.
- This water cannot be separated by gravity or through mechanical means.
- It is separated through electrostatic water separation. This process is called desalting.
- Types of Salt in Crude Oil - These chlorides, except for NaCl, hydrolyze at high temperatures
to hydrogen chloride:
CaCl2  2H 2O  Ca(OH )2  2HCl
MgCl2  2H2O  Mg (OH )2  2HCl
 Hydrogen chloride dissolves in the overhead system water, producing hydrochloric acid, an
extremely corrosive acid.
Desalting process is accomplished through the following steps:
a. Water washing:
- Water is mixed with the incoming crude oil through a mixing valve.
- The water dissolves salt crystals and the mixing distributes the salts into the water,
uniformly producing very tiny droplets.
- Demulsifying agents are added at this stage to aide in breaking the emulsion by
removing the asphaltenes from the surface of the droplets.
b. Heating:
- The crude oil temperature should be in the range of 49-54 ˚C (120–130 F) since the
water–oil separation is affected by the viscosity and density of the oil.
c. Coalescence:
- The water droplets are so fine in diameter in the range of 1–10 mm that they do not
settle by gravity. Coalescence produces larger drops that can be settled by gravity.
- This is accomplished through an electrostatic electric field between two electrodes.
- The electric field ionizes the water droplets and orients them so that they are
attracted to each other.
- Agitation is also produced and aides in coalescence.
d. Settling

Simplified Diagram of an
electrostatic desalte

B. Atmospheric Distillation
 - The vapor from pipestill furnace discharge as a foaming stream into distillation tower.
- The partially vaporized crude is transferred to the flash zone.
- The vapour goes up the tower to be fractionated into gas oil that is called the overhead
product .
- liquid portion of feed go down to bottom of tower.

- The Temperature of tray is progressively cooler from bottom to top.

C. Vacuum Distillation
- To further distill the residual oil from the atmospheric distillation column, the distillation
must be performed at absolute pressures as low as 10 to 50 mmHg so as to limit the
operating temperature to less than 350°C.
- Vacuum distillation is the reduced temperature requirement at lower pressures.
- Vacuum distillation increases the relative volatility of the key components.

2. 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. This oil is also called ‘‘Bright Stock’’ and is used as feedstock for lube oil plant.
- The DAO can also be sent to cracking units to increase light oil production.
 3. Solvent Extraction
- In this process, lube oil stock is treated by a solvent, such as phenol and furfural, 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.
4. 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”.

II. CHEMICAL CATALYTIC CONVERSION

 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.
- The produced naphtha reformate has a much higher octane number than the feed. This
reformate is used in gasoline formulation and as a feedstock for aromatic production
(benzene–toluene–xylene, BTX).
 Hydrotreating
- This is one of the major processes for the cleaning of petroleum fractions from impurities
such as sulphur, nitrogen, oxy-compounds, chloro-compounds, aromatics, waxes and metals
using hydrogen.
- The catalyst is selected to suit the degree of hydrotreating and type of impurity. Catalysts,
such as cobalt and molybdenum oxides on alumina matrix, are commonly used.
 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.
 Alkylation
- Alkylation is the process in which isobutane reacts with olefins such as butylene (C4 ) to
produce a gasoline range alkylate.
- The catalyst in this case is either sulphuric acid or hydrofluoric acid. The hydrocarbons and
acid react in liquid phase.
 - Isobutane and olefins are collected mainly from FCC and delayed coker.

 Isomerization
- Isomerization of light naphtha is the process in which low octane number hydrocarbons (C4,
C5, C6) are transformed to a branched product with the same carbon number. This process
produces high octane number products.
- One main advantage of this process is to separate hexane (C6) before it enters the reformer,
thus preventing the formation of benzene which produces carcinogenic products on
combustion with gasoline.
- The main catalyst in this case is a Pt-zeolite base.

III. Thermal Chemical Conversion Process

 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.
- 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.