PETROLEUM

Petroleum or crude oil is naturally occuring liquid fuel. It is a dark brown or black coloured viscous oil found deep in earths crust. The oil is usually floating over a brine solution and above the oil, natural gas is present. Crude oil is a mixture of paraffinic, olefinic and aromatic hydrocarbons with small amounts of organic compounds like N, O and S.

The average composition of crude oil is as follows Constituents C H S N+O

Classification of Petroleum

Percentage (%) 80 87 11 15 0.1 3.5 0.1 0.5

1.Paraffinic-Base type crude oil 2.Naphthenic (or) Asphaltic Base type crude oil 3.Mixed Base type crude oil

REFINING OF PETROLEUM CRUDE OIL

The crude oil obtained from the earth is a mixture of oil, water and unwanted impurities. After the removal of water and other impurities, the crude oil is subjected to fractional distillation. During fractional distillation, the crude oil is separated into various fractions. Step : 1 Separation of water (Cottrells process) Step : 2 Removal of harmful sulphur compound Step : 3

Fractional distillation

 Step-1Separation of water (Cottrells Process) The crude oil from oil well is an extremely stable emulsion of oil and salt water. The crude oil is allowed to flow between two highly charged electrodes, where colloidal water droplets combine to form large drops, which is then separated out from the oil. Step 2: Removal of harmful sulphur

compounds
Sulphur compounds are removed by treating the crude oil with copper oxide. The copper sulphide formed is separated out by filtration.
Petrolium oil + CuO/Cu2O CuS + Sulphur free oil

Step 3: Fractional distillation

The purified crude oil is then heated to about 400C in an

iron retort, where the oil gets vapourised. The hot vapours are then passed into the bottom of a fractionating column.

The fractionating column is a tall cylindrical tower containing a number of horizontal stainless steel trays at short distances. Each tray is provided with small chimney covered with a loose cap.

When the vapours of the oil go up in the fractionating

column, they become cooler and get condensed at different trays.

The fractions having higher boiling points condense at lower trays whereas the fractions having lower boiling points condense at higher trays.

The gasoline obtained by this fractional distillation is called straight-run gasoline. Various fractions obtained at different trays are given in table

Various fractions, compositions and their uses

Heavy oils on Refractionation gives

CRACKING Definition Cracking is defined as the decomposition of high boiling hydrocarbons of high molecular weight into simpler, low boiling hydrocarbons of low molecular weight. C10H 22
Decane
B.Pt : 174OC

C5H12 + C5H10
n-Pentane
B.Pt : 36OC

Pentane

Necessity for Cracking

The crude oil on fractional distillation yields

- 20% gasoline. This is gasoline.

known

as

only about 15 straight run

The quality of straight run gasoline is not so good. It contains mainly straight chain paraffins, which ignite readily and more rapidly than any other hydrocarbons and hence it produces knocking (unwanted sound) in IC engines.
quality and quantity of gasoline, high boiling fractions are cracked into more valuable low boiling fractions suitable for SI engines. Thus gasoline obtained by cracking is called Cracked Gasoline.

Inorder to overcome these difficulties and also to improve the

 Cracking leads
Straight

chain alkanes are converted to branched chain hydrocarbons. (ii) Saturated higher hydrocarbons are converted to mixture of saturated and unsaturated lower hydrocarbons. (iii)Aliphatic alkanes may also be converted to cyclic compounds. (iv) All the hydrocarbons obtained by cracking have lower boiling point than the parent hydrocarbons.

Types of Cracking

There are two types of cracking.

1. Thermal Cracking.

2. Catalytic Cracking. Thermal Cracking

If the cracking is carried out at higher temperature and pressure without any catalyst, it is called thermal cracking. There are two types of thermal cracking.

Liquid Phase Thermal Cracking

In this method, the heavy oil is cracked at a temperature of 475 530C under high pressure of 100 kg/cm2 to keep the reaction product in liquid state. The cracked products are then separated into various fractions in a fractionating column. The yield of gasoline is about 50 - 60% and the octane number is 65 - 70.

Vapour phase thermal cracking

In this method, the heavy oil is first vapourised and then cracked at a temperature of 600 650C under a lower pressure of 10 20 kg/cm2. The yield of gasoline is about 70%. This process is suitable only for those oils which are readily vapourised.
Catalytic Crakcing If the cracking is carried out at lower temperature and pressure in the presence of suitable catalyst, it is called catalytic cracking. The catalyst used are aluminium silicate or alumina. There are two types of catalytic cracking. Fixed Bed Catalytic Cracking

The heavy oil vapour is heated to 420 450C in a preheater (Fig 4.3). The hot vapours are then passed through a catalytic chamber, maintained at 425 450C and 1.5 kg/cm2 pressure, where catalysts (artificial clay mixed with zirconium oxide), are kept in fixed beds. During this passage, through the catalytic chamber, about 40% of the heavy oil is converted into gasoline and about 2-4 % carbon is formed.

 The carbon gets adsorbed on the catalyst bed. The

cracked vapours are then passed through the fractionating column, where heavy oil gets condensed at the bottom. The vapours of gasoline are then sent through the cooler where gasoline gets condensed along with some gases.

The gasoline containing some dissolved gases is then sent to a stabiliser, where the dissolved gases are removed and pure gasoline is recovered.

After 8-10 hours, the catalyst loses its activity due

to the deposition of carbon. It is reactivated by burning off the deposited carbon.

Moving bed (or) Fluid bed catalytic cracking In this process, the solid catalyst is finely powdered, so that it behaves as a fluid, which can be circulated in oil vapour.

The heavy oil vapour is heated to 420 450C in a

preheater and it is mixed with the catalyst powder.

Then this mixture is forced into the reactor, which is maintained at a temperature of 500C and a pressure of 5 kg/cm2, where cracking takes place. Near the top of the reactor, there is a centrifugal separator (called cyclone), which allows only the cracked oil vapours to pass on to the fractionating column leaving behind the catalyst powder in the reactor itself.

 The catalyst powder gradually becomes heavier, due to

coating of carbon and it settles down at the bottom of the reactor.

Then it is forced into the regenerator maintained at 600C, where carbon is burnt and the regenerated catalyst is again recirculated along with the heavy oil vapour.

From the reactor the cracked oil vapours are passed into

the fractionating column, where heavy oil settles down and the vapours are then passed through the cooler where gasoline condenses along with some gases.

The dissolved gases are separated from gasoline by passing it through a stabiliser.

Advantages of Catalytic Cracking Over Thermal Cracking

1. The yield of petrol is higher. 2. The quality of petrol produced is better. 3. The production cost is very less, since high temperature and high pressure are not required. 4. No external fuel is necessary for cracking. The heat required for cracking is derived by burning the carbon deposited on the catalyst.

5. The percentage of gum and gum forming compounds is very low. 6. The products contain less sulphur compounds. 7. The octane number of cracked gasoline is higher when compared to straight-run gasoline. This is due to the presence of branched paraffins and aromatic hydro carbons in cracked gasol 8. The cracking process can be easily controlled, so the desired products can be maintained

SYNTHETIC PETROL The gasoline, obtained from the fractional distillation of crude petroleum oil, is called straight run petrol. As the use of gasoline is increased, the amount of straight run gasoline is not enough to meet the requirement of the present community. Hence, we are in need of finding out a method of synthesizing petrol.

Hydrogenation

of coal (or) Manufacture of synthetic

petrol

Coal contains about 4.5% hydrogen compared to about 18% in petroleum. coal is a hydrogen deficient compound. If coal is heated with hydrogen to high temperature under high pressure, it is converted to gasoline. The preparation of liquid fuels from solid coal is called hydrogenation of coal (or) synthetic petrol.

There are two methods available for the hydrogenation of coal

1. Bergius process (or direct method). 2. Fischer-Tropsch process (or indirect method). Bergius process (or direct method).

In this process, the finely powdered coal is made into a paste with heavy oil and a catalyst powder (tin or nickel oleate) is mixed with it. The paste is pumped along with hydrogen gas into the converter, where the paste is heated to 400 450C under a pressure of 200 250 atm.

Bergius Process

 During this process hydrogen combines with coal to form saturated higher hydrocarbons, which undergo further decomposition at higher temperature to

yield mixture of lower hydrocarbons.

The mixture is led to a condenser, where the crude oil is obtained. The crude oil is then fractionated to yield (i) Gasoline (ii) Middle oil (iii) Heavy oil. The middle oil is further hydrogenated in vapour phase to yield more gasoline. The heavy oil is recycled for making paste with fresh coal dust. The yield of gasoline is about 60% of the coal used.

Fischer-Tropsch process (or indirect method In this process coal is first converted into coke. Then water gas (CO + H2) is produced by passing steam over red hot coke.

C + H2O

1200 C

CO + H2
Water gas

The water gas is mixed with hydrogen and the mixture is purified by passing through Fe2O3 (to remove H2S) and then into a mixture of Fe2O3 + Na2CO3 (to remove organic sulphur compounds).

The purified gas is compressed to 5 to 25 atm and then led through a converter, which is maintained at a temperature of 200 300C. The converter is provided with a catalyst bed consisting of a mixture of 100 parts cobalt, 5 parts thoria, 8 parts magnesia and 200 parts keiselghur earth.

A mixture of saturated and unsaturated hydrocarbon is produced as a result of polymerisation nCO + 2nH2 CO + 3H2 nCO + (2n + 1) H2 CnH2n + nH2O CH4 + H2O Cn H2n+2 + nH2O

The outcoming gaseous mixture is led to a condenser, where the liquid crude oil is obtained. The crude oil is fractionated to yield (i) gasoline and (ii) heavy oil. The heavy oil is used for cracking to get more gasoline.