PETROLEUM REFINING AND PETROCHEMICALS

SUB CODE: 2180502

MORADIYA MILAN L | 160190105043

ASSIGNMENT NO 3: CRACKING

Question 1: Define Cracking. Classify Cracking operations

Ans: Cracking is the breakdown of a large alkane into smaller, more useful alkenes.
 In petrochemistry, petroleum geology and organic chemistry, cracking is the process
whereby complex organic molecules such as kerogens or long-chain hydrocarbons are
broken down into simpler molecules such as light hydrocarbons, by the breaking of
carbon-carbon bonds in the precursors.
 The rate of cracking and the end products are strongly dependent on the temperature
and presence of catalysts.
 More loosely, outside the field of petroleum chemistry, the term "cracking" is used to
describe any type of splitting of molecules under the influence of heat, catalysts and
solvents, such as in processes of destructive distillation or pyrolysis.

 Classification of Cracking

1. Thermal cracking
 Modern thermal Cracking
 Steam Cracking

2. Catalytic cracking
 Fluid Catalytic Cracking
 Hydrocracking
Question 2: Explain Catalytic Cracking.

Ans: The catalytic cracking process involves the presence of solid acid catalysts, usually
silica-alumina and zeolites. The catalysts promote the formation of carbocations, which undergo
processes of rearrangement and scission of C-C bonds. Relative to thermal cracking, cat cracking
proceeds at milder temperatures, which saves energy. Furthermore, by operating at lower
temperatures, the yield of alkenes is diminished. Alkenes cause instability of hydrocarbon fuels.

1) Fluid Catalytic Cracking

 Initial process implementations were based on low activity alumina catalyst and a reactor
where the catalyst particles were suspended in a rising flow of feed hydrocarbons in a
fluidized bed.

Figure 1: Schematic flow diagram of a fluid catalytic cracker

 In newer designs, cracking takes place using a very active zeolite-based catalyst in a short-
contact time vertical or upward sloped pipe called the "riser". Pre-heated feed is sprayed
into the base of the riser via feed nozzles where it contacts extremely hot fluidized
catalyst at 1,230 to 1,400 °F (666 to 760 °C). The hot catalyst vaporizes the feed and
catalyzes the cracking reactions that break down the high-molecular weight oil into lighter
components including LPG, gasoline, and diesel. The catalyst-hydrocarbon mixture flows
 upward through the riser for a few seconds, and then the mixture is separated via
cyclones. The catalyst-free hydrocarbons are routed to a main fractionator for separation
into fuel gas, LPG, gasoline, naphtha, light cycle oils used in diesel and jet fuel, and heavy
fuel oil.

 During the trip up the riser, the cracking catalyst is "spent" by reactions which deposit
coke on the catalyst and greatly reduce activity and selectivity. The "spent" catalyst is
disengaged from the cracked hydrocarbon vapors and sent to a stripper where it contacts
steam to remove hydrocarbons remaining in the catalyst pores. The "spent" catalyst then
flows into a fluidized-bed regenerator where air (or in some cases air plus oxygen) is used
to burn off the coke to restore catalyst activity and also provide the necessary heat for
the next reaction cycle, cracking being an endothermic reaction. The "regenerated"
catalyst then flows to the base of the riser, repeating the cycle.

2) Hydrocracking
 Hydrocracking is a catalytic cracking process assisted by the presence of added hydrogen
gas. Unlike a hydrotreater, hydrocracking uses hydrogen to break C-C bonds
 The major products from hydrocracking are jet fuel and diesel, but low Sulphur, naphtha
fractions and LPG are also produced.
 The hydrocracking process depends on the nature of the feedstock and the relative rates
of the two competing reactions, hydrogenation and cracking. Heavy aromatic feedstock
is converted into lighter products under a wide range of very high pressures (1,000-2,000
psi) and fairly high temperatures (750°-1,500 °F, 400- 800 °C), in the presence of hydrogen
and special catalysts. The primary functions of hydrogen are, thus:
1. Preventing the formation of polycyclic aromatic compounds if feedstock has
a high paraffinic content,
2. Reducing tar formation,
3. Reducing impurities,
4. Preventing buildup of coke on the catalyst,
5. Converting sulfur and nitrogen compounds present in the feedstock to
hydrogen sulfide and ammonia,
6. Achieving high cetane number fuel.
Question 3: Explain Regeneration of Catalyst in Fluid catalytic Cracking process.
Ans: The spent catalyst which is relatively cold enters the regenerator unit.
 Air enters the vessel through a sparger set up.
 Catalyst is subsequently burnt in the air. This enables both heating the catalyst (which
is required to carry out the endothermic reaction) and removing the coke so as to
regain the activity of the coke.
 catalyst + air after this operation will enter the cyclone separator unit.
 Unlike the FCCR, the CR does not have a riser.
Therefore, air enters a dense phase of
catalyst and also enables the movement of
the catalyst to a dilute phase of catalyst + air
 The cyclone separators separate the flue gas
and catalyst as a solid fluid operation.
 activity regained catalyst is sent to the riser
through a pipe.
 this entire operation, the catalyst
temperature is increased to 620 – 750 oC
 The flue gas is obtained at 600 -760 oC and is
sent for heat recovery unit to generate
steam.
 These are old generation catalytic cracking
reactors
 There are basically four sections namely
reactor, generator, catalyst engaging hopper Figure 2: Flow diagram of catalyst regeneration unit
and catalyst disengaging hopper.
 Catalyst disengaging hopper feeds the regenerated
catalyst to the reactor.
 Reaction, the products are recovered from the unit.
 The bed moves to the regenerator unit where air is used to regenerate the catalyst
 The regenerated catalyst enters the engaging hopper unit from where using lift media
the catalyst is moved to the disengaging hopper unit.
Question 4: Discuss Thermal Cracking.

Ans: Thermal technique of cracking is sub-classified into two types:

• Modern thermal cracking: Unlike conventional thermal cracking technique, the modern
thermal cracking methods employ the use of high pressure along with high temperatures to carry
out the degradation of large molecular weight hydrocarbons into smaller fragments. The modern
technique of high pressure coupled thermal cracking involves reaching absolute pressures as high
as 7000kPa. The process involves homolytic emission of the carbon bonds where each fragment
of the high molecular weight hydrocarbon compound retains one electron on each side which
then couple together or condense to lead to the formation of small molecules of lesser molecular
weight like alkenes. These reactions are also important industrially for the production of certain
polymers which involve alkynes as their basic structural units; the most common example is one
of the most popular plastic – polythene whose basic structural unit is the smallest alkyne that
exists namely ethylene. Thermal cracking has been redefined and improved greatly since it earlier
process in the early 1900. It is now used to produce industrially useful small molecular fragments
obtained from the crude large hydrocarbons. The lighter fractions of these hydrocarbons
produced are used as burner fuels. As one of the process variants, thermal cracking is sometimes
carried out at a relatively milder temperature (about 500 C, unlike normal operating temperature
which ranges from about 750 C to 900 C). This process is also known as delayed coking. This is
done to obtain a one carbon-rich solid compound known as needle coke, which is a highly
crystalline form of coke obtained from petroleum and is used in the production of carbon
electrodes used in the aluminium and iron or steel industry.

• Steam Cracking: As the name suggests, this type of thermal cracking is carried out by using heat
energy from the steam. This technique is also known as pyrolysis. This method of thermal
cracking is more efficient and productive as compared to the conventional heat-based thermal
cracking method. This is because steam possesses more latent heat of energy as compared to
the normal heat source. Steam cracking is a very useful technique industrially as it is currently
the most widely used source of production of low molecular weight alkenes (also known as the
ole􀃒ns). The most useful alkene obtained from this method is ethene (or ethylene) which is
widely used in the polymer industry and is one of the most common basic structural units of
plastics. Another such useful alkene produced is propene (also commonly known as propylene).
In the process of steam cracking, raw materials such as liquid petroleum gas, naphtha, butane,
propane and ethane are pumped into the source which is then supplied with high energy steam
to produce light and small molecular weight hydrocarbons. The yield of the molecules produced
in this process is generally dependent upon the ratio of raw materials and steam present in the
chamber and also on the initial composition of the raw materials used. This process is usually
carried out in the absence of oxygen and the temperature of the actual reaction recorded is
approximately about 800°C to 850 C. In the modern-day variants of this technique, the speed at
which the steam is passed through the raw materials is increased thereby resulting in the
decrease in the total time of the reaction.
Question 5: Differentiate Catalytic Cracking and Thermal Cracking

Ans:

Catalytic Cracking Thermal Cracking

Catalytic cracking is the breakdown of large Thermal cracking is the process of breakdown
compounds into small hydrocarbons using an large compounds into small compounds at
acid catalyst high Temperature and /pressure

Involves cracking by adding catalyst along Involves cracking by adding catalyst along
with moderate temperature and pressure with High temperature and pressure

The temperature ranges between 475 – 530 The temperature ranges between 500 – 700
Degrees Celsius Degrees Celsius

Pressure used is about 20 atm Pressure used is about 70 atm

Used to obtain fuel with octane number 65 – Used for visbreaking, thermal gasoline
70 production and delayed coking

Does require Regenerator Does not require Regenerator

Coke formation is less Coke formation is large