Cracking  

Week Topic
1 Introduction. History of the Petroleum Industry, Chemistry of Petroleum
2 Petroleum processing equipment, Storage tanks, rectification columns;
3 Heat Exchange apparatus in refinery processes, pipe furnaces, Pipe lines and fittings;
4 compressors and pump.
5 Brief description; Refinery Preliminary processing. Refinery Thermal processes;
6 Brief description; Refinery Preliminary processing. Refinery Thermal processes;
7 Catalytic cracking / Thermal Cracking
8 Catalytic reforming;
9 Hydrogenation processes;
10
11 Hydro-cracking
 Cracking
• Cracking, in petroleum refining, the process by which heavy
hydrocarbon molecules are broken up into lighter molecules by
means of heat and usually pressure and sometimes catalysts. 
• Cracking is the most important process for the commercial production
of gasoline and diesel fuel.
 Cracking
• Cracking of petroleum yields light oils (corresponding to gasoline), middle-
range oils used in diesel fuel, residual heavy oils, a solid carbonaceous
product known as coke, and such gases as methane, ethane, ethylene,
propane, propylene, and butylene.
• Depending on the end product, the oils can go directly into fuel blending,
or they can be routed through further cracking reactions or other refining
processes until they have produced oils of the desired weight.
• The gases can be used in the refinery’s fuel system, but they are also
important raw materials for petrochemical plants, where they are made
into a large number of end products, ranging from synthetic rubber and
plastic to agricultural chemicals.
 Cracking
• Increasing the relative proportions of lighter or more volatile components of an
oil by breaking down the larger hydrocarbon molecules into smaller molecules.
• Thermal cracking is effected solely by the action of temperature and pressure
and is characterized by a high yield of coke and light product.
• Catalytic cracking involves the use of catalysts that enable more extensive and
more selective conversion of heavier fractions to gasoline and middle distillates
atlower temperatures.
• Hydrocracking A cracking process carried out in the presence of hydrogen and
with the aid of catalysts, in which heavy hydrocarbons are cracked to significantly
lighter products, with process efficiencies and product qualities superior to those
obtained with conventional catalytic cracking.
• Catalytic cracking is an important process in the oil industry where
petroleum vapor passes through a low-density bed of catalyst, which
causes the heavier fractions to ‘crack’ producing lighter more valuable
products.
• Thermal cracking is a process in which hydrocarbons present in crude
oil are subject to high heat and temperature to break the molecular
bonds and breaking down long-chained, higher-boiling hydrocarbons
into shorter-chained, lower-boiling hydrocarbons.
 Difference Between Hydro Cracking And
Catalytic Cracking
• The basis of catalytic cracking is carbon rejection, while hydrocracking
is a hydrogen addition process.
• Catalyst cracking uses an acid catalyst, while hydrocracking uses a
metal catalyst on acid support.
• Another difference is that catalyst cracking is an endothermic process
while hydrocracking is an exothermic process.
 Difference Between Thermal Cracking And
Catalytic Cracking
• The main difference between thermal cracking and catalytic cracking
is that thermal cracking uses heat energy for the breakdown of
compounds whereas catalytic cracking involves a catalyst to obtain
products.
 Cracking
• Cracking of petroleum yields light oils (corresponding to gasoline), middle-
range oils used in diesel fuel, residual heavy oils, a solid carbonaceous
product known as coke, and such gases as methane, ethane, ethylene,
propane, propylene, and butylene.
• Depending on the end product, the oils can go directly into fuel blending,
or they can be routed through further cracking reactions or other refining
processes until they have produced oils of the desired weight.
• The gases can be used in the refinery’s fuel system, but they are also
important raw materials for petrochemical plants, where they are made
into a large number of end products, ranging from synthetic rubber and
plastic to agricultural chemicals.
 Cracking and alkenes
• Cracking is a reaction in which larger
saturated hydrocarbon molecules are
broken down into smaller, more useful
hydrocarbon molecules, some of which
are unsaturated:
• the original starting hydrocarbons are
alkanes
• the products of cracking include alkanes
and alkenes, members of a different
homologous series
• For example, hexane can be cracked to
form butane and ethene:
• hexane → butane + ethene
• C6H14 → C4H10 + C2H4
• The starting compound will always fit
the rule for an alkane, CnH2n+2. The
first product will also follow this rule.
The second product will contain all the
other C and H atoms. The second
product is an alkene, so it will follow the
rule CnH2n.
 Cracking Question
• Question • C16H34 → C10H22 + C6H12
• C16H34 is an alkane which can be
used as the starting chemical in
cracking.
• One of the products of cracking
this compound is an alkane
which has 10 carbon atoms in it.
• Write a balanced symbol
equation for this cracking
reaction
 Thermal Cracking
• Thermal cracking is a process in which hydrocarbons present in crude
oil are subject to high heat and temperature to break the molecular
bonds and breaking down long-chained, higher-boiling hydrocarbons
into shorter-chained, lower-boiling hydrocarbons..
 Thermal Cracking
• In thermal cracking, high temperatures (typically in the range of 450°C
to 750°C) and pressures (up to about 70 atmospheres) are used to
break the large hydrocarbons into smaller ones.
• Thermal cracking gives mixtures of products containing high
proportions of hydrocarbons with double bonds - alkenes.
• Thermal cracking doesn't go via ionic intermediates like catalytic
cracking. Instead, carbon-carbon bonds are broken so that each
carbon atom ends up with a single electron. In other words, free
radicals are formed.
 Catalytic Cracking
• Catalytic cracking in the usual commercial process involves contacting
the feedstock with a catalyst under suitable conditions of
temperature, pressure, and residence time.
• By this means, a substantial part (>50%) of the feedstock is converted
into gasoline and lower boiling products, usually in a single pass.
 Catalytic Cracking
• Modern cracking uses zeolites as the catalyst.
• These are complex alumino-silicates, and are large lattices of
aluminum, silicon and oxygen atoms carrying a negative charge.
• They are, of course, associated with positive ions such as sodium ions.
• You may have come across a zeolite if you know about ion exchange
resins used in water softeners.
• The alkane is brought into contact with the catalyst at a temperature
of about 500°C and moderately low pressures.
 Catalytic Cracking
• The zeolites used in catalytic cracking are chosen to give high
percentages of hydrocarbons with between 5 and 10 carbon atoms -
particularly useful for petrol (gasoline).
• It also produces high proportions of branched alkanes and aromatic
hydrocarbons like benzene.
• The zeolite catalyst has sites which can remove a hydrogen from an
alkane together with the two electrons which bound it to the carbon.
• That leaves the carbon atom with a positive charge. Ions like this are
called carbonium ions (or carbocations). Reorganization of these leads
to the various products of the reaction.
 The Catalyst
• The catalyst used in modern cat crackers is a marvel of evolution.
• It used to be made of natural alumina-based clay, but now refiners
buy only the much-improved synthetically produced cat cracking
catalysts called zeolytes.
• The particles have three unusual characteristics. If you had a jar of cat
cracker catalyst and shook or tilted it, the powder, which looks like off-
white baby powder, would slosh around just like a fluid.
• This behavior, so important to the design of the whole process, gave
rise to another name refiners often use, fluid cat cracking.
 The Catalyst
• The second characteristic is not apparent to the naked eye.
• Using an electronic microscope, you would be able to see that each
catalyst particle has a large number of pores and, as a consequence, a
tremendous surface area, especially in relation to the size of the
particle.
• If the particles were the size of the planet Earth, the pores would be
deeper than the Grand Canyon and spaced every few miles or so over
the surface.
• The influence of the catalyst depends on contact with the cat feed, so
the huge surface area is vital to the process.
 The Catalyst
• The third characteristic in the modern cat cracker catalysts comes from technology leaps.
• The old alumina-based clay catalyst already had the minerals necessary to promote the cracking
reactions.
• Nowadays the catalysts are synthesized to exacting dimension and mineral content.
• The pores are designed and fabricated so minutely that they will let in just one molecule at a
time, and only molecules of a certain size, at that.
• That way the types of molecules that are catalyzed can be controlled and refiners can end up
with designer outturns (well, almost).
• The catalyst suppliers can furnish refiners with catalysts that will favor (but not deliver 100%)
the creation of high octane gasoline components or, perhaps, the light olefins (propylene and
butylenes).
• Other catalysts are designed to permit the use of heavier feeds, or not to create so much coke,
or to reduce the temperature of the reaction to save energy, and so on.
 Catalytic Cracking – The Process
• During the cracking process, lots of phenomena occur:
• As the large molecules crack, there is not enough hydrogen to go
around, so some small amounts of carbon form coke, which is
virtually pure carbon atoms stuck together.
• As the large molecules break up, a full range of smaller molecules
from methane on up are formed. Due to the deficiency of hydrogen,
many of the molecules are olefins (those double-bonded paraffins).
• Where the large molecules in the feed are made up of several
aromatic or naphthene rings stuck together, smaller aromatic or
naphthenic compounds plus some olefins can result.
 Catalytic Cracking
• Finally, the large molecules, made up of several aromatic or
naphthenic rings plus long side chains, are likely to crack where he
side chains are attached.
• The resulting molecules, though lower in carbon count, may be more
dense or heavier; that is, their specific gravity is higher and their API
gravity is lower.
• They also tend to have higher boiling temperatures. Ironically these
molecules can form a product heavier than the feed.
Catalytic Cracking Unit
 Catalytic Cracking
• The products of cat cracking are the full range of hydrocarbons, from
methane through to residue, plus coke.
• Three main parts make up the cat cracking hardware:
• the reaction section,
• the regenerator,
• and the fractionator.
Catalytic Cracking - the reaction section
• The guts of the cat cracker is the
reaction section , consisting of
the cat feed heater and the riser,
which is a pipe from ground level
up to a water tank–like vessel
called a disengagement
chamber.
• The heater (not shown in figure)
raises the temperature of the cat
feed to about 700ºF.
 Catalytic Cracking - the reaction section
• The feed mixes with hot catalyst being fed into the riser, and steam is
introduced with the catalyst to give the whole mixture enough lift to
climb up to the bottom section of the disengagement chamber.
• All that raises the temperature to 900ºF to 1,100ºF, promoting the
cracking.
• Almost all the cracking reactions take place in the riser, even though
residence time in the riser is only about a second.
• In the older cat crackers, the disengagement chamber was called the
reactor because it was thought that was where most of the cracking
took place. The newer crackers use this vessel only to separate the
catalyst from the hydrocarbon.
Catalytic Cracking - the reaction section
• As the hydrocarbon/catalyst mixture hits the disengagement
chamber, it encounters a cyclone, a mechanical device that spins the
mixture.
• The catalyst being heavier, the centrifugal motion slaps it against the
walls of the cyclone, where it slides to the bottom and out the piping,
exiting the disengagement chamber via gravity.
• The hydrocarbon, mostly in vapor form but with some liquid droplets,
rises from the cyclone to the top of the chamber, encounters another
cyclone that does a final catalyst separation, and then exits the top.
Catalytic Cracking - the reaction section
• Refiners had a purpose in switching to a design where all the
reactions take place in the riser instead of in the reactor—to lengthen
the contact time between the feed and the catalyst.
• However, on some riser crackers, as the new vintage of CCUs is
sometimes called, the hardware is set up to allow some feed to be
introduced further up the riser to reduce the contact time.
• That allows refiners to segregate the feed from different crudes, since
feeds with different compositions often respond to the catalysts at
different rates.
Catalytic Cracking - The regenerator
• During the cracking process, some portion of
hydrocarbon cracks all the way to coke and ends
up as a deposit on the catalyst.
• As the catalyst surface is covered up, the
catalyst becomes inactive (or spent), which
reduces its effectiveness.
• To remove the carbon, the spent catalyst flows
by gravity to a vessel called a regenerator (fig).
• Heated air, about 1,100ºF, is mixed with the
spent catalyst, and a chemical reaction takes
place that removes the coke from the catalyst:
 Catalytic Cracking - The regenerator
• This process, oxidation of coke, is similar to burning coal or briquettes
in that carbon unites with oxygen and gives off carbon dioxide (CO2),
perhaps carbon monoxide (CO), and a large amount of heat.
• Part of the heat transfers to the catalyst, which leaves the
regenerator as hot regenerated catalyst, en route to the riser.
• The rest leaves as hot CO2, which can be used as source for heating
the feed or elsewhere.
• In the older cat crackers, the CO/CO2 is sent to a CO furnace, where
oxidation of the rest of the CO to CO2 is completed.
 Catalytic Cracking - The regenerator
• The regenerator has its own cyclone at the top that separates the
catalyst from the CO/CO2.
• The regenerated catalyst flows from the cyclone, again by gravity, out
of the regenerator, ready to be mixed with cat feed and steam and
sent up the riser once more.
• Thus the catalyst is in continuous motion going through the
cracking/regeneration cycle.
 Catalytic Cracking - The regenerator
• Small amounts of brand new, fresh catalyst are continually added.
Some of the circulating catalyst will have ended not on the catalyst
side of the cat cracker but as catalyst fines in the bottom of the cat
cracker fractionator.
• Also some escapes with the CO2 stream. In addition, some crude oils
have metals in them that deactivate some catalyst particles, which
then need replacement.
 Catalytic Cracking – The fractionator
• Meanwhile, back on the hydrocarbon side, when the cracked product leaves the
disengagement vessel, it is charged to a fractionating column (fig) dedicated to the cat
cracker products.
• The products separated generally are the gases (C4 and lighter), cat-cracked gasoline,
cat-cracked gas oil, and the fractionator bottoms, called slurry oil because it contains
some of the catalyst that did not get caught by the cyclones.
• A variety of things can be done with the slurry oil, but the most popular is to mix it
with the fresh cat feed and run it through the reaction again.
• Some of the slurry oil may crack each time through the reactor. By recycling enough,
all the slurry oil may be made to disappear.
• The process has the ominous designation recycling to extinction. Sometimes the most
stubborn molecules just keep going around in a circle with no further cracking, so a
small amount of cycle oil can be drawn off continuously.
Catalytic Cracking – The fractionator
• After sitting in a settling tank
where the catalyst settles to the
bottom, the clarified slurry oil
can be blended off to heavy fuel
oil.
 Catalytic Cracking – The fractionator
• The cat-cracked gas oil may be separated into light and heavy gas oil.
Both are sometimes called cycle oil (light cycle oil, heavy cycle oil).
• In the past both have sometimes been recycled to the reaction section
also.
• Nowadays most refiners send the gas oil streams elsewhere.
• The cat-cracked heavy gas oil can be used as feed to a hydrocracker or
as a residual fuel component.
• The light gas oil makes a good blending stock for distillate fuel (but not
diesel fuel).
• The cat-cracked gasoline is a good motor gasoline blending component.
 Catalytic Cracking – The fractionator
• There is quite a bit of latitude in the cut point between the gasoline and light
gas oil stream.
• Refiners use this as one way to regulate the balance between gasoline and
distillate as the seasons change.
• As the winter heating oil season comes on, many refineries go into a max
distillate mode.
• They make adjustments to the CCU fractionator to lower the end point of the
cat-cracked gasoline to push more volume into the cat light gas oil.
• In the summer, during a max gasoline mode, the shift is in the other direction.
• The products from the fractionator are different in composition than those
from the crude distilling column light ends.
 Catalytic Cracking – The Fractionator
• The cracking process results in the creation of olefins, so the C4 and lighter
stream contains not only the four paraffins (methane, ethane, propane, and
butanes) but also ethylene, propylene, and butylenes.
• Because of these extra components, this stream is sent to be separated at the
cracked gas plant.
• This is in contrast to the gas from operations like distilling (and, as discussed
later, the hydrotreater, hydrocracker, reformer, and others), where the gases
contain only saturated compounds.
• These end up in the sats gas plant for separation.
• The isobutane, propylene, and butylenes from the cat cracker will be of special
interest when discussing alkylation, a process that converts these compounds
into gasoline blending components
 Catalytic Cracking – The fractionator
• The other heavier products also differ in composition.
• During the cracking process, many of the heavy, complex molecules will crack at the
connection between the aromatics rings and the side chains.
• Consequently, the cat cracker products tend to be rich in aromatics, the molecules replete
with benzene rings somewhere in their structure.
• That is good news for boosting octane numbers and making gasoline, but as you will find
out later, bad news for making jet fuel and diesel fuel.
• All pieces fit together as shown in fihure below.
• You can see there are two circular flows going on.
• On the left side, the catalyst goes through the reaction, is regenerated, and gets charged
back to the reaction again.
• On the right side, hydrocarbon comes in and goes out, but the slurry oil provides
continuous circulation of at least some of the hydrocarbon components.
Catalytic Cracking Unit