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FCC Refinery Article
FCC Refinery Article
Introduction
Fluid catalytic cracking units without any doubt belong to the most important refinery
technologies. This process converts heavy atmospheric residues and vacuum distillates into
fractions of motor fuels, mainly gasoline. The history of the beginning of the cracking of
heavier crude molecules to lighter lead to the beginning of the crude oil applications in
combustion engines. The need to upgrade less valuable petroleum products into gasoline has
been recognized since around 1910. The cracking of long-chain hydrocarbons is the most
important petroleum-refining process; the method of cracking long-chain hydrocarbons has
evolved over the years, though the end goal always remained the same.
Short history of crude-oil, kerosene and gasoline
Until the mid-nineteenth century, most people used candles for indoor light or lamps
that burned whale oil. As whaling depleted the supply of oil from whales, petroleum-based
illuminants began to take its place. Crude petroleum that seeped in USA into ponds and
creeks could be refined by simple methods to produce kerosene, good illuminating oil, and a
small industry to produce kerosene from crude oil arose in the 1850s. The growth of the
industry was limited by very small supply of naturally-surfacing crude oil. To supply the
demand for indoor light, the petroleum industry needed to tap the reservoirs of oil that existed
underground. The great effort for looking for the underground supplies of crude oil started
with success in different parts of Earth. Early refiners obtained kerosene by heating the crude
oil in tanks. The kerosene was then treated with an acid and then an alkali to remove its odor
and to improve its color.
The milestone in the crude-oil utilization was the development of the use of the light
fraction of crude oil gasoline (that was used before as solvent) as fuel in combustion engine.
Very soon with the developing of the automobile industry, the supply of straight-run gasoline
as fuel for automobile engines was insufficient. The solution of this problem was in two ways:
1 to increase the exploitation of crude together with the capacities of refineries, or 2 to
convert the heavy crude oil fraction (atmospheric residues) into atmospheric distillates. The
second alternative was realized by the development of thermal and later catalytic cracking.
History of Thermal Cracking
Burton and Humphreys, two American chemists, started to crack diesel oil fraction at
elevated temperatures and elevated pressure to receive the gasoline with of acceptable quality.
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
From a barrel of crude oil, twenty percent could be produced as "straight-run" gasoline
through distillation. Thermal pressure cracking added another twenty percent. In January
1913 they began producing cracked gasoline, at about the time that Ford perfected his method
of mass-producing automobiles. By this time, the history of cracking of a heavy crude oil
fraction into light fraction started. When in 1899, the United States produced about six million
barrels of gasoline, for use mainly as cleaning solvents, by 1919, mostly to supply motor
vehicles, U.S. gasoline production had climbed to 99.7 million barrels, of which 15.5 million
(16%) was cracked gasoline.
The Burton process was limited in one important way: it produced cracked gasoline
only in batches and had to stop every two days so that the stills could be cleaned of carbon
residue that built up in the refining process. The effort was made to develope a thermal
cracking processes that could go for longer periods between cleanings. One such process was
invented by Jesse Dubbs and his son (patented between 1915 and 1919). The Dubbs process
could feed crude oil in and out of pressure stills on a nearly continuous basis, removing
carbon residue as it did so.
During the 1920s, however, the petroleum refining industry faced a third challenge.
The gasoline produced for motor vehicles suffered from a serious problem called engine
knock, in which the gasoline failed to ignite evenly. As automobiles developed stronger
engines to drive faster on newly paved roads, the problem became worse. It was found that
adding tetraethyl lead to gasoline could sharply reduce engine knock. The anti-knock
properties of gasoline were expressed by Octane number, that was 0 (severe knockink) for nheptane and 100 (no detectable knocking) for iso-octane.
By 1930, gasolines had achieved octane ratings between 60 and 70. But distillation
and thermal pressure cracking could not raise the octane any higher. Newer and more
powerful engines required higher octane gasoline, and aircraft engines needed fuel with
octane ratings of nearly 100. Only the discovery of efficient catalytic cracking by the French
engineer Eugene Houdry in the 1920s produced higher octane gasoline and also increased the
supply.
The era of thermal cracking was generally in between 1913 (the start of Burton
thermal cracking) via 1915 start of Dubbs thermal cracking up to about 1936. In the present
days thermal cracking is working in refineries in the form of visbreaking and coking.
History of catalytic cracking
Already Burton and Humphreys at the beginning of 20th century had tried at first to
use a catalyst, aluminum chloride, to crack petroleum but this catalyst proved uneconomical
and the two shifted to thermal cracking. Houdry believed that the next great advance in
refining lay in finding an economical catalyst. Houdry tried hundreds of possible catalysts.
Finally in 1927, Houdry found that oxides of silicon and aluminum cracked heavier petroleum
molecules. Houdry proved that gasoline cracked in this way was as good as the best gasoline
on the market. The reason was in the different mechamisms of catalytic cracking in
comparison with thermal cracking. While thermal splitting of C-C bond proceeds via radical
mechanisms, producing mainly linerar cracking products, catalytic cracking proceeds in the
presence of acid catalysts via carbocations giving much more branched products with high
octane number.
Houdrys breakthrough came when he showed that his solid catalyst could be
regenerated. As the catalyst was used, deposits of coke would form on the surface and slow
or stop its ability to perform. Houdry realized that this coke could simply be burnt off, reexposing the catalyst surface. This process was called regeneration. The Houdry fixedbed process was the result of this work, and in 1936 the first commercial catalytic cracking
plant opened.
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
Houdry's process came to be called "fixed-bed" catalytic cracking. Fuel oil passed
through beds of small pellets of silica-alumina in the reactor at temperatures of 800 to 1000
degrees Fahrenheit but at pressures lower than those in thermal cracking. A carbon residue
accumulated on the catalysts with repeated use, but by regularly burning the catalysts with air
and heat, the residue could be removed. For continuous work, the process was composed of
several separate reactors and proceeded as a cyclic process (Fig. 1). While in some reactors
cracking proceeded, in others the catalyst was regenerated by coke burning with air. Purging
of reactors with inert gas was necessary before and after each regeneration cycle. Each reactor
was equipped with a molten salt heat removal system to remove the heat evolved during the
regeneration step. Heat from the regeneration step was transferred to the reaction step. The
original catalyst used in Houdry process was acid-treated bentonite clays, probably in the
form of pellets. It was first commercialized in 1937 and, by 1940, there were 14 such units built.
Product
fractionation
Flue Gas
Air
Feedstock
(heated)
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
Fig. 7 Examples of spray-dryers with nozzle (A) and rotary (B) atomizers
NH4Y + Na
NH4Y (500 C)
HY + NH3
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
|
|
|
O
O
H+ O
|
|
|
|
O Si O Al- O Si O
|
|
|
O
O
O
|
|
|
Fig. 8 The nature of Broensted acid centers in zeolite structure
But, such prepared HY-zeolite was still not stabile in the conditions of FCCtechnology - the presence of 100% steam at high temperature: in riser, reactor and stripper
about 550 C, in regenerator more than 700 C. At such hydrothermal conditions, the
hydrolysis of framework aluminium occurs and the frameworks strongly dealuminates,
causing partial and even total collapse of zeolite Y structure.
The first solution of the Y-zeolite instability was ion-exchange with rare-earths cations
similarly as in the case of X-zeolites. REY zeolites were for long-time the most used zeolites
in FCC-catalysts.
Later, the method of stabilitation of zeolite Y structure without RE-cations was
developed: ammonium-exchanged zeolite was treated in special conditions by 100% steam at
the temperature up to 800 C, causing partial dealumination of framework, creation of extraframework aluminium (weak Lewis acid centers), but in the framework still rest strong
Broensted acid sites necessary for cracking. Such treated Y-zeolites were extremely stable,
and were called as ultrastable zeolites Y USY. This kind of Y-zeolites represented the
new generation of acid component in FCC-catalysts.
The great advantage of the USY zeolites was that during hydrothermal dealumination
with steam at the high temperature the secondary mesoporou structure was created in zeolite
crystals (Fig. 9).
Fig. 9 Creation of secondary mesopores in
zeolite Y structure during hydrothermal
stabilization in 100% steam at 800 C
45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic
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The created mesopores in Y.zeolites increase its cracking activity from the point of
view of improving the diffusivity of greater molecules into zeolite crystals to acid catalytic
centers.
Generally, the philosophy of the FCC-catalyst preparation is: to have weak acid
centers in macroporous part of catalyst particles to insure pre-crack the great molecules of
residue to smaller molecules which could enter to the mesopores with stronger acidity.
Product of cracking in mesopores could finally enter the zeolite micropores to crack over
strongest zeolite acid centers into the smaller molecules, mainly gasoline fraction (Fig. 10).
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stable acid component of FCC catalyst from mesoporous molecular sieves was not successful;
aluminium in its structure is not as stable as in Y-zeolite.
Fig. 11 Comparisom of pore structure of zeolites ZSM-5 (0,55nm), VPI-5 (1,2 nm) and
mesoporous molecular sieve MCM-41 (3.5 nm) inTEM
Special types of FCC catalyst is zeolite ZSM-5 containing catalyst, used as additive to
standard FCC catalyst to increase RON of produced gasoline and/or to increase the propylene
yield. This ZSM-5 zeolites has strong reactant selectiviy and crack predominantly nalkanes. Because the cracking over acid centers proceeds via cracking of beta C-C bond to
created secondary (or terciary) carbenium ions, the main product of cracking of longer nalkanes is propene (or butenes).
Conclusions
FCC-technology represents one of the most expanded processes producing motor fuels
from heavy distillates and residues. On the one side, the FCC technology from the
engineering point of view is one of the most sophisticated equipment in the chemical industry.
On the other side, the key factor in such technology is good active, stabile and selective
tailor-made catalyst, converting specific feed of heavy distillates and residues into desired
products. Market with FCC-catalysts is the greatest one in all kinds of catalysts, and at the
same time it is the greatest consumer of zeolites (Y, partially ZSM-5) besides of zeolite A in
detergents. There is still great effort to look for more active, selective and stabile materials as
acid components of FCC catalysts to improve their desired performance.