SORAN UNIVERSITY

PETROLEUM ENGINEERING DEPARTMENT

Petroleum Refinery
NAZIR MAFAKHERI

OCTOBER 2018

Lecture 6
HYDROCRACKING
Hydrocrackers can produce gasoline components from light or heavy
gas oils, cracked gas oils, or straight run gas oils from the crude
distilling unit
process of more recent vintage than cat cracking
It can stand alone in a refinery as the only cracking unit.
It can also work in concert with a cat cracker or coker to extend the
flexibility and capability of a refinery.
Plopped in the middle of a refinery, hydrocracking can take care of
many of the headaches that refiners experience as the market changes
from month to month or season to season.
HYDROCRACKING
It can produce light distillates (jet fuel and diesel fuel) from heavy gas
oils.
Hydrocrackers produce isobutane, a handy supply for the alky plant.
best of all, hydrocrackers produce no bottom-of-the-barrel leftovers
(coke, pitch, or residue).
move from max diesel and distillate fuels in the winter to max gasoline
and maybe even jet fuel in the summer
HYDROCRACKING
• The Process
it is catalytic cracking in the presence of hydrogen
various combinations of hydrogen, catalyst, and operating conditions
permit cracking a wide range of feedstocks
 from kerosene to straight run residue or the cycle oils from the cat
cracker, coker, or thermal cracker
Hydrocrackers run in one, two, or three stages, with the latter ones
sequentially upgrading: heavy stuff to middle distillates, and middle
distillates to gasoline range components.
HYDROCRACKING
• The Process
hydrocracking makes excellent distillate blending stocks but lower
quality gasoline blending stocks.
 The hydrocracker products have lower aromatics-type molecules and
higher naphthenes and paraffins.
Lower aromatic gas oil burns cleaner and has a higher diesel index.
Low aromatics gasoline has a lower octane number.
HYDROCRACKING
• The Process

Why does every refinery not have one of these

machines?
Even though about a dozen different types of hydrocrackers are
presently popular, they all are expensive to build and operate. The units
HYDROCRACKING
• The Hardware and the Reactions
• Hydrocracking catalysts are fortunately less precious and expensive
than reforming catalysts
• Usually they are compounds of sulfur with cobalt, molybdenum, or
nickel plus alumina
• In contrast to cat cracking but like cat reforming, most hydrocracker
designs have their catalysts in a fixed bed
• Just a few units such as the H-Oil, Hycon, LC-Fining, and OCR models
have fluidized beds with moving catalyst
HYDROCRACKING
• The Hardware and the
Reactions
Feed (in this example, cracked
heavy gas oil) is mixed with
hydrogen vapor, heated to 550ºF
to 750ºF, pressurized to 1,200
psi to 2,000 psi, and charged to
the first stage reactor. As it
passes through the catalyst,
about 40% to 50% of the feed is
cracked to gasoline range
material (below the 400ºF end
point).
HYDROCRACKING
• The Hardware and the
Reactions
Why is the unusually high
pressure used?
The gas oils that are most
suitable for hydrocracking are
from other cracking processes,
cat cracking and coking. These
gas oils are normally replete
with benzene-ringed
compounds. To crack these
tough molecules apart needs
high pressure and moderate
temperature.
HYDROCRACKING
• The Hardware and the
Reactions
In the hydrogen separator, the
hydrogen/methane stream is
split out for recycling to the
feed. The liquid is charged to a
fractionator
Whatever products are desired
(gasoline components, jet fuel,
and gas oil), the fractionator
cuts them outof the first stage
reactor effluent, leaving a
bottoms stream ready for the
next, second stage, reactor
HYDROCRACKING
• The Hardware and the
Reactions
In other words, kerosene
range and light gas oil range
material could be taken as
separate side draw products
from the fractionator. They
could instead be included in
the fractionator bottoms
iffurther conversion to
gasoline range material is the
object.
HYDROCRACKING
• The Hardware and the
Reactions
 The bottoms stream is again mixed
with a hydrogen stream and
charged to the second stage. Since
this material has already been
subjected to some hydrogenation,
cracking, and reforming in the first
stage, the operations of the second
stage are more severe (higher
temperatures and pressures). Like
the outturn of the first stage, the
second stage product is separated
from the hydrogen and charged to
the (same) fractionator.
HYDROCRACKING
• The Hardware and the Reactions
The hydrogen and the catalyst are complementary in several ways.
 the catalyst causes long chain molecules to crack the rings in aromatic
compounds to open up.
Both these reactions need heat to keep them going. They are
endothermic processes.
Cracking forms olefins, which could join together to form normal
paraffins.
HYDROCRACKING
• The Hardware and the Reactions
On the other hand, once the cracking takes place, momentarily
creating an olefin
the excess hydrogen floating around saturates (fills out) the molecules,
a process that gives off heat.
This process, called hydrogenation, is exothermic. Thus, hydrogenation
gives off the heat necessary to keep the cracking and ring opening
going.
The catalyst and hydrogen also complement each other in the
formation of isoparaffins.
HYDROCRACKING
• The Hardware and the Reactions
Hydrogenation rapidly fills out all the double bonds, often forming
isoparaffins, preventing reversion to less desirable molecules.
(Isoparaffins have higher octane numbers than normal paraffins.)
After the hydrocarbon leaves the first stage, it is cooled enough for
virtually all but the methane and hydrogen to liquefy.
HYDROCRACKING
• The Hardware and the Reactions
• Different reactions take place in each stage:
I. In the first stage, the catalyst opens up the rings of complicated
molecules the contaminants, sulfur and nitrogen, might be
embedded. The hydrogen forms H2S and NH4, hydrogen sulfide and
ammonia. At the same time the hydrogen fills out many of the
opened double bonds, forming simpler, lighter compounds.
HYDROCRACKING
• The Hardware and the Reactions
• Different reactions take place in each stage:
II. In the second stage, run more severely, the catalyst opens up more
rings of the heavy, complicated molecules and cracks others,
forming light products.
III. In the third stage, a kind of polishing job takes place where the
olefins and aromatic compounds are saturated, forming
naphthenes, paraffins, and especially isoparaffins
HYDROCRACKING
• The Hardware and the Reactions
Since hydrocracker reactors operate at really severe conditions—up to
2,000 psi and 750ºF—imagine the hardware necessary to contain the
reactions.
The 6-inch specialty-steel reactor walls have to resist hydrogen
intrusion, which can lead to stress fractures. The possibility of runaway
cracking creates further critical worry.
Since the overall process is exothermic, the temperature can rise
rapidly, accelerating the cracking rates dangerously,which only gives off
more heat as hydrogenation then takes place. Elaborate quench
systems are built into most hydrocrackers to control runaway.
HYDROCRACKING
• Yields.
Another satisfying feature of the hydrocracker is a 10%–20% gain in
volume, again what refiners sometimes call “fluffing up the barrel.” The
cracking/hydrogenation combination results in products whose
average gravity is 10º–20º API higher than the feed. The table below
shows typical yields from hydrocracking cat-cracked cycle oil and cat-
cracked gas oil. The primary products, blending components heading
for the gasoline blending pool, are called hydrocrackate.
HYDROCRACKING
• Yields.
 Another satisfying feature
of the hydrocracker is a
10%–20% gain in volume,
again what refiners
sometimes call “fluffing
up the barrel.” The
cracking/hydrogenation
combination results in
products whose average
gravity is 10º–20º API
higher than the feed. The
table below shows typical
yields from hydrocracking
cat-cracked cycle oil and
cat-cracked gas oil. The
primary products,
blending components
heading for the gasoline
blending pool, are called
hydrocrackate.
HYDROCRACKING
• Yields.
The hydrogen-to-carbon ratio in larger molecules is lower than smaller
molecules
Cracking heavier feed requires more hydrogen than lighter feed.
Larger molecules tend to have more hydrogendeficient aromatic rings.
 For the same gasoline yield, 20ºAPI heavy gas oil may require twice the
hydrogen consumption as 33ºAPI light gas oil.
HYDROCRACKING
• Yields.
The heavier part of the hydrocrackate contains a lot of aromatics
precursors (types of molecules that easily convert to aromatics in a
reformer).
 Refiners often split out this naphtha and feed it to the reformer for
upgrading
The kerosene range material makes a good jet fuel or a distillate
blending stock because of its low aromatic content, a consequence of
hydrogen saturating those double bonds.
HYDROCRACKING
• Yields.
Residue hydrocracking:
A handful of hydrocrackers have been designed and constructed to use
straight run residue or flasher bottoms as feed
The yields are more than 90% residual fuel.
The purpose of and the sulfur compounds, forming H2S, hydrogen
sulfide. Residue with the operation is to remove sulfur by the catalytic
reaction of the hydrogen a sulfur content of about 4% or less can be
converted to heavy fuel oil with less than 0.3% sulfur.
HYDROCRACKING
• Yields.
Residue hydrocracking:
 They pump enormous amount of hydrogen into the reactions to break up the
very heavy molecules and require lots of recycling of the heavy ends back
through the reactor to make them go away.
A residue hydrocracker costs a relatively large bundle of money just to convert
high sulfur residual fuel to low sulfur residual fuel, and even more to convert
it to light products
 Special circumstances including location, access to cheap, heavy crude oil,
and lack of any high sulfur residual fuel market might make this economically
viable.