Distillate Hydrocracking

Or
Catalytic Hydrocracking
Or
Hydrocracking

Dr. Arun Kumar Jana

Chemical Engineering Department, SVNIT, Surat

Dr. A. K. Jana, SVNIT, Surat 1

 Hydrocracking

A versatile catalytic refining process that upgrades

petroleum feedstocks by adding hydrogen, removing
impurities, and cracking to a desired boiling range.

Requires the conversion of a variety of types of molecules

and characterized by the fact that the products are of
significantly lower molecular weight than the feed.

Feeds can range from heavy vacuum gas oils and coker
gas- oils to atmospheric gas oils.
Products usually range from heavy diesel to light naphtha.

Hydrocrackers are designed for and run at a variety of

conditions depending on many factors such as type of feed,
desired cycle length, expected product slate.
Dr. A. K. Jana, SVNIT, Surat 2
Dr. A. K. Jana, SVNIT, Surat 3
 Flow schemes
Various licensors have slightly different names for their
hydrocracker flow schemes, but in general, they can be
grouped into major two categories: single stage and two
stage.

Dr. A. K. Jana, SVNIT, Surat 4

With the exception of the H-Oil and LC-Fining processes, all
hydrocracking and hydroprocessing processes in use today
are fixed-bed catalytic processes with liquid downflow.

Dr. A. K. Jana, SVNIT, Surat 5

 Single stage once-through hydrocracking

Figure 7.1: Single stage once-through hydrocracking

unit.

Dr. A. K. Jana, SVNIT, Surat 6

Feed mixes with hydrogen and goes to the reactor.

Reactor effluent goes to fractionation, with the unconverted

material being taken out of the unit as unconverted material.

This type of unit is the lowest cost hydrocracking unit with

simplest configuration.

Can process heavy, high boiling feed stocks and produces

high value unconverted material which becomes feed stock for
FCC units, ethylene plants or lube oil units.

The conversion of the feed stock to products is 60–70 vol%,

but can range as high as 90 vol%.

Dr. A. K. Jana, SVNIT, Surat 7

 Single stage with recycle hydrocracking

Figure 7.2: Single stage hydrocracking unit with

recycle.
Dr. A. K. Jana, SVNIT, Surat 8
The most widely found hydrocracking unit is the single stage
with recycle in which the unconverted feed is sent back to the
reactor section for further conversion.

It is the most cost-effective design for 100% (or near 100%)

conversion and is especially used to maximize diesel product.

A more detailed flow diagram of the reactor section in a single

stage hydrocracking unit (than those shown in either Figures
7.1 and 7.2) is shown in Figure 7.3.

Dr. A. K. Jana, SVNIT, Surat 9

Figure 7.3: Typical flow diagram of reactor section of single stage
hydrocracker (or first stage of a two stage hydrocracker).

Dr. A. K. Jana, SVNIT, Surat 10

The fresh feed is passed downward through the catalyst in
presence of hydrogen, after being preheated to reaction
temperature by passing it through heat exchangers and a
heater.

The effluent from the reactors goes through a series of

separators where hydrogen is recovered and, together with
make up hydrogen, is recycled to the reactors.

The liquid product is sent to fractionation where the final

products are separated from unconverted oil.

In once-through units, the unconverted oil is sent out of the

unit.
In units designed to operate with recycle, the unconverted
oil combines with the fresh feed, as shown in Figure 7.3.
Dr. A. K. Jana, SVNIT, Surat 11
The reaction section fulfills two functions: pre-treating and
cracking.

This is shown in Figure 7.3 as separate reactors, though both

functions can be achieved in a single reactor when using
amorphous catalyst.

When using a pretreat and cracking catalyst configuration, the

first catalyst (a hydrotreating catalyst) converts organic sulfur
and nitrogen from hetero compounds in the feedstock to
hydrogen sulfide and ammonia, respectively.

The deleterious effect of H2S and NH3 on hydrocracking

catalysts is considerably less than that of the corresponding
organic hetero compounds.
Dr. A. K. Jana, SVNIT, Surat 12
The hydrotreating catalyst also facilitates the hydrogenation of
aromatics.

In the single stage, two-reactor configuration, the products from

the first reactor are passed over a hydrocracking catalyst in the
second reactor where most of the hydrocracking takes place.

The conversion occurs in the presence of NH3, H2S, and small

amounts of unconverted amounts of hetero compounds.

The hydrotreating catalyst in the first reactor is designed to

convert the hetero compounds in the feed stock.

Typically, such catalysts comprise sulfided molybdenum and

nickel on alumina support.

Dr. A. K. Jana, SVNIT, Surat 13

The reactor operates at temperatures varying from 570oF to
800oF (300–425oC) and hydrogen pressures between 1,250
and 2,500 psig (85–170 bar).

Under these conditions, in addition to heteroatom elimination,

significant hydrogenation occurs, and some cracking also
takes place.

The cracking reactor operates at the same hydrogen

pressures but at temperatures varying from 570 to as high as
840oF (300–450oC) for amorphous hydrocracking catalysts
and up to 440oC (825oF) for zeolite containing catalysts.

Dr. A. K. Jana, SVNIT, Surat 14

Two stage recycle hydrocracking

Figure 7.4. Two stage hydrocracking.

Dr. A. K. Jana, SVNIT, Surat 15

The two stage hydrocracking process configuration is also
widely used, especially for large throughput units.

In two stage units, the hydrotreating and some cracking takes

place in the first stage.

The effluent from the first stage is separated and fractionated,

with the unconverted oil going to the second stage.

The unconverted oil from the second stage reaction section

goes back to the common fractionator.

A simplified schematic of a two stage hydrocracker is shown in

Figure 7.4.

The catalysts in the first stage are the same types as those
used in the single stage configuration. 16
The catalyst in the second stage is operating in near absence
of ammonia, and depending on the particular design, in the
absence or presence of hydrogen sulfide.

The near absence of NH3 and H2S allows the use of either
noble metal or base metal sulfide hydrocracking catalysts.

Dr. A. K. Jana, SVNIT, Surat 17

 Separate hydrotreat two stage hydrocracking

Figure 7.5. Separate hydrotreat two stage hydrocracking.

Dr. A. K. Jana, SVNIT, Surat 18

A variation of the typical two stage hydrocracking with
common hydrogen circulation loop is the separate hydrotreat
hydrocracking shown in Figure 7.5.

In which each stage has a separate hydrogen circulation

loop, allowing for operation of the second stage in the near
absence of hydrogen sulfide (and ammonia).

Dr. A. K. Jana, SVNIT, Surat 19

Figure 7.2 Two-stage hydrocracker.
Dr. A. K. Jana, SVNIT, Surat 20
 Hydrocracking Chemistry
Hydrocracking converts the heavy feed stock to lower molecular
weight products, removes sulfur and nitrogen and saturates olefins
and aromatics.
The organic sulfur is transformed into H2S, the nitrogen is
transformed into NH3 and the oxygen compounds (not always
present) are transformed into H2O.

The reactions can be classified in two categories: desirable and

undesirable. Desirable are the treating, saturation, and cracking
reactions. Undesirable reactions are contaminant poisoning as well
as coking of the catalyst.
There are two types of reactions taking place in hydrocracking
units: treating (also called pre-treating) and cracking (also
called hydrocracking).

The cracking reactions require bi-functional catalyst, which

possess a dual function of cracking, and hydrogenation.
21
 Treating Reactions
The treating reactions that will take place are: sulfur removal,
nitrogen removal, organo-metallic compound removal, olefin
saturation, oxygen removal, and halides removal.

The first three types of compounds are always present though

in varying amounts depending on the source of feed stock.

In general, the treating reactions proceed in the following

descending order of ease: (organo) metals removal, olefin
saturation, sulfur removal, nitrogen removal, oxygen removal,
and halide removal.

Some aromatic saturation also occurs in the pre-treating

section.

Hydrogen is consumed in Dr.

allA. K.treating reactions.
Jana, SVNIT, Surat 22
The desulfurization reaction consumes 100–150 SCFB/wt%
change (17–25 Nm3/m3/wt% change) and the denitrogenation
reaction consumes 200–350 SCFB/wt% change (34–59
Nm3/m3/wt% change).

The heat released in pre-treating is about 0.02oF/SCFB H2

consumed (0.002oC/Nm3/m3 H2).

Figure 7.6. Postulated mechanism for hydrodesulfurization.

Dr. A. K. Jana, SVNIT, Surat 23

The postulated mechanism for the desulfurization reaction is
shown in Figure 7.6: first, the sulfur is removed followed by
the saturation of the intermediate olefin compound.

In the example (next slide) the thiophene is converted to

butene as an intermediate which is then saturated into butane.

Figure 7.7 shows several desulfurization reactions arranged in

increasing order of difficulty.

The denitrogenation reaction proceeds through a different

path. In the postulated mechanism for hydrodenitrogenation
the aromatic hydrogenation occurs first, followed by
hydrogenolysis and, finally denitrogenation (Figure 7.8).

Figure 7.9 shows a few typical examples of denitrogenation

reactions. Dr. A. K. Jana, SVNIT, Surat 24
Figure 7.7. Typical desulfurization reactions.

Dr. A. K. Jana, SVNIT, Surat 25

Figure 7.8. Postulated mechanism for hydrodenitrogenation.

Dr. A. K. Jana, SVNIT, Surat 26

Figure 7.9. Typical denitrogenation reactions.

Dr. A. K. Jana, SVNIT, Surat 27

 Cracking Reactions
Hydrocracking reactions proceed through a bifunctional
mechanism.

A bifunctional mechanism is one that requires two distinct

types of catalytic sites to catalyze separate steps in the
reaction sequence.

These two functions are the acid function, which provide for
the cracking and isomerization and the metal function, which
provide for the olefin formation and hydrogenation.

The cracking reaction requires heat while the hydrogenation

reaction generates heat.

Dr. A. K. Jana, SVNIT, Surat 28

Overall, there is heat release in hydrocracking, and just like in
treating.
It is a function of the hydrogen consumption (the
higher the consumption, the greater the exotherm).

Hydrogen consumption in hydrocracking (including the pre-

treating section) is 1200–2400 SCFB/wt% change (200–420
Nm3/m3/wt% change) resulting in a typical heat release of 50–
100 Btu/SCF H2 (2.1–4.2 kcal/m3 H2) which translates into a
temperature increase of about 0.065◦F/SCF H2 consumed
(0.006◦C/Nm3/m3 H2).

This includes the heat release generated in the treating

section.

Dr. A. K. Jana, SVNIT, Surat 29

Hydrocracking reaction starts with the generation of an olefin or
cycleolefin on a metal site on the catalyst.

Next, an acid site adds a proton to the olefin or cycloolefin to

produce a carbenium ion.

The carbenium ion cracks to a smaller carbenium ion and a smaller

olefin.

These products are the primary hydrocracking products. These

primary products can react further to produce still smaller secondary
hydrocracking products.

The reaction sequence can be terminated at primary products by

abstracting a proton from the carbenium ion to form an olefin at an
acid site and by saturating the olefin at a metal site.
Dr. A. K. Jana, SVNIT, Surat 30
Figure 7.10. Postulated hydrocracking mechanism of n-paraffins.
Dr. A. K. Jana, SVNIT, Surat 31
Summary:
Hydrocracking occurs as the result of a bifunctional mechanism that
involves olefin dehydrogenation–hydrogenation reactions on a metal
site.

Carbenium ion formation on an acid site, and isomerization, and

cracking of the carbenium ion.

The hydrocracking reactions tend to favor conversion of large

molecules because the equilibrium for olefin formation is more
favorable for large molecules and because the relative strength of
adsorption is greater for large molecules.

In hydrocracking, the products are highly isomerized, C1 and C3

formation is low, and single rings are relatively stable.

Dr. A. K. Jana, SVNIT, Surat 32

Dr. A. K. Jana, SVNIT, Surat 33
Dr. A. K. Jana, SVNIT, Surat 34
Dr. A. K. Jana, SVNIT, Surat 35
 Catalysts

Hydrocracking catalysts are dual function catalysts.

For the cracking reaction to occur (as well as hydroisomerization

and dehydrocyclization), both metallic sites and acidic sites must
be present on the catalyst surface.

Hydrocracking catalysts have a cracking function and hydrogenation

function.

The cracking function is provided by an acidic support, whereas the

hydrogenation function is provided by metals.

Dr. A. K. Jana, SVNIT, Surat 36

The acidic support consists of amorphous oxides (e.g., silica-alumina,
a crystalline zeolite (mostly modified Y zeolite)) plus binder (e.g.,
alumina), or a mixture of crystalline zeolite and amorphous oxides.

Cracking and isomerization reactions take place on the acidic support.

The metals providing the hydrogenation function can be noble

metals (palladium, platinum), or non-noble (also called “base”) metal
sulfides from group VIA (molybdenum, tungsten) and group VIIIA
(cobalt, nickel).

These metals catalyze the hydrogenation of the feedstock, making it

more reactive for cracking and heteroatom removal, as well as
reducing the coking rate.

They also initiate the cracking by forming a reactive olefin

intermediate via dehydrogenation.
Dr. A. K. Jana, SVNIT, Surat 37
The ratio between the catalyst’s cracking function and hydrogenation
function can be adjusted in order to optimize activity and selectivity.

Activity and selectivity are but two of the four key performance
criteria by which hydrocracking catalysts are measured:

Initial activity, which is measured by the temperature required to

obtain desired product at the start of the run.
Stability, which is measured by the rate of increase of temperature
required to maintain conversion.
Product selectivity, which is a measure of the ability of a catalyst
to produce the desired product slate.

Product quality, which is a measure of the ability of the process to

produce products with the desired specifications, such as pour point,
smoke point, or cetane number.
Dr. A. K. Jana, SVNIT, Surat 38
Hydrocracking catalyst to be effective, it is important that there be a
rapid molecular transfer between the acid sites and hydrogenation
sites in order to avoid undesirable secondary reactions.

Rapid molecular transfer can be achieved by having the

hydrogenation sites located in the proximity of the cracking (acid)
sites.

Dr. A. K. Jana, SVNIT, Surat 39

Dr. A. K. Jana, SVNIT, Surat 40
 Hydrocracking Process Variables

The proper operation of the unit will depend on the careful selection
and control of the processing conditions.

By careful monitoring of these process variables the unit can

operate to its full potential.

The primary reaction variables are reactor temperature and pressure,

space velocity, hydrogen consumption, nitrogen content of feed, and
hydrogen sulfide content of the gases.

The effects of these are as follows:

Dr. A. K. Jana, SVNIT, Surat 41

Reactor Temperature
Reactor temperature is the primary means of conversion control.

At normal reactor conditions a 20°F (10°C) increase in temperature

almost doubles the reaction rate.

Increase in rate does not affect the conversion level as much

because a portion of the reaction involves material that has already
been converted to materials boiling below the desired product end
point.

As the run progresses it is necessary to raise the average

temperature about 0.1 to 0.2°F per day to compensate for the loss
in catalyst activity.

Dr. A. K. Jana, SVNIT, Surat 42

Reactor Pressure

The primary effect of reactor pressure is in its effects on the partial

pressures of hydrogen and ammonia.

An increase in total pressure increases the partial pressures of both

hydrogen and ammonia.

Conversion increases with increasing hydrogen partial pressure and

decreases with increasing ammonia partial pressure.

The hydrogen effect is greater, however, and the net effect of raising
total pressure is to increase conversion.

Dr. A. K. Jana, SVNIT, Surat 43

Space Velocity
The volumetric space velocity is the ratio of liquid flow rate, in
barrels per hour, to catalyst volume, in barrels.

The catalyst volume is constant, therefore the space velocity varies

directly with feed rate.

As the feed rate increases, the time of catalyst contact for each barrel
of feed is decreased and conversion is lowered.

In order to maintain conversion at the proper level when the feed rate
is increased, it is necessary to increase the temperature.

Dr. A. K. Jana, SVNIT, Surat 44

Nitrogen Content

The organic nitrogen content of the feed is of great importance as the

hydrocracking catalyst is deactivated by contact with organic
nitrogen compounds.

An increase in organic nitrogen content of the feed causes a decrease

in conversion.

Dr. A. K. Jana, SVNIT, Surat 45

Hydrogen Sulfide

At low concentrations the presence of hydrogen sulfide acts as a

catalyst to inhibit the saturation of aromatic rings.

This conserves hydrogen and produces a product with a higher octane

number because the aromatic naphtha has a higher octane than does
its naphthenic counterpart.

However, hydrocracking in the presence of a small amount of

hydrogen sulfide normally produces a very low-smoke-point jet fuel.

At high hydrogen sulfide levels corrosion of the equipment becomes

important and the cracking activity of the catalyst is also affected
adversely.

Dr. A. K. Jana, SVNIT, Surat 46

Heavy Polynuclear Aromatics (HPNA)

Heavy polynuclear aromatics are formed in small amounts from

hydrocracking reactions.

When the fractionator bottoms is recycled, HPNA can build up to

concentrations that cause fouling of heat exchanger surfaces and
equipment.

Steps such as reducing feed end point or removal of a drag stream

may be necessary to control this problem.

Dr. A. K. Jana, SVNIT, Surat 47