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CHAPTER
02

Hydro-cracking
Processes

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CHAPTER

02
Hydro-cracking
Processes

Recent Advances in Hydro-cracking:

Hydrocracking is a versatile catalytic refining process that upgrades petroleum feedstocks
by adding hydrogen, removing impurities and cracking to a desired boiling range.
Hydrocracking requires the conversion of a variety of types of molecules and is
characterized by the fact that the products are of significantly lower molecular weight
than the feed. Hydrocracking 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 but in general they will operate at the
following range of conditions: LHSV - 0.5-2.0 hr-1, H2 circulation - 5,000-10,000 SCFB
(850-1,700 NM3/M3), H2PP 1,500- 2,000 Pisa (103-138 bars) and SOR temperatures
ranging between 675 and 725 F (357-385 C). Hydrocracking is particularly well suited to
generating products that meet or exceed all of the present tough environmental
regulations.

Brief History:

The large scale industrial development of hydrogenation in Europe, Particularly in

Germany, was due entirely to military considerations. Germany used hydrogenation
extensively during World War II to produce Gasoline: 3.5 million tons were produced in
1944.The emergent availability of Middle Eastern crude after World War II removed the
incentive to convert coal to liquid fuels, so continuing the development of hydro cracking
technology became less important.

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Even though hydrogenation has been of interest to the petroleum industry for many
years, little commercial use of hydrogen-consuming processes has been made because of
the lack of low-cost hydrogen. That changed in the early 1950s with the advent of
catalytic reforming, which made available byproduct hydrogen. That brought up an
extensive and increased interest in processes that will utilize this hydrogen to upgrade
petroleum stocks.
Another factor was that in the mid-1950 the automobile industry started
manufacturing high performance cars with high-compression ratio engines, which
required high-octane gasoline. Thus catalytic cracking expanded rapidly and generated, in
addition to gasoline, large quantities of refractory cycle stock that was difficult to convert
to gasoline and lighter products. This need to convert refractory stock to gasoline was
filled by hydro cracking. Furthermore, the switch of railroads from steam to diesel
engines after World War II and the introduction of commercial jet aircraft in the late
1950s increased the demand for diesel fuel and jet fuel. The flexibility of the newly
developed hydro cracking processes made possible the production of such fuels from
heavier feed stocks.

Flow Schemes:

Various licensors have slightly different names for their hydrocracking units flow schemes, but in
general, they can be grouped into major two categories: single stage and two stages. Table below
shows the general evolution of flows schemes, generally driven by improvements in catalysts.

Single Stage Once-Through Hydrocracking:

Figure below shows a schematic of a single stage, once through hydrocracking unit,
which is the simplest configuration for a hydrocracker. It is a variation of the single stage
hydrocracking with recycle configuration . The feed mixes with hydrogen and goes to the
reactor. The 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, 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. In

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general, the conversion of the feed stock to products is 60-70 vol%, but can range as high as
90 vol%.

Single Stage with Recycle Hydrocracking:

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. Figure below
depicts this type unit. It is the most cost-effective design for 100% (or near 100%)
conversion and is especially used to maximize diesel product.

Two Stage Recycle Hydrocracking

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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 hydrocracker is shown in Figure 4. The catalysts in the first
stage are the same types as those used in the single stage configuration. 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.

Separate Hydrotreat Two Stage Hydrocracking

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

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Characteristics of Petroleum Products

Hydrocracking

 Purpose: process gas oil to break carbon-carbon bonds of large

carbon bonds of large aromatic compounds & remove contaminants.
 Hydrogenation (addition of hydrogen)
 Cracking (carbon-carbon scission) of aromatic bonds

 Typically creates distillate range products, not gasoline range products.

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1. Hydrocracking Technologies

Hydro cracking Feeds

Typical feeds
 Cat cracker “cycle oil”
i) Highly aromatic with sulfur, small ring & polynuclear aromatics, catalyst
fines; usually has high viscosity
ii) Hydrocracked to form high yields of jet fuel, kerosene, diesel, & heating oil
 Gas oils from visbreaker
(a) Aromatic
 Gas oil from the delayed coker
a) Aromatic, olefinic, with sulfur
b) Usually more economical to route atmospheric & vacuum gas oils to the
c) cat cracker to produce primarily gasoline & some diesel

Gas Oil Hydrocracker Feed

 Hydrocracking does a better job of processing aromatic rings without
coking than catalytic cracking.
o Hydrogen used to hydrogenate polynuclear aromatics (PNAs)

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o Reduces frequency of aromatic condensation

 Hydrocracking not as attractive as delayed coking for resids high in
resins, asphaltenes & heteroatom compounds
o Heteroatoms & metals prevalent in resins & asphaltenes poison
hydroprocessing catalysts
o High concentrations of resins & asphaltenes will still ultimately coke
 Feeds limited to a Conradson Carbon Number (CCR) of 8 wt%
 Feeds require high pressures & large amounts of hydrogen

Gas Oil Hydrocracker Products

 Hydrocracking primarily to make distillates.
o In US hydrocracking normally a specialized operation used to optimize
catalytic cracker operation
o In US cat cracking preferred to make gasoline from heavier fractions
 Hydrocracking capacity is only about 8% of the crude distillation
Capacity
o Not all refineries have hydrocrackers
 Intent is to minimize the production of heavy fuel oil
o Light ends are approximately 5% of the feed.
o Middle distillates (kerosene, jet fuel, diesel, heating oil) still contain
uncracked polynuclear aromatics
 All liquid fractions are low in sulfur & olefins

Hydrocracking Chemistry

Cracking reactions Hydrogenation Isomerization Condensation

Reactions Reactions Reactions

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Exothermic giving off heat Isomerization provides Suppressed by

Saturated paraffins cracked
to form lower molecular
weight olefins & paraffins
Side chains cracked off small
ring aromatics (SRA) &
cycloparaffins (naphthenes)
Side chains cracked off resins
& asphaltenes leaving
thermally stable polynuclear
aromatics (PNAs)
But condensation
(dehydrogenation) also
occurs if not limited by
Hydrogenation
Hydrogen inserted to branching of alkyl groups of hydrogen
saturate newly formed paraffins and opening of
molecule from aromatic naphthenic rings
cracking
Olefins are saturated to form
light hydrocarbons,
especially butane
Aromatic rings hydrogenated
to cycloparaffins
(naphthenes)
Carbon-carbon bonds
cleaved to open aromatic &
cycloparaffins (naphthenes)
rings
Heteroatoms form hydrogen
sulfide, ammonia, water,
hydrogen chloride

Hydrogen Consumption
 Carbon bonds with heteroatom broken & saturated
o Creates light ends
 Heavier distillates make more light ends from breaking more compl
ex
molecules
o Sulfur converted to hydrogen sulfide
o Nitrogen converted to ammonia
o Oxygen converted to water
o Organic chlorides converted to hydrogen chloride
 Saturation of carbon-carbon bonds
o Olefins saturated to form light hydrocarbons.
 Consumption stoichiometric —one hydrogen molecule added for
each
double bond
o Aromatic rings hydrogenated to cycloparaffins (naphthenes).
 Severe operation —hydrogen consumption strong function of
complexity
of the aromatics

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 Isomerization reactions generally not present

 Metals deposited directly on the catalysts
o Excess metals reduce catalyst activity & promote dehydrogenation
(produces coke & hydrogen)
 Have cracking of carbon-carbon bonds

o Severe operation —hydrogen consumption strong function of complexity

of the aromatics
 Hydrogen lost in mixture with products
o Equilibrium with light gases
 Significant —may double amount required for sulfur removal
o Absorbed in liquid products
 Usually small compared to hydrogen used for sulfur removal
o Lost with purge gas

Single Stage Hydrocracking

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Severe Two Stage Hydrocracking

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Hydro-Cracking processes