Vacuum Distillation

Refining-Petrochemicals-Chemicals-Engineering
———
VACUUM DISTILLATE HYDROCRACKING
I - PURPOSE OF HYDROCRACKING AND INTEGRATION WITH IN THE

REFINING SCHEME.................................................................................................................. 1
II - PROCESS CHARACTERISTICS............................................................................................... 8
1 - Chemical reactions .......................................................................................................................8
2 - Hydrorefining catalysts ...............................................................................................................10
3 - Hydrocracking catalysts..............................................................................................................10
4 - Main catalyst constraints ............................................................................................................14
III - HYDROCRACKER OPERATING CONDITIONS .................................................................... 15

1 - Feed circuit .................................................................................................................................15
2 - Reactor section...........................................................................................................................15
3 - Refrigeration - HP and MP separators........................................................................................15
4 - Distillation section .......................................................................................................................16
5 - Hydrocracking catalyst activation ............................................................................................... 16
6 - Catalyst regeneration..................................................................................................................16
IV - HYDROGEN PRODUCTION.................................................................................................... 18
1 - Principle of the reaction ..............................................................................................................18
2 - Hydrogen production plant..........................................................................................................19
RA HCR - 00111_A_A - Rev. 3 04/03/2009

© 2009 - IFP Training
1
I- PURPOSE OF HYDROCRACKING AND INTEGRATION WITHIN THE REFINING SCHEME

Distillate hydrocracking is a sophisticated conversion process that simultaneously involves heat, several
types of specific catalysts and the addition of hydrogen to promote and control heavy hydrocarbon
cracking reactions.
It is characterized by significant upgrading of heavy feeds that are converted largely into high quality light
and intermediate products.
Unlike other conversion processes, hydrocracking has the additional advantage of offering considerable
operating flexibility which makes it possible to a certain extent to adapt unit production to market
requirements.
A typical material balance at total conversion and main product characteristics, are shown below.
YIELDS
PRODUCTS REMARKS
% wt of feed
INPUT
Catalyst constraints: limited metal, nitrogen,

Distillate feed 100 Conradson carbon residue content
Hydrogen 3 Substantial consumption of hydrogen requiring

production plant
TOTAL INPUT 103.0
OUTPUT
- sulfur plant required for H2S treatment

Gas (H2S, C1, C2, C3, NH3) 4.3 - process water stripping
Butane 4.6
Light gasoline 14.1 Rich in isoparaffins, high RON
Heavy gasoline 18.0 Rich in N - Excellent RON after reforming -

Requires appropriate reforming capacity
Kerosene 38.0 Good cold condition characteristics – Sulfur free
Gas oil 24.0 High cetane number – Sulfur free
TOTAL OUTPUT 103
This example shows:
- the excellent process selectivity with respect to gasoline, kerosene and gas oil fractions
- the absence of heavy products as produced by FCC
- the substantial hydrogen consumption
00111_A_A © 2009 - IFP Training

2
COMPARISON FCC/HYDROCRACKING
Catalytic cracking Hydrocracking
Operating conditions
H2 No Yes
Total pressure 1 bar > 100 bar
Temperature (°C) 500-600 350-430
Cycle duration A few seconds 1 to 3 years

(between two regenerations)
Contact time A few seconds 1 hour
Product quality
Gasoline Relatively good Good after cat reforming
Gas oil Very poor Excellent

(CN ≥ 20) (CN > 55)
Base oil Unsuitable Excellent

(VI > 110)
Feed processed
VGO + Low metal VR well cut VGO

3
STRUCTURE OF THE PRODUCT YIELDS OBTAINED

BY THE DIFFERENT CONVERSION PROCESSES
Ranking of ++ very good

product + good
quality - poor F. C. C.
-- very poor %
0
10 GAS + LPG +
20
• VGO 30 +
from crudes
or
• Vacuum residues 40 Gasolines –
PRODUCTS
FCC FEEDS
with low metal

content 50
• VGO 60
from visbreaker
• etc. 70
LCO –
80
90 HCO + Slurry –
Coke* D PCD 334 C
100
* self consumed
HYDROCRACKING
0 GAS + H2S
+
10 Light
Gasoline *
20
Heavy ++
30
VACUUM
FEEDSTOCKS
40
PRODUCTS
++
DISTILLATES 50 Kerosene
60
360 - 550°C
70
80 360 - ++
Gas oil
90
D PCD 343 B
100 102.5
* After catalytic reforming

00111_A_A
HYDROCRACKER CONFIGURATION : SINGLE STAGE - TWO STAGE HCK
CRACKING REACTION AND HYDROCRACKING CONFIGURATION
Gas-oil
CUT VGO Naphtha Gas
Kero
number
C32 C16 C8 C4
of Caverage
4

USA
Maxi naphtha objective
TWO STAGE HCK (NH3-H2S removed after first stage)
Outside USA
Maxi gas oil objective
D PCD 1173 A
SINGLE STAGE HCK = ONCE THROUGH OR RECYCLE WITH ONE OR TWO REACTORS (HDT-HDC)
00111_A_A
Single-stage once through Single-stage with liquid recycle
Amorphous silica-alumina catalyst

5
SINGLE-STAGE

D PCD 2100 D
Series flow once through Series flow with liquid recycle

Zeolite cracking catalyst
6
TYPICAL HYDROCRACKING PROCESS

— Flow schemes —
One-stage process
Make up H2 H2 recycle FRACTIONATION

LPG
1 or 2 REACTORS
NAPHTHA
FRESH
FEED MIDDLE
DISTILLATES
D PCD 1174 A
SEPARATION
FUEL OIL
RESIDUE RECYCLE
Two-stage process
Make up H2 H2 recycle
1st STAGE
REACTOR FRACTIONATION
FRESH LPG
FEED
NAPHTHA
2nd STAGE
REACTOR MIDDLE
DISTILLATES
SEPARATION
D PCD 1174 B
FUEL OIL
RESIDUE RECYCLE

7
The incorporation of the hydrocracking process within the refining scheme requires a complex that
includes the following units:
- a specific vacuum distillation unit allowing separation of distillate feeds that meet purity
specifications with respect to metals, Conradson carbon residue, etc.
- a hydrogen production plant using the steam reforming process which enables hydrogen
production from light hydrocarbons (methane, fuel gas, butane, etc.)
- a hydrocracking unit, consisting of a reaction section operating at high pressure (around

160 bar) and high temperature (360-400°C) and a complex separation section
- a sulfur plant including facilities for amine washing of gaseous effluent for H2S recovery
and for sulfur production
- a stripper for process water which contains large amounts of ammonia and H2S
A typical hydrocracker flow scheme is shown below.
LIGHT SULFUR
HYDROCARBONS UNIT SULFUR
WATER GAS
H2S
WATER
STRIPPER AMINE
HYDROGEN WASHING FUEL GAS
STEAM WATER
PRODUCTION GAS
UNIT
(steam reforming) MILD
NAPHTHA
HYDROCRACKING
HYDROGEN • Reaction
HYDROCRACKED
• Separation GASOIL
Hy coker
gas oil
GAS OIL
VACUUM
ATMOSPHERIC
RESIDUE DISTILLATION
DISTILLATE
D PCD 1172 A
VACUUM RESIDUE

8
The hydrocracking process does not enable separation of the distillate feed into light and intermediate
products in one run. The conversion per run is therefore determined as the ratio of gas oil and lighter
products (370°C–) obtained to the feed rate.
370°– product rate

Conversion per run = x 100
feed rate
and the normal value is in the range of 60 - 70%.
Consequently the fraction heavier than gas oil has to be recycled to the reaction section, which
obviously reduces the amount of fresh feed that can be run.
II - PROCESS CHARACTERISTICS
1- CHEMICAL REACTIONS
The operating conditions used in hydrocracking processes:
- temperature of 360 - 400°C

- high hydrogen pressure
- use of hydrorefining and hydrocracking catalysts
result in complex chemical reactions that can, for the sake of simplicity, be classified under the
following three headings: conventional hydrorefining reactions, hydrogenation reactions and actual
hydrocracking conversion reactions.
a - Hydrorefining reactions
They are similar to the chemical conversions already encountered in conventional hydrotreating. Due
to the severity of operating conditions the reactions are virtually complete, resulting in highly
purified products. The reactions involve heavy compounds of sulfur, nitrogen and oxygen and lead
to the formation of H2S, NH3, H2O and light products.
H 2S
Sulfur, nitrogen and hydrogen saturated, lighter hydro-
NH3 +
compounds + hydrogen carbon compounds
H 2O
These reactions are exothermic and moderately hydrogen consuming. One important property is their
removal of heavy nitrogen compounds which are poisons for acid hydrocracking catalysts.
The effectiveness of hydrorefining reactions obviously depends on the amount of sulfur and nitrogen
impurities in the distillate feedstock.

9
b - Hydrogenation reactions
The degree of hydrogen pressure used in hydrocracking processes combined with the hydrogenating
properties of the catalysts results in virtually complete hydrogenation of the unsaturated chemical
compounds. This applies in particular to aromatic hydrocarbons and explains at the same time why
hydrocracked products are largely composed of saturated paraffinic and naphthenic hydrocarbons.
A typical chemical equation of the hydrogenation of a heavy aromatic compound is shown below.
+ hydrogen
Heavy aromatic heavy naphthenic

hydrocarbon hydrocarbon
It leads to the formation of naphthenic hydrocarbons.
Hydrogenation reactions are very exothermic and hydrogen consuming.
c - Hydrocracking reactions
They are an essential factor in this conversion process because they lead to the formation of products
lighter than those in the feed. They apply to all types of hydrocarbons.
heavy hydrocarbons + H2 light

P, N or A hydrocarbons
For example
C30H62 + H2 C15H32 + C15H32
The amount of hydrogen consumed is equivalent to the degree of saturation of the short molecules
cracked. At the same time these reactions are very exothermic.
It should be noted that the action of the catalyst in this process is to orient the shortest paraffinic
molecules produced toward isomerized forms. This explains the high octane number of the light
gasoline.
OVERALL it can be seen that the DIFFERENT CHEMICAL REACTIONS involved in the hydrocracking
process are all hydrogen consuming, which explains the high input of this component in the material
balance of the unit. Another common factor is the exothermic nature of the reactions, which means
that precautions have to be taken to avoid any runaway of the reaction section.

10
2- HYDROREFINING CATALYSTS
The first stage of the hydrocracking process is similar to conventional hydrotreating and uses
hydrorefining catalysts not very different from those used in hydrodesulfurization of kerosene and
gas oil. These catalysts are of the NiMo type and are composed of an alumina support bearing active
nickel and molybdenum sulfides. They promote desulfurization and denitrogenation, and also
hydrogenation.
They are used in the first reactor, known as the HYDROREFINING REACTOR, designed to
hydropurify the feed before it undergoes the actual cracking process. Typical operating conditions for
the first reactor are as follows:
• Pressure : 160 bar, chiefly due to hydrogen
• Temperature : approximately 375°C
• Catalyst : NiMo on alumina
• Exothermicity : hydrogen quench between the two beds
At the reactor outlet the reaction mixture is therefore composed of the hydropurified and partially
hydrogenated feed, hydrogen, and H2S, NH3 and H2O formed by the chemical reactions.
3- HYDROCRACKING CATALYSTS
Like the catalytic reforming process, hydrocracking requires dual-purpose catalysts that are used in a
second reactor called the CONVERSION REACTOR. The catalysts must simultaneously satisfy the
following requirements:
- they must promote cracking reactions, which calls for an acid catalyst. Synthetic silica-
alumina catalysts are amorphous (non-crystalline) solids with acid properties and have been
widely used in cracking processes.
they have currently been replaced, however, by crystalline silica-alumina systems called
ZEOLITES which are significantly more acidic.
- they must possess hydrogenating properties to be able to hydrogenate the heavy hydro-
carbons in the feed and to saturate the cracked species with hydrogen. This action can be
provided by sulfide combinations of the NiMo or NiW type and in some formulations even by
precious metals such as palladium.
The fundamental property of hydrocracking catalysts probably lies in the acidity of the silica-alumina
support. It is the acid support that is directly subject to the poisonous action of the alkaline nitrogen
compounds not converted in the refining reactor, and of ammonia.

11
The basic pattern of the silica-alumina structure is a tetrahedron. The four peaks of the tetrahedron are
occupied by oxygen atoms (valence = 2) and the centre by a silicon atom (valence = 4) or by an
aluminium atom (valence = 3). These two basic patterns are shown below.
Oxygen Negative charge

Si AI
D CH 1000 C
Basic patterns of silica-alumina structures
As can be seen, due to the tri-valence of the aluminium atom, the tetrahedron in question has a
residual negative charge.
Assembly of the elementary tetrahedra is based on the valence of the oxygen atoms that remains free.
The tetrahedra may be assembled by their peaks, by their surfaces or by their edges, resulting in a
random assembly in space. This leads to a structure of varying porosity, characteristic of
AMORPHOUS or non-crystalline silica-alumina. The figure below shows a portion of such an
assembly.
Na+
Na+
– –
Al
Si Si Al
Na+
Si Al Si Si
– Na + Na +
Al –
Si Si Al
D CH 1000 B
Positively charged sodium ions Na+ appear in the structure to compensate for the negative charges
due to the presence of aluminium atoms in the silica-alumina. Acidity is achieved by an acid treatment
that replaces the Na+ ions by H+ ions.

12
ZEOLITES or MOLECULAR SIEVES are silica-alumina systems that have a specific crystalline
structure. There are a great variety of them but the basic element is always the same SiO4 or AlO4
tetrahedron.
Unlike the amorphous silica-alumina systems, these elementary tetrahedra assemble exclusively by
their peaks, which produces the basic crystalline pattern (known as sodalitic pattern) of the zeolites
used in acid catalysis.
D CH 306 A
In the figure all the oxygen, silicon and aluminium atoms are shown. To simplify the sodalitic pattern
and make it easier to see, first all the oxygen atoms not located on the edges are removed (a), and
then only the silicon and aluminium atoms are shown (b).
(a) (b)
D CH 303 A
Sodalitic pattern
The polyhedron has 6 square surfaces and 8 hexagonal surfaces. The structures are assembled either
by the square surfaces or by the hexagonal surfaces.

13
• Assembly by the square surfaces: A SIEVE
These assembled structures are repeated in space and produce very regular, interconnected cavities
which give the solid a very specific crystalline structure.
Location
of "cages"
Lattices assembled
by their square faces
D CH 146 B
Assembly by the square surfaces
The openings to the cavities in the A sieves vary from 3 to 5 Å, in size according to the nature of the
positively charged ions incorporated in their structure.
A-type sieves are used in industry for gas purification (drying) or for separating the constituents of a
mixture according to the size of their molecules, hence the term molecular sieves.
Assembly by the hexagonal surfaces: X or Y SIEVES (according to the proportions of silicon and
aluminium)
Hexagonal face lattice assembly

D CH 147 B
Assembly by the hexagonal surfaces

14
Assembly by the hexagonal surfaces produces cavities of larger volume and openings exceeding 10 Å.
This crystalline structure of X or Y sieves is therefore more suited to the adsorption of heavy hy-
drocarbon molecules which in addition can circulate within the zeolite due to the interconnecting
cavities.
At the same time the ion exchange that acidifies the sieves gives them much greater acidity than the
amorphous silica-alumina systems which explains why they are used for hydrocracking.
Typical conversion reactor operating conditions are as follows:
• Pressure : 160 bar approximately
• Temperature : ≈ 360 - 400°C

• Catalyst : 3 beds of hydrocracking catalyst
1 bed of hydrorefining catalyst
• Exothermicity control : hydrogen quench between the second

and third bed
The use of the last hydrorefining catalyst bed is to remove the sulfur compounds that may have formed
due to the action of H2S on the intermediate products of the reaction.
4- MAIN CATALYST CONSTRAINTS

a - Constraints connected with the feed. They concern
- nitrogen compounds and ammonia which de-activate the catalyst. This requires an
increase in the temperature or reduction of the feed rate in order to obtain the desired
conversions
- sulfur. Concentration of H2S should be within a bracket that ranges from a minimum value
necessary to maintain the sulfur forms of the active species to a maximum value beyond
which catalyst activity deteriorates
- metals, concentration of which is strictly limited. An initial amount is nevertheless removed

by the hydrorefining catalyst
- asphaltenes and resins that may be entrained in vacuum distillation and are coke promo-
ters. Conradson carbon residue is related to these compounds
b - Constraints connected with operating conditions
- moderate temperature to avoid excessive coking of the catalyst
- very high H2/HC ratio for the same reason as above
- large amount of catalyst in relation to the feed rate to ensure a sufficiently long catalyst-feed
contact time.

15
III - HYDROCRACKER OPERATING CONDITIONS (Figure 1)

1- FEED CIRCUIT
The feed circuit includes a pump capable of raising the pressure of the liquid distillate feed to a value
higher than that of the process, and heat exchangers allowing recovery of heat from the hot effluents
from the reaction section.
The first reactor inlet temperature is controlled by a mixture of hydrogen-rich gas which is over 90%
pure. The hydrogen alone is heated in a furnace controlled by the reactor inlet temperature. This
avoids risks of coking. The latter is liable to occur if the feed is heated directly in the furnace.
Hydrogen pressure on the catalyst in the reactor is determined by hydrogen dilution. It is calculated
in m3 of pure hydrogen per m3 of feed. The design value is in the region of 750 - 800 m3/m3.
2- REACTOR SECTION
The refining reactor includes two catalyst beds. A rise in temperature is observed in the first bed due
to the exothermic hydrorefining and hydrogenation reactions.
A hydrogen quench lowers the temperature before the feed is subjected to the second bed, bringing it
more or less to the first reactor inlet temperature. The rise in temperature in the second bed is again
the result of the exothermicity of the reactions.
At the first reactor outlet the recycle is added to the mixture. The injection of hot hydrogen regulates
conditions at the conversion reactor inlet, i.e. a slightly higher temperature than in the first reactor
and greater dilution (approximately 1200 m3 H2/m3).
The exothermicity of the hydrocracking reactions results in a difference in temperature (Δt) between
the inlet and outlet of the 3 beds. Temperatures are controlled by two hydrogen quenches.
The reactors operate at the pressure required by the process (around 160 bar). The differences in
pressure between inlet and outlet are due to pressure drops in the mixture as it moves through the
reactor. Pressure drops increase with catalyst coking, fouling and plugging.
3- REFRIGERATION - HP AND MP SEPARATORS

At the second reactor outlet the mixture of hydrogen and cracked products is cooled by heat exchange
with the feed, the hydrogen and the liquid effluent of the MP separator. Condensation is completed by
air coolers upstream of the HP separator. It should be noted that injection of process water before the
air coolers can prevent condensation to solid state of salts such as ammonium sulfide formed by the
action of H2S or NH3. Figure 2 indicates the conditions for formation of solid ammonium sulfide. The
separator is maintained at 160 bar and separates:
- a gas phase rich in hydrogen to which is added make-up hydrogen from the hydrogen
plant via the make-up compressors. The resulting mixture is compressed by the recycle
compressors and routed to the reaction section
- a liquid phase including the products of the process water reaction. The process water is
separated and treated
The resulting liquid is expanded before being routed to the MP separator. The gas phase in the
separator contains H2, H2S and light hydrocarbons and is routed to the HP amine washing installation.
The liquid phase is reheated to the required temperature and fed to the fractionation section.

16
4- DISTILLATION SECTION
The section includes:
- a debutaniser that separates C4 gases from gasoline and heavier fractions
- a depropaniser that produces a C1 - C2 - C3 - H2S - NH3 gas fraction for amine washing,
and a butane fraction
- an atmospheric distillation column that separates light gasoline, heavy gasoline and ke-
rosene fractions
- a vacuum distillation column that separates the gas oil fraction from the recycle
5- HYDROCRACKING CATALYST ACTIVATION

Hydrocracking catalysts are manufactured as oxides (usually by metals salts impregnation on a
support, followed by calcination) and need to be sulfided before use.
• Sulfidation:
- MoO3 + 2 H2S + H2 ∅ MoS2 + 3 H2O

- 3 NiO + 2 H2S + H2 ∅ Ni3S2 + 3 H2O
• Sulfiding methods
Under H2 pressure, with a sulfiding agent added in gas phase, or more frequently in the liquid, which
decomposes into H2S and hydrocarbons.
Dimethyl disulfide DMDS
200°C
CH3 — S — S — CH3 + 3 H2 2 H2S + 2 CH4
• Passivation
The cracking function of the zeolite is very active and has to be passivated to avoid early coking of the
catalyst, this is done by an injection of aniline. The aniline breaks in NH3 which temporarily neutralizes
the active sites of the catalyst. The catalyst activity is then restored by a temperature increase which
desorbs NH3.
6- CATALYST REGENERATION
The deactivation is the result of coke deposition. The activity is recovered by burning the coke. It is
done either in-situ or ex-situ after catalyst unloading under inert atmosphere.
However metals contamination is irreversible.
Regeneration consists in a controlled coke burn off. Sulfides are also converted back to oxides.

17
• Reactions
7
Mo S2 + O Mo O3 + 2 SO2
2 2
7
Ni3 S2 + O 3 Ni O + 2 SO2
2 2
C + O2 CO2
1
H2 + O H 2O
2 2
• In-situ method
- shutdown unit
- nitrogen purge
- combustion of coke
- presulfiding
• Ex-situ method
The used catalyst is pyrophoric and the contact with air should be avoided. The catalyst should be
unloaded under nitrogen in drums and sent to an outside company for regeneration.

18
IV - HYDROGEN PRODUCTION
1- PRINCIPLE OF THE REACTION
The hydrogen required by a hydrocracking unit comes chiefly from the hydrogen atoms linked to the
carbon atoms in the light hydrocarbon molecules constituting the feed of a hydrogen production plant.
The thermal breakdown of hydrocarbons produces hydrogen gas. Thus methane, for example, gives
the following result:
CH4 Csolid + 2 H2
thermal
breakdown
Hydrogen production is automatically accompanied by solid carbon deposition which makes the
process unusable.
The carbon deposit can be eliminated by operating in the presence of steam. At high temperature the
water reacts chemically on the solid carbon and forms two gaseous products, carbon monoxide and
hydrogen.
Csolid + H 2O CO + 3H2
The breakdown of methane in the presence of steam leads to the following reaction:
CH4 + H 2O CO + 3H2
The hydrogen so formed comes partly from the methane and partly from the water which is
chemically broken down by the reaction.
The process based on this principle is called STEAM REFORMING.
The reaction involved in reforming is extremely endothermic (60 kcal consumed per mole of methane
converted). It is promoted by high temperatures and the operating temperature is generally around
800°C. It also requires moderate pressure of around 20 bar, a substantial amount of excess steam
(about 3 tons of steam per ton of hydrocarbon feed) and a specific catalyst (Nickel on Alumina) to
direct the conversion process toward maximum hydrogen production and to limit carbon deposition.
In addition to the steam reforming reaction, the carbon monoxide formed may react on the excess
steam, producing supplementary hydrogen gas:
CO + H2O CO2 + H2
This conversion is called the CO CONVERSION reaction or SHIFT reaction.
Unlike the reforming reaction, CO conversion is exothermic (10 kcal per mole of CO converted). High
temperatures have a negative effect on the reaction and a high rate of conversion is obtained only
with a moderate temperature. The reaction also requires a specific catalyst (Iron or Chromium).
As can be seen, hydrogen production consequently has to be divided into two successive chemical
stages:
- first, the steam reforming reaction that takes place at high temperature
- second, supplementary hydrogen production by CO conversion, carried out at low
temperature after cooling the reformer effluent.

19
2- HYDROGEN PRODUCTION PLANT

The principle of the hydrogen production plant is shown in Figure 3 and the plant in Figure 4. A number
of important operations are involved.
a - Preparation of the feed
The catalysts used in the hydrogen plant are very sensitive to some POISONS, mainly SULFUR and
CHLORINE.
The light hydrocarbons used as feed for the unit:
- CATALYTIC REFORMING PURGE gas

- HP and LP FUEL GAS after AMINE WASHING
- commercial BUTANE
must therefore be carefully purified.
The purge gas from the catalytic reformer contains traces of hydrochloric gas (HCl) and is
dechlorinated on beds of specific ADSORBENT (caustic soda). After compression and reheating to
the required temperature, intensive desulfurisation of the feed is performed by conventional
CATALYTIC HYDROTREATMENT in a reactor containing a catalyst consisting of cobalt molybdenum
on an alumina support. The H2S generated by the desulfurization reactions is chemically trapped by
the ZINC oxide contact mass.
b - Steam reformer furnace
The purified feed, combined with the superheated MP steam (approximately 3 tons of steam per ton of
feed) is routed to the reformer furnace. The reforming reaction requires substantial addition of very
high temperature heat, which calls for original technology. The feed mixture is distributed evenly in a
large number of tubes 10 m long and placed vertically in the radiation chamber of the reformer furnace.
The feed circulates from top to bottom of the tubes heated by the radiation of the burner flames and on
its way it contacts the catalyst which is present inside the tubes in the form of small rings about 1 cm in
size. NICKEL, on an inert alumina support, is the active substance of the catalyst. It also contains
POTASSIUM which activates breakdown of the water and thereby limits carbon deposition.
Operating pressure is in the region of 20 bar and temperature is around 800°C.
A significant amount of heat is recovered from the very hot flue gases leaving the radiation zone of
the furnace. It is used to generate HP and MP steam, to preheat the feed and the furnace combustion
air.
c - CO conversion
The effluent leaving the furnace contains a large amount of hydrogen (70 - 80% volume excluding
steam), a small amount of carbon dioxide and non-converted methane, and a non-negligible amount
of carbon monoxide (generally over 10% volume). After cooling to around 350°C by heat exchange in
a steam generator, the CO conversion reaction takes place. The converter reactor contains a fixed
bed of iron and chromium based catalyst. The carbon monoxide is partially converted by the steam
into hydrogen. The reaction is exothermic and the temperature rises as the effluent passes through
the catalyst bed. At the converter outlet the gaseous effluent is hydrogen enriched and its carbon
monoxide content has been drastically reduced (to about 1% volume on dry gas).

20
d - Hydrogen purification
The converter effluent is cooled and the dilution water is condensed. The final hydrogen purification is
performed by adsorption. The hydrogen passes through a fixed adsorbent bed and the impurities are
fixed on the adsorbent. Once it is saturated the adsorbent has to be regenerated. The normal
regeneration method is to raise the temperature of the bed by circulating a hot gas through it which
desorbs the impurities. The bed then has to be recooled before it can be used again for adsorption.
Although this method of desorption by temperature variation, known as thermal swing adsorption
(TSA) is very effective, it nevertheless has a disadvantage. The heating and cooling phases are time
consuming and consequently it cannot be applied to frequent cycle operation.
It also possible to regenerate adsorbent beds at ambient temperature by reducing the operating
pressure. This method is known as pressure swing adsorption (PSA). Its advantage is that it is very
fast and therefore lends itself to operation by cycles in close succession, thus making it possible to
process large quantities of gas effluent with a high impurity content.

"SERIES FLOW" HYDROCRACKER
— Figure 1 —
— Simplified flow scheme —
60
FRESH
HYDROGEN
RECYCLE
HYDROTREATMENT CONVERSION COMPRESSOR
REACTOR M
REACTOR
Process 3.5
360 380 water
185
AUXILIARY
170 COMPRESSOR
+ NH3
GAS
+ H2S
HP PROPANE
quench GAS
SEPARATOR
quench SEPARATION BUTANE
20
LP
SEPARATOR
C 4- DEBUTANIZER
vacuum LIGHT
FURNACE FURNACE 420 GASOLINE
420
HEAVY
GASOLINE
VACUUM
FEED 125
COLUMN
VACUUM KEROSENE
DISTILLATE
Vacuum distillate
Recycle
ATMOSPHERIC
C 5+ COLUMN
D PCD 315 B
GASOIL
HYDROTREATMENTS — Figure 2 —
– Ammonium sulfide formation –
• Favorable conditions for NH4 HS formation depending on temperature and partial pressures
For any temperature t
Possible formation
of solid NH4 HS
Partial pressure H2S
NH3 (g) + H2S (g) NH4HS (s)

No solid
NH4 HS Te
mpe
ra
tur
e
Partial pressure NH3
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.80.9 1 2 3 4 5 6 7 8 9 10

10 10
Partial pressure H2S (bar)
9 9
8 8
7 7
6 6
5 5
4 4
3 3
2 2
Te
m pe
rat
ure
1 40 45 1
0.9
° ° C 0.9
0.8 C 0.8
0.7 35 0.7
0.6
°C 0.6
30
0.5
°C 0.5
0.4 25 0.4
°C
0.3 20 0.3
°C
0.2 15 0.2
°C
10
°C
D PCD 908 B
0.1 0.1
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.80.9 1 2 3 4 5 6 7 8 9 10
Partial pressure NH3(bar)
PRINCIPE OF HYDROGEN PRODUCTION PROCESS — Figure 3 —
HYDROGEN FROM
MP AND FUEL GAS
CATALYTIC BUTANE
FROM AMINE WASH
REFORMER
HCI VAPORISATION
REMOVAL
Hydrogen from PSA HYDRO- 340

DESULFURATION
24
H2S
REMOVAL
MP STEAM
STEAM 800 t °C
REFORMING
% Vol. 23
P bar
H2 73.3
CH4 6.0 CO 340
CO2 9.7 CONVERSION
CO 11.0 22
+ H20 100.0
CONDENSATE
RECOVERY
% Vol.
H2 78.9
CH4 5.2 PSA
CONDENSED WATER % Vol.
CO2 14.5 PURIFICATION
CO 1.4 H2 29.0
CH4 17.5
+ traces H20 100.0
CO2 46.0
CO 7.5
% Vol.
100.0
H2 99.99
CH4 traces PURGE GAS
CO2 ≤ 20ppm TO FUEL
D PCD 2002 B
CO
TO HYDROCRACKER
100.0

Vaporiser MP
FG HYDROGEN UNIT
E 01 steam
LIQUID FG 44 tubes per row
BUTANE — Figure 4 —
11burners per row
FG
A-B-C
Steam
H2 K01
from PSA E 02 water
Preheater
M
Gas
from Steam
E 03
PSA water
F 01
HP FG
EA 01 R 02
HP FG B 01 REFORMER FURNACE
Hydro
desulfurisation MP GENERATOR
To PSA E 04
REACTOR Water and steam
H2
RAW
from CATALYTIC
H2 to PSA
REFORMER
E 05 EA 02
R 01 B R 03 A à 08
R 03 B
R 04 B 04 B 05
R 01 A
Temperature (°C)
To PSA
HCI H2 S CO
D PCD 1175 A
Pressure (bar)
ABSORBERS ABSORBERS CONVERTER Condensates
Flowrate (t/h)
HYDROGEN PRODUCTION UNIT - STEAM REFORMING
— Figure 5 —
— Flow scheme —
STEAM
(3 t/t)
CH 4 100% %
FEED
CH 4 6
SULFUR - FREE
LIGHT H2 79
STEAM REFORMING
HYDROCARBONS CO 2 14
FURNACE
CO 1
Fuel 100
Stack CATALYTIC
gases
CONVERSION HYDROGEN HYDROGEN
OF RESIDUAL 99.9%
PURIFICATION
25 CO
bar
340°C (PSA)
20 bar
800°C
Catalyst
tubes
CO
CO2
CH 4
Steam reforming reaction CO conversion reaction

CH4 + H2O CO + 3 H2 % CO + H2O CO2 + H2
CH 4 6
CO conversion reaction H2 73
CO + H2O CO2 + H2 CO 2 10
D PCD 316 B
CO 11
100
HYDROGEN PRODUCTION UNIT - PARTIAL OXIDATION (POX)
— Figure 6 —
— Process flow scheme —
OXYGEN HP regulating steam

32.5 13.1
i.e. 60,000 Nm3/h

28.6 Steam 5.7
HP
HYDROGEN
BURNERS (X2) 40
FEEDS 99.5%
68
70 66
Visbroken vacuum
Feed
residue bitumen WATER CONVERSION
+
sp.gr.15 = 1.169 Carbon WASHING OF CO P S A
4 1300
6% wt sulfur OF GASES CO + H2O CO2 + H2
1450
Ni + V = 800 ppm weight
Water Purge
to fuel
Water gas
CO2 ELIMINATION
Separation H2 S H2S and CO2
carbon-ashes
to CLAUS unit
Ashes
+
metals
D PCD 317 B
Water
From "Petroles et Techniques" - Sept. - Oct. 1994 (Texaco Process)
To waste
water treatment

Vacuum Distillation

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Refining-Petrochemicals-Chemicals-Engineering

VACUUM DISTILLATE HYDROCRACKING

I - PURPOSE OF HYDROCRACKING AND INTEGRATION WITH IN THE

III - HYDROCRACKER OPERATING CONDITIONS .................................................................... 15

RA HCR - 00111_A_A - Rev. 3 04/03/2009

I- PURPOSE OF HYDROCRACKING AND INTEGRATION WITHIN THE REFINING SCHEME

Catalyst constraints: limited metal, nitrogen,

Hydrogen 3 Substantial consumption of hydrogen requiring

TOTAL INPUT 103.0

- sulfur plant required for H2S treatment

Light gasoline 14.1 Rich in isoparaffins, high RON

Heavy gasoline 18.0 Rich in N - Excellent RON after reforming -

Kerosene 38.0 Good cold condition characteristics – Sulfur free

Gas oil 24.0 High cetane number – Sulfur free

TOTAL OUTPUT 103

This example shows:

00111_A_A © 2009 - IFP Training

Catalytic cracking Hydrocracking

Total pressure 1 bar > 100 bar

Temperature (°C) 500-600 350-430

Cycle duration A few seconds 1 to 3 years

Contact time A few seconds 1 hour

Gasoline Relatively good Good after cat reforming

Gas oil Very poor Excellent

Base oil Unsuitable Excellent

VGO + Low metal VR well cut VGO

00111_A_A © 2009 - IFP Training

STRUCTURE OF THE PRODUCT YIELDS OBTAINED

Ranking of ++ very good

with low metal

* After catalytic reforming

00111_A_A © 2009 - IFP Training

© 2009 - IFP Training

Amorphous silica-alumina catalyst

© 2009 - IFP Training

Series flow once through Series flow with liquid recycle

TYPICAL HYDROCRACKING PROCESS

Make up H2 H2 recycle FRACTIONATION

00111_A_A © 2009 - IFP Training

- a hydrocracking unit, consisting of a reaction section operating at high pressure (around

A typical hydrocracker flow scheme is shown below.

00111_A_A © 2009 - IFP Training

370°– product rate

and the normal value is in the range of 60 - 70%.

- temperature of 360 - 400°C

00111_A_A © 2009 - IFP Training

Heavy aromatic heavy naphthenic

It leads to the formation of naphthenic hydrocarbons.

Hydrogenation reactions are very exothermic and hydrogen consuming.

heavy hydrocarbons + H2 light

00111_A_A © 2009 - IFP Training

• Pressure : 160 bar, chiefly due to hydrogen

• Temperature : approximately 375°C

• Catalyst : NiMo on alumina

• Exothermicity : hydrogen quench between the two beds

00111_A_A © 2009 - IFP Training

Oxygen Negative charge

00111_A_A © 2009 - IFP Training

00111_A_A © 2009 - IFP Training

• Assembly by the square surfaces: A SIEVE

Hexagonal face lattice assembly

Assembly by the hexagonal surfaces

00111_A_A © 2009 - IFP Training