14 - K Overview Conversion

Refining-Petrochemicals-Chemicals-Engineering
———
S.C. PETROTEL-LUKOIL S.A.
REFINING PROCESSES AND PETROLEUM PRODUCTS
K - OVERVIEW OF CONVERSION PROCESSES

FOR HEAVY CUTS
INTRODUCTION ....................................................................................................................... 1
I - ORIGINS AND CHARACTERISTICS OF CONVERSION UNIT FEEDS .................................. 2
II - HEAVY FEED CONVERSION PROCESSES ........................................................................... 6
1 - Cracking techniques of heavy hydrocarbons ............................................................................... 6

2 - Heavy feed cracking processes ...................................................................................................8
3 - Capacity evolution ........................................................................................................................ 9
III - THERMAL CRACKING PROCESSES .................................................................................... 10
1 - Visbreaking of vacuum residue .................................................................................................. 10

2 - Delayed coking .......................................................................................................................... 14
3 - Fluidized coking - Gasification or flexicoking ............................................................................15
IV - HEAVY FEED CONVERSION BY CATALYTIC CRACKING WITHOUT HYDROGEN .......... 16

1 - Catalytic cracking catalysts ........................................................................................................ 16
2 - Cracking conditions and yields ...................................................................................................18
3 - Process outline ...........................................................................................................................19
4 - Catalytic cracker operation .........................................................................................................20
5 - Treatments and valorization of FCC products ............................................................................22
6 - C 2– gas treatment .....................................................................................................................23
7 - C 3 cut: propane - propylene.......................................................................................................23
8 - C 4 cut: butane - butenes............................................................................................................ 24
9 - FCC gasolines............................................................................................................................ 27
V - CONVERSION OF HEAVY FEEDS BY HYDROCRACKING.................................................. 31

1 - Vacuum gas oils hydrocracking.................................................................................................31
2 - Hydrogen production unit ...........................................................................................................34
3 - Vacuum residue hydrotreatment and hydroconversion .............................................................. 37
RA CON - 00012_A_A - Rev. 12 11/05/2007
 2007 ENSPM Formation Industrie - IFP Training

K1
INTRODUCTION
An imbalance exists between the market for petroleum products and the yields in terms of cuts obtained from
crude oils because heavy fuel oil demand has decreased due to energy conservation and nuclear power
development, and the demand for light products has remained stable or has increased due to growing
consumption of motor fuels. This raises the problem of the conversion of heavy products into light
products such as gasoline, kerosene and diesel fuel for the production of motor fuels.
0 0 0
LIGHT
CUTS
10 LIGHT 10 10
CUTS LIGHT
20 20 PRODUCTS 20 38 - 41%
(LPG, naphthas, automotive
30 30 gasoline) 30
INTERMEDIATE
CUTS
40 INTERMEDIATE 40 40
CUTS
50 50 50
INTERMEDIATE
60 60 PRODUCTS 60
(Jet fuel, kerosene, gas oil, 40 - 41%
heating oil))
70 70 70
HEAVY
CUTS HEAVY
80 80 80
CUTS
HEAVY PRODUCTS
90 90 (Heavy fuel oils, bitumen, 90
17 - 21%
D PPC 106 B
lubricants, coke)
100 100 100
Arabian light Brent WORLD MARKET (forecast: 2000)
The refining facilities in which this type of conversion is carried out are known as conversion units.
Feedstocks for this type of unit are petroleum fractions composed of heavy hydrocarbons with high boiling
points, generally in excess of 380°C. This temperature is normally considered the maximum boiling point for
hydrocarbon gas oil components in view of cold weather specifications.
Whatever the process used, the desired conversion is obtained through chemical reactions produced by
cracking heavy hydrocarbon molecules. Cracking consists in breaking the carbon-carbon bonds in the
hydrocarbon chains, which produces molecules with shorter chains and lower boiling points. A heavy feed is
thus converted, at least partially, into light products.
The first step in integrating the conversion processes into current and future refining schemes is to determine
the characteristics of the different feeds to be converted that are obtainable by refinery processes for
separating heavy products, i.e. atmospheric and vacuum distillation and solvent deasphalting.
The next step is to determine the characteristics of the cracking processes, i.e. thermal cracking, and
catalytic cracking with and without the addition of hydrogen (the former is known as hydrocracking).
The last step is to work out the different possibilities, on the basis of feed characteristics, technical and
economic process constraints, and trends in supply and product markets, for incorporating the numerous
conversion processes into the heavy product processing scheme.
00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

K2
I- ORIGINS AND CHARACTERISTICS OF CONVERSION UNIT FEEDS

The simplified scheme below shows the origins of the main heavy feeds that can be processed in conversion
units.
GAS + GASOLINE
CRUDE ATMOSPHERIC KEROSENE

OILS DISTILLATION
GAS OIL
ATMOSPHERIC RESIDUE
ATMOSPHERIC
RESIDUE
approx. 380°C +
VACUUM DISTILLATES
VACUUM CONVERSION
or VGO
DISTILLATION 380°C-560°C
UNITS
VACUUM RESIDUE
VACUUM Deasphalted VR or
D PCD 324 B
RESIDUE DAO
approx. 560°C +
SOLVENT
DEASPHALTING
ASPHALT
These feeds consist chiefly of:
- atmospheric residue which is more or less equivalent to a 380°C+ cut

- vacuum distillates, often known as VGO or Vacuum Gas Oil, which are the distillable
fraction of atmospheric residue ranging from 380 to 560°C approximately
- vacuum residue 560°C+ cut
- deasphalted vacuum residue, known as DAO or deasphalted oil

K3
The DAO cut is obtained by solvent deasphalting of vacuum residue. This operation is made possible by
the particular structure of vacuum residue. This takes the form of a colloidal solution composed of a
continuous oily medium containing micellae or aggregates of juxtaposed heavy molecules called
asphaltenes. They contain carbon and hydrogen and a great many hetero-atoms such as sulfur, nitrogen,
oxygen and metals.
The oily medium is composed of hydrocarbons and heavy aromatic compounds called resins which are
located at the interface between the asphaltene micellae and the hydrocarbons and therefore stabilize the
colloidal solution.
The addition of light liquid hydrocarbons to this solution greatly modifies the characteristics of the oily medium,
causing precipitation of the asphaltenes and sometimes even of the resins.
PRINCIPLE OF DEASPHALTING Deasphalting solvent

Light hydrocarbons
(butane, pentane)
Vacuum residue Oil
Asphaltene
precipitation
D PCD 325 B
Continuous
Asphaltene oily medium
Asphalt
and resin micellae (hydrocarbons)
The quantity of precipitate depends on operating conditions and on the nature of the liquid light hydrocarbon
used. The NF T 60 115 standard defines as asphaltenes products precipitated by n-heptane at its boiling
temperature.
This precipitation is performed industrially with propane or a mixture of propane and butane for base oils, and
with butane or heavier hydrocarbons of the C5- gasoline type when preparing feeds for conversion units.
The precipitated product is called asphalt and the non-precipitated fraction is known as DAO.
The scheme and the table on the following page gives the main characteristics of these feeds based on an
ARABIAN LIGHT crude.

K4
VGO 1
ARABIAN LIGHT ATM. VAC. 23
Solvent DAO
DIST. DIST. VGO 2 deasphalting 14.85
100 2.75
D PCD 326 A
A. R. V.R. Asphalt
3.70
44.3 18.55
ARABIAN LIGHT CRUDE
Atmospheric VGO/ VGO/

Vacuum
residue Distillate Distillate D.A.O. Asphalt
residue
371 °C+ 1 2
Yield on cude
44.3 23.0 2.75 18.55 14.85 3.70
wt%
15 0.962 0.912 0.943 1.031 0.973 >1

sp.gr4
Viscosity at
36.9 6 24.5 1130 120 -
100°C cSt
wt% S 3.1 2.2 2.8 4.2 3.65 6.2
not
wt% N not measured 0.075 0.12 0.2 -
measured
Conradson
10.8 < 0.1 2.1 25.7 8.5 69
carbon wt%
Asphaltenes
2.6 - < 0.05 6.9 < 0.05
wt%
Ni + V
42 <1 <2 102 21 420
wt ppm
Note that VGO/distillates contain a very small amount of asphaltenes and metals but on the other hand
their nitrogen content is not negligible. Metals are actually largely concentrated in the asphaltenes which
explains their high content in residues and in asphalt. DAO characteristics are a great improvement on
those of vacuum residue, with very low asphaltene content and limited metal content.
• High sulfur and nitrogen content on HS crude

Vacuum distillates
D.A.O. ➞ • Metal content virtually zero for distillates and low
for DAO
• High Conradson carbon residue

Vacuum residue ➞ • High asphaltene content
• High metal content, variable in terms of crude

K5
Arabian Light may be considered a medium crude in terms both of volatility and quality. The table below
provides a comparison between the characteristics of Arabian Light atmospheric residue and those of other
heavier crudes.
ATMOSPHERIC RESIDUE
TIA JUANA HEAVY

ARABIAN LIGHT ARABIAN HEAVY
(Venezuela)
Yield on crude
44.3 54.8 80.2
wt%
15 0.962 0.995 1.017

sp.gr4
Viscosity at 100°C
36.9 180 810
cSt
wt% S 3.1 4.4 3.18
Conradson carbon wt% 10.8 15.3 15.5
Asphaltenes wt % 2.6 7.0 7.2
Ni + V (wt ppm) 42 125 550
Note that cracker feeds from heavy crudes have a very high impurity content, particularly asphaltenes and
metals.
Note that the heavy cut yields increase when moving from ARABIAN LIGHT to ARABIAN HEAVY and TIA
JUANA heavy crudes and that the quality is downgraded with the increase of the quantity of heavy
products to be converted. The atmospheric residue characteristics of Tia Juana heavy crude are similar to
those of Arabian Light vacuum residue.

K6
II - HEAVY FEED CONVERSION PROCESSES
1- CRACKING TECHNIQUES OF HEAVY HYDROCARBONS

The cracking techniques and the resulting processes can be differentiated by the means used to get
the hydrocarbon chain breaking (20 to 25 carbon atoms minimum) from heavy hydrocarbons.
Three main techniques can be distinguished:
Cracking techniques Parameters
THERMAL CRACKING Temperature
Temperature
CATALYTIC CRACKING +
Catalyst
Temperature
CATALYTIC +
HYDROCRACKING Catalysts
+
Hydrogen
According to the techniques the resulting cracking is different and therefore it is interesting to analyse
the influence of each parameter.
a - Temperature
The crackability threshold of heavy hydrocarbons is in the range of 400-420°C. However, the
industrial thermal processes operate at a minimum temperature of 440-450°C in order to reach the
required cracking performances.
Together with temperature, the residence time when the heavy feedstock is at high temperature is
also an important factor. Similar cracking intensities are obtained either using a high temperature for a
short residence time or, on the contrary, a lower temperature for a longer residence time.
The figure below displays the evolution of the range of products obtained by thermal cracking of a
vacuum residue when the cracking severity is increased with temperature and/or residence time.

K7
VISBREAKING COKING
wt %
products
100
COKE
HEAVY POLY-
AROMATIC
PRODUCTS
NON-CONVERTED
FEEDSTOCK
FEEDSTOCK
GASOLINE - GAS OIL - VGO
GAS
D PCD 327 B
0
EVOLUTION by increasing the temperature and the residence time
It shows that the formation of lighter products than the feed, distillates, gas oil, gasoline, gas, is
associated with the formation of heavier products such as tars, coke from a certain level of cracking
intensity.
This phenomenom can be explained from the fact that heavy molecules which are activated by
temperature combine together to generate very heavy polyaromatic compounds. Beyond a given size,
they are called coke.
The scheme also shows the operating conditions for two thermal cracking processes of vacuum
residues:
- the VISBREAKING: a low-severity thermal cracking (450°C - 20 minutes) which looks like a
very moderate conversion process operating at the threshold of coke formation
- the COKING: a severe thermal cracking (550°C - several hours) which completely changes
the feed but produces solid coke with a significant yield.
b - Catalysts
The cracking catalysts which modify the reaction mechanism and selectively accelerate the chemical
reactions allow to reduce the temperature level required in the processes and to achieve a better
yield pattern, specifically less gas and coke and more gasoline.
Cracking catalysts are solids with acidic properties which drive reactions towards products of
improved quality.
c - Hydrogen
Due to its presence, hydrogen brings the advantages of hydrotreating to cracking process: purified
products which are saturated with hydrogen. Besides, hydrogen prevents the catalyst from coking, as
already mentioned, and allows to further improve cracking selectivity.

K8
2- HEAVY FEED CRACKING PROCESSES

In addition to above comments, it is well known that thermal or catalytic cracking without hydrogen
input generates unsaturated compounds, such as OLEFINS and in some cases DIOLEFINS.
Therefore, the terminology and the characteristics of the different processes can be summarized as
follows:
THERMAL PROCESS • Low-selectivity processes: producting a lot of gas

and coke
• Poor quality products, rich in olefins and diolefins

• Visbreaking
• No catalysts required: this allowing to process heavy
• Delayed coker feedstock with high metal content PROCESS
SPECIFICALLY APPROPRIATE FOR VACUUM
• Flexicoker (EXXON deep conversion unit)
RESIDUE CONVERSION
CATALYTIC CRACKING • More selective cracking

PROCESSES - less gas
- less coke
• Fluid Catalytic Cracking(FCC) for vacuum - good gasoline yield (50%)
distillates (VGO)
• Medium-quality products, with olefins
• Fluid catalytic cracking processes for
blends of vacuum distillate and vacuum • Due to the catalyst, high poisonous metal feedstocks
residue are not allowed to be processed on these plants
- R2R (TOTAL - IFP): 1 reactor - 2 regenerators
- HOC (Kellog Phillips) Heavy oil cracking • Process appropriate for CONVERSION OF VGO AND
- RCC (UOP): Resid Catalytic Cracking LOW METAL CONTENT VACUUM RESIDUE
HYDROCRACKING • Very high cracking selectivity

PROCESSES Complete conversion of feed into high-quality products:
gasoline, kerosene, gas oil
• Vacuum distillate Hydrocracking • No coke production thanks to hydrogen
• Vacuum residue Hydrotreating and • High hydrogen consumption requiring an hydrogen

Hydroconversion production unit
- Fixed-bed
HYVAHL (ELF - TOTAL - IFP) • Catalysts requiring high-purity feedstock: PROCESS
ARDS/VRDS (Chevron) APPROPRIATE FOR VACUUM DISTILLATE
- Moving-bed CONVERSION
LC Fining (Lummus)
H-Oil (HRI) • Processes possible for deep conversion of vacuum
D PCD 328 B
HYCON (SHELL) residues with appropriate complex technologies

requiring

K9
3- CAPACITY EVOLUTION
The table below shows the current status of refining facilities worldwide in terms of conversion capacity
(expressed in million tons per year):
Catalytic Residue
cracking Coking hydrotreatment
Visbreaking Hydrocracking
(FCC) incl. flexiconing hydroconversion
North America 290.0 10.6 94..3 77.9 18.8
Latin America 76.6 32.2 15.6 4.1 1.3
Western Europe 103.6 75.4 15.7 31.1 6.0
Africa 9.3 4.0 0.8 1.3 0.6
Middle East 13.7 17.3 3.9 25.1 13.4
Japan 38.9 – 4.0 6.5 21.5
Others Asia-Oceania 83.7 19.2 21.1 25.7 12.8
Total 615.8 158.7 155.4 171.7 74.4
Source: Oil and Gas Journal - December 22, 1997
FCC and visbreaking capacities increased strongly between 1975 and 1990 in Western Europe in
order to meet the growing demand for motor fuels and compensate for the decline in demand for heavy
fuel oil.
These conversion capacities are compared below with global refining capacities in the different
regions :
Atmospheric Vacuum Conversion capacity/

Number
distillation distillation distillation
of refineries Mt/year Mt/year Atm. capacity
North America 191 815 420 60%
Latin America 76 320 122 40%
Western Europe 109 715 251 32%
Africa 45 146 25 11%
Middle East 44 285 95 26%
Japan 38 248 81 29%
Others Asia-Oceania 103 600 89 27%
Total 606 3,129 1,083
Source: Oil and Gas Journal - December 22, 1997

K10
III - THERMAL CRACKING PROCESSES
1- VISBREAKING OF VACUUM RESIDUE

The visbreaking is a relatively mild thermal cracking process whose main objective is to reduce
vacuum residue viscosity in order to minimize heavy fuel oil production of the refinery.
a - Heavy fuel oil production without visbreaker
The refineries without visbreaker generally produce most of their heavy fuel oils by fluxing vacuum
residues as shown below:
HEAVY FUEL OIL MANUFACTURING

VR FROM VACUUM RESIDUE
1,000 to 3,000
cSt
at 100°C
HFO n°2
TO
40 cSt maxi
MARKET
at 100°C
Gas oil as
flux 1 cSt
D PPC 107 B
at 100°C
The blend of vacuum residue and gas oil flux should meet the HFO market viscosity specification of
40 cSt max at 100 °C.
Such an operation has two drawbacks for the refinery:
- a large heavy fuel oil production which is very often higher than the market demand
- a financial penalty when product at gas oil parity is downgraded to fuel oil.
In this context, the visbreaker improves the operations above. Therefore, most of the refineries in
Western Europe have been equipped with vacuum residue visbreakers, as the HFO demand has been
decreased since the mid 70's and idle distillation capacities were available.

K11
b - Visbreaker principle and operations
The thermal cracking involved in the process is relatively mild, resulting in limited conversion without
coke formation.
The operation is generally carried out in two steps. First the feed is heated to the required temperature
(around 450°C) in the visbreaker furnace, then maintained at this temperature in a soaker in which
cracking reactions continue for about twenty minutes (figure 2).
The effluent from the soaker is then routed to a recovery section including:
- either an atmospheric distillation column

- or a more complex unit comprising an atmospheric and a vacuum distillation columns
(figure 2)
A typical yield pattern of the visbreaker is shown below:
++ very good
Ranking of
+ good
product – poor VISBREAKER
quality –– very poor
%
0
Gas + LPG
Gasoline –
10
Gas oil –
20
Vacuum distillate –
30
VACUUM
40 PRODUCTS
RESIDUE
FEED
50
560°C + CUT
60
Cracked vacuum –
70 residue
80
90
D PCD 330 B
100
The products are generally rich in sulfur, in nitrogen and in unsaturated compounds and they are of
relatively poor quality.

K12
c - Heavy fuel oil production with and without visbreaker
From 100 tons of a vacuum residue 2000 cSt at 100°C, the schemes below show the amounts of on-
specs heavy fuel oil produced in both cases: a refinery either with or without a visbreaker.
100 TONS 53 tons 153 tons

VACUUM RESIDUE diluent (gas oil type) HFO n°2
2,000 cSt at 100°C 1 cSt at 100°C 40 cSt at 100°C
4.5 tons 124.5 tons

VISBREAKER gas + gasolines
HFO n°2
40 cSt at 10°C
95.5 tons
gas oil
vacuum distillate
residue
100 cSt at 100 °C
29 tons
diluent (gas oil type)
D PCD 331 B
1 cSt at 100°C
Thus, for 100 tons of vacuum residue, based on the above

example, visbreaking allows:
• a reduction of heavy fuel oil production

of 153 - 124.5 = 28.5 tons
• a supplementary production of gas oil

of 53 - 29 = 24 tons
It should nevertheless be pointed out that cracking severity must be carefully controlled otherwise the
fuel oil produced will be unstable.
The modification of the asphaltene structure during the cracking process and the change in the
characteristics of the oily medium may effectively destabilize the colloidal solution and cause
precipitation of the asphaltenes. The degree of cracking must therefore be limited in order to avoid
this phenomenon, since the resulting product is unusable.

K13
d - Other valorizations of visbreaker effluents with a vacuum distillation unit
When other HFO flux are available in large quantities in the refinery, for example LCO from FCC, a
better valorization than in the HFO pool is often looked for by the refiners for the visbroken gas oil and
VGO:
- the visbroken gas oil (typical yield of 10 %) can be routed to the gas oil pool after severe
hydrotreating to take into account sulfur and unsaturated compounds
- the visbroken VGO (typical yield of 20%) can be sent to FCC as an additional feed to be
converted for more than 60% into gas and gasoline.
In this scheme, the heavy fuel oil is produced from the cracked vacuum residue of very high viscosity
and the heavy products from FCC (LCO, HCO) used as diluent. The cracked vacuum residue after
minor fluxing is also used as high viscosity fuel within the refinery itself.

K14
2- DELAYED COKING (FIGURE 3)

This process applies mainly to vacuum residue but also to atmospheric residue. The cracking
conditions are relatively severe, with a high temperature in the 550°C range and a long residence
time in a large drum, which produces:
- converted light products i.e. gas, gasoline, gas oil and distillates which leave the top of the
drum in vapor form and are then separated by distillation.
- a solid product called green coke which accumulates in the drum. It is periodically
recovered and continuous operation of the process requires at least two coke drums. The
duration of the complete cycle including filling and coke recovery is about 48 hours.
A typical yield pattern of the coker is shown below:
Ranking of + + very good

+ good
product
– poor COKER
quality – – very poor
%
0
GazGAS
+ GPL
10
Gasoline ––
20
30 Gas oil ––
VACUUM
PRODUCTS
40
FEED
RESIDUE
50
560°C+ Vacuum –
60 gas oil
70
SOUS
80
Coke
D PCD 332 B
90
100
The main characteristics of the process are as follows:
- total elimination of the vacuum residue

- relatively high production of converted products which require upgrading in view of their poor
quality
- substantial production of coke. After crushing and calcination to eliminate the volatile
compounds, it can be used as an electrode in the aluminium industry on condition that it does
not contain too many impurities, particularly metals such as vanadium. Otherwise standard coke
is used as fuel.
This is a relatively old process. It was developed on a large scale in the United States to reduce fuel oil
production and increase gasoline production. The gas oil and distillates produced by the process can
be converted into gasoline in ancillary catalytic conversion units such as the FCCU. Few units of this
type exist in European refineries.

K15
3- FLUIDIZED COKING - GASIFICATION OR FLEXICOKING (FIGURE 4)

Fluidized coking and gasification, for which the technology was developed by EXXON, is a thermal
conversion process requiring a temperature in the 500°C range. The heat required by the process is
provided by the gasification of the coke produced.
This is achieved by the circulation of coke, in the form of pellets 0.4 to 2 mm in diameter and in
fluidized state, through three different vessels (Figure 4):
- the reactor, which receives the vacuum residue feed and the hot coke and in which the
thermal cracking reactions take place. The converted products are evacuated in gaseous
state at the top of the reactor. The coke produced accumulates on the pellets, increasing
their diameter before they are sent to another vessel.
- the heater, in which the coke pellets are heated by the hot gases from the gasifier.
- the gasifier, in which the coke from the heater reacts at very high temperature with a
mixture of air and steam. The coke is converted into a gaseous mixture containing
hydrogen, carbon oxide, nitrogen, carbon dioxide, steam and hydrogen sulfide. The gas is
then sent to the heater to heat the coke from the reactor and is then hydrotreated. After
cooling in the heater and treating, it constitutes a low heating value fuel gas.
The advantage of this process lies in the fact that it virtually eliminates the entire quantity of coke
produced, assuming nevertheless that there is a local outlet for the gas produced, since its low heating
value and the low pressure at which it is available mean that it cannot be transported over long
distances.
A typical yield pattern of the flexicoker is shown below:
FLEXICOKER
(thermal cracking and
coke gasification)
%
0
Gaz + GPL
GAS –
10
Gasoline ––
20
30
Gas oil
––
VACUUM
PRODUCTS
40
FEED
RESIDUE 50
Vacuum
560°C + 60 gas oil
coke fines
70
–– + H2S
80 Gasified and
desulfurized coke
D PCD 333 B
90 (NCV 900 kcal/Nm3)
100
The liquid products must be severely hydrotreated, and therefore cost of such a plant is very much
increased. This plant is a deep conversion unit as it nearly convert the whole vacuum residue.
Five flexicokers of total capacity of 8 mt/yr operate in the world, one plant is at design stage.

K16
IV - HEAVY FEED CONVERSION BY CATALYTIC CRACKING WITHOUT HYDROGEN
1- CATALYTIC CRACKING CATALYSTS

In addition to the heat and the temperature factors that characterize thermal conversion, this first type
of catalytic conversion process involves a cracking catalyst. The catalyst is generally solid and
composed of silica and alumina which has the acid property required for the catalysis of the cracking
reactions. It looks like a fine powder (a grain of a 60 µ average diameter) which circulates in a
fluidized state within the unit.
CRACKING CATALYST
Acid alumina-silica
First catalyst: acidic natural clay

From the 1940s: amorphous synthetic (non crystalline) alumina-silica
From the 1960s: blend of amorphous silica-alumina and cristyllized silica-
alumina, called zeolite or molecular sieves
Silicon atom
or aluminium ion
The zeolites (about 40% of present
catalysts) have a very high acidity
which has increased substantially
Sodalite type structure FCC catalyst activity. Their basic
cristallyne structure is shown on the
D CH 143 B
6 square faces
opposite figure.
8 hexagonal faces
The crystal is a polyhedron whose surface area is composed of the regular assembly of 8 hexagonal
faces and 6 square faces. The lattices may be joined either by their square faces or by their hexagonal
faces.
• Assembly by the square faces - 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

K17
A sieves have "entrance windows" to the inner area. Their size ranges from 3 to 5 Å, so only small
molecules such as water and H2S can enter. They can therefore be used for drying and purifying. In
addition, 5 Å sieves can be used to separate n-paraffin/isoparaffin mixtures (e.g. MOLEX process).
• Hexagonal face assembly - X and Y SIEVES
Hexagonal face lattice assembly
D CH 147 B
This crystalline structure is very different from the preceding one. X and Y sieves have large entrance
windows up to 10 Å accessible to large molecules. This type of sieve can therefore be used as a
cracking catalyst for heavy fractions. Y sieves are characterized by a higher silica content and have
increased thermal stability, especially in the presence of steam. They are currently the most widely
used. The addition to zeolites of rare earths such as lanthanum and cerium considerably increases
their cracking activity. The degree of activity is in fact too high for direct industrial use and zeolite
cracking catalysts contain 10 - 40% molecular sieves dispersed throughout the amorphous structure of
the conventional cracking catalyst.
The use of this type of catalyst considerably improves the selectivity of the operation, compared to
thermal cracking. However, these catalysts can be poisoned by metal contaminants which have to
be in a limited amount in the feeds.

K18
2- CRACKING CONDITIONS AND YIELDS

Typical conditions in catalytic cracking are:
High temperature 500-530°C

Low pressure 2-3 bar
Specific cracking catalyst
The feed processed in Europe are vacuum distillates (VGO), vacuum distillates from visbreaker and
also vacuum residues with acceptable low metal contents.
A typical yield pattern is shown below:
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 –
P R O D U CT S
FCC FEEDS
with low metal

content 50
• VGO 60
from visbreaker
• etc. 70
LCO –
80
90 HCO + Slurry –
D PCD 334 C
Coke*
100
* self consumed
The main product is gasoline (40 to 50 wt %). Sizeable quantities of gas and LPG are also produced.
A gas oil cut, named LCO (Light Cycle Oil) due to its aromaticity, and heavy cuts, named HCO
(Heavy Cycle Oil) and slurry are also produced.
Coke is self consumed and its production yield is about 5%.

K19
3- PROCESS OUTLINE
All catalytic cracking processes operate on the same principle, illustrated in the diagram below.
SPENT CATALYST
Cracked products
Flue gas to fractionation
Coke Catalyst circulation REACTOR Cracking

REGENERATOR
combustion 10 to 20 t/min 520°C to 540°C reactions
700°C to 750°C
D PCD 335 C
Air Feed
REGENERATED CATALYST
The catalytic section consists of:
- a reactor or riser in which the cracking chemical reactions of the feed in contact with the
catalyst take place at temperatures in the 500 to 530°C range and at low pressure (2 - 3
bar). Coke is deposited on the catalyst, which destroys its catalytic activity.
- a regenerator in which the coke deposited on the catalyst is burned with the injection of
combustion air. The heat thus released reheats the catalyst to a temperature generally in
the 670 -750°C range. The regenerated, coke-free catalyst can thus be re-used in the
reactor.
- reactor-regenerator connections allowing circulation of the catalyst from one vessel to

another. The heat recovered by the catalyst in the regenerator is restored, so to speak, to
the reactor.
The reactor effluent is then routed to a separation section consisting of a number of distillation
columns. The products are rich in unsaturated compounds, as in thermal cracking, but they contain
few unstable diolefins.

K20
4- CATALYTIC CRACKER OPERATION

An example of a fluidized bed catalytic cracking process flow scheme is given in Figure 5. The unit
comprises two main sections: the catalytic section in which the cracking reactions and the catalyst
regeneration take place, and fractionation section in which the cracked effluents are separated. These
two sections are described below.
Catalytic section
• Reactor - Riser
The feed, generally a VGO, is pre-heated in a long vertical tube, called a RISER, extending into the
reactor. It contacts the catalyst coming from the regenerator at very high temperature (around 700°C).
The feed vaporizes and cracks as it ascends the riser toward the reactor in which pressure is
maintained at a low level (2 barg.). The reactor temperature stabilizes at around 500°C. Modern
facilities use very active zeolite-based catalysts and characteristically the cracking reactions take place
entirely in the riser. Hence the term "all riser" or "riser cracking " unit.
At the top of the riser a baffle plate effects an initial separation of the hydrocarbon vapors and the
catalyst which falls toward the lower part of the reactor. The catalyst entrained with the gas is
recovered by two stages of cyclones in series located inside the reactor dome. The catalyst-free
reactor effluents are then sent to the fractionator.
• Stripper
The bottom part of the reactor constitutes the stripper. Steam is injected to partially remove the
hydrocarbons entrained or adsorbed by the spent catalyst. The latter flows down a sloping tube called
the standpipe connecting the bottom of the stripper to the regenerator. The opening is controlled by a
slide valve which maintains a constant level of catalyst in the stripper.
• Regenerator
In the regenerator the flow of air required for combustion is provided by a compressor generally called
a blower. High temperature combustion removes the coke deposited on the catalyst. Part of the heat
released by combustion is recovered by the catalyst which flows down a sloping tube toward the
bottom of the riser, thus providing the heat required for vaporizing and cracking the feed. The flow rate
of the regenerated catalyst is controlled by a slide valve.
Modern catalytic crackers are generally equipped with a regenerator operating at high temperature
(around 700°C) allowing complete combustion of the coke to carbon dioxide (CO2). Catalysis of
combustion is often achieved by adding a small quantity of precious metals such as platinum or
palladium to the cracking catalyst, since they are combustion promoters.
Entrained catalyst is removed from the combustion gases by two stages of cyclones located in the
regenerator. These high temperature flue gases are available at low pressure and can be used to
produce energy before being released into the atmosphere.
• Energy recovery from the flue gas
An expander turbine recovers mechanical energy which generally suffices to drive the air compressor.
The installation of a turbine of this type requires a third stage of cyclones outside the regenerator to
remove the catalyst fines and reduce wear by erosion. The expanded flue gases are then routed to a
boiler where the sensible heat is recovered for steam production.

K21
• Catalyst circulation-fluidization
The catalyst circulates at a very high rate (several tons per minute) and this is made possible by
injecting air, gas or steam into the catalyst transportation tubes thereby maintaining the catalyst in
fluidized state. In the regenerator, catalyst fluidization is ensured by the combustion air, and by the
cracked gases and the stripper steam in the reactor. The capacity of the catalyst to become fluid and to
flow like a liquid through the vessels due to the effect of elevation and pressure is closely related to the
grain size of the catalyst powder.
Generally speaking, no catalyst circulation problems or significant catalyst loss through the cyclones
are observed when the particle diameter of the catalyst is in the 20 - 150 micron range and when 50 -
70% of the catalyst grains are within the 40- 80 micron bracket.
Separation section of the catalytic cracking unit
• Main distillation column
The feed input to the main fractionator is the effluent from the reactor in vapor state. It is fed into the
base of the column and de-superheated by circulating slurry cooled in heat exchangers.
The column has two side stream drawoffs: LCO and HCO, equipped with steam strippers. HCO is
mixed with slurry to constitute a fuel oil base. Two circulating refluxes remove heat from the side
streams.
The overhead vapor products are partially condensed and a portion of the condensates is recycled to
the main column.
• Gas compression - Gas and gasoline recovery section
The gases leaving the overhead drum are compressed by the cracked gas compressor. Together with
the condensates from the overhead drum, they constitute the feed of the gas/gasoline separation
section. This section comprises several distillation and absorption columns that produce the following
products:
- fuel gas
- C 3 cut
- C 4 cut
and generally a light gasoline cut
and a heavy gasoline cut.
These cuts require different purification treatments before they can be routed to the storage or to other
plants.

K22
5- TREATMENTS AND VALORIZATION OF FCC PRODUCTS

The table below indicates the typical yields and the essential characteristics of each of the products
obtained by the catalytic cracking of a vacuum distillate and the required treatments.
Products Yield wt % Product characteristics - Complementary

Treatments - Valorizations
• large amount of H2S produced with high

sulfur feeds
GAS C 2– AND H2S 3-5 • requiring purification treatments (amine
washing-Claus plant)
C3 CUT • 70% propylene in the C3 fraction

• propylene recovery by distillation for
 Propane 5-9
 further use in petrochemicals
 Propylene
• 50-60% butenes in the C4 fraction

C4 CUT • possible valorization of butenes in
 Butanes ALKYLATION plant to increase gasoline
6 - 12

 Butenes production
• selective valorization of isobutene in
MTBE-ETBE plant
• most desirable product

• moderate octane number
RON 92-93 MON 79-80
• 25 to 30% of gasoline blend
• rich in olefins (> 30% vol.)
• contain corrosive and bad odor
GASOLINE C5 - C11 45 - 55 mercaptans which require sweetening by
a MEROX or SULFREX type process
• High sulfur content on HS Feed
(1000 to 1500 ppm wt)
• possibility to reduce olefins and sulfur
content by hyydrotreating
• possibility to improve octane numbers by
separating a gasoline heart cut and then
reforming it after hydrotreating
• very aromatic
GAS OIL 15 - 20 • low cetane number
(LCO) • S % generally high
• good diluent for heavy fuel oil
HEAVY STREAMS 6 - 10 • very aromatic products

(HCO + SLURRY) • diluents for heavy fuel oil
COKE 4-6 • self-consumed as fuel in the regenerator

K23
6- C2– GAS TREATMENT
FCC produces 3 to 5 wt % of C2 – gas (a bit of hydrogen, methane, ethane, ethylene) which also
contains most of the H2 S which has been generated through cracking of the sulfurous heavy
molecules. Generally speaking, it is considered that half of the sulfur contained in the feed is recovered
as H 2 S after the cracking reactions.
Gas is washed with ethanolamines (MEA or DEA) to extract H2S before sending it to the gas network
of the refinery. H2 S which has been separated is treated in a CLAUS unit to be transformed into
sulfur.
7- C3 CUT: PROPANE - PROPYLENE

Taking into account the present development of propylene in petrochemistry (for polypropylene
production), many refineries invest in propylene recovery through distillation.
Its separation from propane is very difficult as volatilities are very similar and consequently high
distillation column is necessary.
PROPYLENE RECOVERY
PROPYLENE
99.5% purity
to petrochemistry
Propane cut (30%) Separation throngh

Propylene cut (70%) distillation
from FCC about 150 trays
—
often two
columns in series
PROPANE
to commercial
D PCD 336 B
propane

K24
8- C4 CUT: BUTANE - BUTENES

The C 4 cut can be valorized two ways: through alkylation and/or for MTBE/ETBE manufacture.
a - Alkylation, a complementary unit to catalytic cracking

The alkylation unit can be used to increase the gasoline production of the catalytic cracker by
processing the excess LPG produced by FCC. The alkylation reaction consists in the addition of an
olefin, generally C4 (butene), to isobutane. This reaction produces a gasoline rich in isoparaffinic C8
with a high octane rating as shown in the diagram below. It involves the use of catalysts that are liquid
acids, i.e. hydrofluoric acid (HF) or sulfuric acid (H 2SO4).
PROCESS
FEEDS PRODUCTS
ALKYLATION
Butane to
Cut C4 from FCC commercial butane
with about 50% of butenes Addition of isobutane
50% of butanes on butenes ALKYLATE
Gasoline base
- at low temperature C8 cut rich in paraffins
with a
- in liquid phase high octane number
Isobutane - in presence of RON 94 - 97
MON 92 - 95
(C4 cuts from catalyst = liquid acid
atmospheric distillation HF hydrofluoric acid
D PCD 337 B
and reforming) or H2SO4 sulfuric acid
EXAMPLE OF ALKYLATION REACTION

C C
| |
C— C + C=C–C C— C — C — C — C
| | | |
C C C C
isobutane isobutene isooctane

C4H 10 C 4H 8 C8H18
RON = 100
MON = 100
Figure 6 shows the simplified process flow scheme for an alkylation unit using hydrofluoric acid.
The unit feed is composed of:
- the FCC C 4 fraction, rich in olefins

- the isobutane obtained by distillation from C4 crude distillation and catalytic reformer
streams

K25
The reaction is very exothermic and takes place in liquid phase in an exchanger type reactor in which
the temperature is maintained at 30°C approximately by circulation of cooling water. The catalyst for
the alkylation reaction is liquid hydrofluoric acid (HF). The hydrofluoric acid is decanted in the acid
settler and can then be recirculated to the reactor. Gasoline or alkylate with a very high octane number
(RON 94 - 97) is recovered in the separation section. Before storage the alkylate undergoes potash
treatment to neutralize any traces of HF that may have been entrained.
Considerable isobutane recycle to the reactor is necessary to minimize undesirable olefin

polymerization reactions that would produce compounds heavier than gasoline.
The normal butane which is charged with the FCC C4 fraction and which is not affected by the
alkylation reaction is also separated and routed to LPG storage.
The incentive of the alkylation unit as a complementary unit to FCC is to improve octane numbers
of gasoline bases which are generated from FCC complex and specifically Motor Octane Number. In
parallel, alkylation unit allows to increase gasoline bases production, as shown below:
EXAMPLE OF GASOLINE YIELD INCENTIVE

FROM AN ALKYLATION UNIT
Isobutane
10
ALKY. RON 94 - 97
FEED C4 cut MON 92 - 95 To
F.C.C. gasoline
FCC gasoline pool
100 60
RON 92 - 93
D PCD 338 B
50 MON 79 - 80
Alkylation Unit Capacity in the world reached 84 million tons in 1997, including more than 50 million
tons in the US and 8 million tons in West Europe.
b - MTBE or ETBE manufacture
MTBE and ETBE are manufactured with two components:
- an alcohol: methanol (CH3OH) produced from gases, petroleum cuts or coal, or ethanol
from fermentation
- isobutene (C 4H 6) originated from:
• FCC C 4 cut (about 10% isobutene)

• steam cracker C 4 cut after butadiene extraction (50% isobutene)
• isobutane dehydrogenation
• tertio butyl alcohol (TBA) dehydratation

K26
In refineries, their implementation scheme is the following:
PROCESS
FEEDS MTBE or ETBE PRODUCTS

UNIT
C4 cut
with isobutene C4 to storage
Selective chemical reaction
• FCC C4 cut
• SC C4 cut Methanol + isobutene MTBE
Ethanol + isobutene ETBE
MTBE
or
METHANOL ETBE
(industrial alcohol) Liquid phase reaction
to gasoline
or
ETHANOL - Low temperature ≅ 80°C
- Medium pressure ≅ 20 bar
D PCD 339 B
(alcohol from fermentation)
- Catalyst: acid resins
MTBE, ETBE, TAME production capacities increased very rapidly due to the unleaded gasoline
outburst. Recent environmental constraints in USA may limitor reverse their development.
In the United States, the Clean Air Act has led refiners since 1990, to incoporporate oxygenated
compounds to automotive gasolines, especially in those commercialized in highly polluted areas.
The MTBE production in North America exceeds 10 million ton/year. The world-wide production is
about 25 million ton/year.
A future use of the MTBE is however not sure, because of underground water pollution problems faced
in California. This pollution characterised by the strong MTBE odor, is the consequence of leaks and
the MTBE solubility in water. In California, the MTBE use is banned as from 1101/2004.

K27
9- FCC GASOLINES
a - General characteristics
FCC naphtha, which is the main product from the FCC with a yield of about 50% accounts for about
25 to 30% of the European gasoline pool of which the typical current composition (% wt) is given
herebelow:
Butane 4%
MTBE 5%
Light naphtha 1%
Isomerate 6%
Alkylate 6%
Reformate
49%
FCC
D PPC 1105 B
gasoline 29%
The main FCC gasoline characteristics with regard to the finished gasoline pool composition are as
follows:
- moderate octane number, more specifically a 79-80 MON
- high sulfur content taking into account to the new sulfur specifications of finished
gasolines. FCC naphtha sulfur content is between 0.01% (100 ppm wt) and 0.15% (1500
ppm wt) depending upon the sulfur content of the processed feedstock
FCC naphtha is the major contributor of sulfur in the gasoline pool and thus is directly affected by the
reduction of the sulfur content of finished gasolines.
Moreover, 10 to 20% of the sulfur in FCC naphtha is made of mercaptans with odor and
corrosion problems. Therefore a MEROX type sweetening unit is usually required to treat
the FCC naphtha.
- high olefins content: generally above 30% volume which is will above the specifications of
finished gasolines (18% vol max in 2000, 15% vol max in 2005). Also due to the high
cracking temperatures of the FCC, the FCC naphtha may contain diolefins.
b - Typical actions to reduce the sulfur content and to increase the octane number
Several options for directly controlling the FCC naphtha sulfur content are available:
- processing feedstock from low-sulfur crude
- reducing the FCC naphtha end point so that the heaviest part of the FCC naphtha
particularly rich in sulfur is diverted to the distillate pool

K28
• Split and upgrade the FCC "heart cut" gasoline
This is due to the fact that the octane numbers of the hydrocarbons of the full-range FCC naphtha have
not the same values throughout the 20°C-210°C boiling point range.
20°C C
5
RON - MON
The “heart cut”, essentially C7 and C8
Light gasoline + hydrocarbons in the 85-90°C/125-130°C
boiling range, has a lower octane number
85°C than the light and heavy gasolines.
RON - MON
"Heart-cut" gasoline This intermediate cut can be separated
- by distillation and then be properly
125°C hydrotreated to remove the impurities
before being fed to the catalytic reformer
RON - MON after blending with straight-run heavy
170°C
Heavy gasoline naphtha.
+
D PCD 340 B
210°C
C
11
The processing scheme is shown hereafter:
TREATMENT OF "HEART-CUT" FCC GASOLINE
FCC light gasoline
desulfurized
DISTILLATION HDT Heart-cut denitrogenized
FCC FCC gasoline hydrogenated
gasoline heart-cut
FCC heavy gasoline
Straight-run Catalytic To gasoline

heavy naphtha reforming pool
D PCD 341 B
As shown in the above scheme, the heaviest part of the FCC naphtha, rich in sulfur can be
blended in the distillate pool which contributes to reduce the sulfur content of the finished gasoline.

K29
c - Adaptation to new specification
However, with the stringent new specifications of sulfur in gasolines (10 ppm wt 1101/2009)
further solutions have to be investigated such as:
- FCC feed hydrotreating (pretreating)

- desulfurization of the FCC naphtha
FCC feed hydrotreating
Hydrotreating the feed directly with possibly a mild conversion (mild hydrocracking or MHC) to
increase the distillate production has the following advantages:
- increased conversion to naphtha and LPG
- SOx emissions reduction from the FCC
- large reduction of the sulfur content of the FCC naphtha allowing to meet the new gasoline
specifications if the FCC feed pretreatment is deep enough
The olefins content of the FCC naphtha remains however unchanged. To be deep enough, the
hydrotreating must be under high pressure, which with the additional hydrogen consumption, raises the
cost of installing and operating the feed pretreating unit.
FCC naphtha desulfurization
The desulfurization is done by hydrotreating. However the sulfur removal must be done with a
minimum of octane loss due to the hydrogenation of the olefins which have a fair octane number.
The French Institute of Petroleum (IFP) has developed and commercialized the proprietary
hydrotreating processes PRIME G and PRIME G + which can be applied to part or whole of the FCC
naphtha according to the sulfur pool level of the finished gasoline.
• Hydrodesulfurization of the heavy cracked naphtha only
PRIME G
20-125°C light naphtha Extractive To gasoline
sweetening pool
Disulfides
Full range • Mercaptans conversion to disulfides
cracked Disulfurised
naphtha Hydrodesulfurization
gasoline to
Prime G
gasoline pool
D PCD 2528 C
H2
Heavy naphtha 125°C+ • Heavy naphtha desulfurisation
This first solution removes selectively the sulfur from the cut with the highest sulfur content. More than
60% of the sulfur of the full range cracked naphtha is in the heavy naphtha. The extractive sweetening
of the light naphtha removes as well some sulfur from it.
Overall a sulfur level below 150 ppm can be achieved through this scheme.

K30
• Hydrotreating of the FCC naphtha and hydrodesulfurization of the heavy cracked naphtha
PRIME G+ Light naphtha

H2
Full range
cracked Hydrotreating Very low
Hydrodesulfurization
naphtha sulfur
• Diolefins hydrogenation Prime G+
FCC
• Light naphtha sulfur elimi- gasoline
D PCD 2529 B
nates by formation of Heavy
H2
sulfur compounds Heavy naphtha
• Heavy naphtha desulfuration
• Minimum olefins saturation
In this second solution, in a first step the diolefins are hydrogenated, the mercaptans are eliminated
and the olefins are isomerized. These is no need to sweeten the light gasoline. The heavy naphtha is
then desulfurized selectively with minimum olefin saturation and octane loss. This scheme allows the
meet the 10 ppm wt S for the finished gasolines produced by the refinery.

K31
V- CONVERSION OF HEAVY FEEDS BY HYDROCRACKING
1- VACUUM GAS OILS HYDROCRACKING
a - Product yields and qualities
In addition to the cracking process itself, hydrocracking processes purify the products by removing
virtually all impurities such as sulfur and nitrogen and the cracked molecules are saturated by
hydrogen. Further, operation with considerable excess hydrogen prevents coke formation on the
catalysts.
The typical yield structure is illustrated below.
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
It shows that:
- the process consumes a large amount of hydrogen (2 to 3% weight of the feed) which
means that a hydrogen production unit is required
- products are very high quality because they are rich in saturated paraffinic and
naphthenic compounds and contain very few impurities
- conversion is complete which implies that unconverted heavy products are recycled to the
cracking zone;

K32
With respect to product quality:
- light gasoline has a relatively high octane number due to its high isoparaffin content
- heavy gasoline is rich in naphthenes and constitutes an excellent catalytic reforming

feedstock
- the kerosene and gas oil cuts constitute both very high quality jet fuel (good low
temperature operability and low aromatic content) and diesel fuel (good low temperature
operability and high cetane number)
- the unit also produces saturated LPG and a gas containing large amounts of H2S and also
some ammonia (NH3)
In addition, the process offers some flexibility in the range of products. For instance, production may
be oriented to gasoline or to intermediate products according to market demand.
b - The hydrocracker complex
The scheme below shows how the hydrocracker is integrated within the refining scheme. It illustrates
the need firstly for vacuum distillation to prepare the feed which should not contain metal impurities,
and secondly for a hydrogen production unit. Two processes are used for this purpose - steam
reforming which produces hydrogen from light hydrocarbons, and partial oxidation which achieves
the same result using bitumen or heavy residues, but at much higher cost.
HYDROCRACKER COMPLEX Sulfur
CLAUS UNIT Fuel gas

(Amine washing)
Steam
Propane
HYDROGEN
HYDROGEN
PRODUCTION Butane
UNIT HYDROCRACKER Light
Gas Steam reforming 2.5 gasoline
light Reaction Heavy
hydrocarbons 350 - 400°C gasoline
160 - 180 bar to reformer
100
VACUUM KEROSENE
Separation
Distillates
(Vacuum gas oil) GAS OIL
DISTILLATION
Atmospheric
residue Recycle (non-cracked products)
D PCD 344 C
Vacuum
residue

K33
The gases produced by the hydrocracker contain a large amount of H2S and have to be treated in a
sulfur removal unit. In spite of the severe cracking conditions a large proportion of the feed (30 - 40%)
is not converted and the heavy bottom product, called recycle, is returned to the reaction section until it
is totally eliminated.
c - Distillate hydrocracking process
The process requirements are as follows:
- Temperature in the 350-400°C range. It should be limited to avoid coking the catalyst.
- Pressure between 150 and 200 bar to obtain the very high partial hydrogen pressure
required for hydrogenation and cracking reactions.
- exothermic chemical reactions which require reactors with several catalyst beds and cold
hydrogen quench.
The operation of the unit is shown in Figure 7. It illustrates how the feed is mixed with hydrogen and
then treated in two successive reactors.
HYDROCRACKING REACTIONS
- Hydrotreatment of the feed is performed in the first reactor or REFINING REACTOR. Sulfur
and nitrogen are removed and unsaturated products are hydrogenated. It operates with a
hydrotreatment type catalyst suited to heavy feeds that is very effective in removing
nitrogen.
- Cracking of the purified feed and the recycle is performed in the second reactor or
CONVERSION REACTOR. It operates with a dual-purpose catalyst that has both ACID and
HYDROGENATING functions. Acidity is generally provided by a silica-alumina carrier in the
form of a zeolite on which metal sulfides are generally deposited.
These two catalysts are very sensitive to metal poisoning so all the necessary precautions should be
taken at the feed preparation stage.
On leaving the reaction section, the conversion reactor effluents are cooled and then separated.
- Hydrogen-rich gas is recovered in the HP separator drum (170 bar) and is then mixed with
make-up hydrogen and recycled to the reactors.
- Acid gas is released in the LP separator drum (20 bar).
- C 4 gases are separated from gasoline and heavier components in the debutanizer column.
- Gasoline, the kerosene cut, the gas oil cut and the residue or non-converted recycle are
recovered in atmospheric and vacuum distillation columns. The bottom product is then
recycled to the conversion reactor.

K34
2- HYDROGEN PRODUCTION UNIT (figure 8)

a - Steam reforming
The principle of this process is to make the LIGHT HYDROCARBONS react chemically with steam in
accordance with the following chemical reaction (the example is that of methane)
STEAM REFORMING REACTION
CH4 + H2O CO + 3H2
– reaction conditions
• temperature in the 800°C range
• pressure in the 20 bar range
• substantial heat input (endothermic reaction)
• specific catalysts
The reaction takes place under very severe conditions in a furnace as shown in the schematic in
Figure 9.
At the same time as the steam reforming reaction another reaction takes place, that of CO
conversion, also called the Shift reaction.
CO SHIFT CONVERSION REACTION
CO + H2O CO 2 + H2
– reaction conditions
• reaction partially performed in the high temperature

furnace
• exothermic reaction favorized by low temperature
• specific catalyst
The second reaction continues downstream of the furnace after cooling of the effluents and increases
hydrogen production. This is the function of the CO catalytic conversion section. The final gaseous
mixture is often treated in a separation unit using molecular sieves.
This process uses solid zeolites that retain CO 2 and CH4 but not hydrogen.
There are two alternate cycles. In the adsorption cycle the zeolites adsorb the gases to purify the
hydrogen and in the desorption cycle the zeolites are regenerated. The adsorption and desorption
cycles are performed at different pressures and the process is known as pressure swing absorption
or P.S.A.
The purified hydrogen (purity of > 99%) generally leaves the unit at low pressure and has to be
compressed to feed the hydrocracker.

K35
PSA SEPARATION
Gas to be Pure H2
treated
PSA
H2
CH4 CH4
CO2
D PCD 2124 A
CO2, CO CO
b - Partial oxidation (POX)

Gasification or partial oxidation process produces a synthesis gas from heavy petroleum residues
and is a useful mean of eliminating the latter.
Synthesis gas is essentially composed of hydrogen and carbon monoxyde after impurities absorption
(mainly H2 S). It can be used to produce energy (electricity and steam) but it can also be a source of
hydrogen.
The process consists in implementing the controlled combustion of the heavy hydrocarbons in a
special burner with pure oxygen in the presence of steam according to the following reaction.
PARTIAL OXIDATION REACTION

x y
C x H y + O 2 → CO + H 2
2 2
• combustion by pure oxygen in the presence of steam
• temperature: 1300 to 1450°C
• pressure: 70 bar
• production of carbon, ashes and metals which are
separated
The gases generated by combustion are washed with water and routed to a CO conversion section
similar to that found in steam reforming units.
CO CONVERSION REACTION
CO + H2O CO2 + H2
• temperature: approx. 300°C

• pressure: 65-70 bar
• specific catalyst
The gaseous mixture is then treated to remove H2S and CO2 and the last step is PSA separation
which produces 99.5% pure hydrogen at high pressure. A simplified version of the process scheme
can be seen in Figure 10.
It should be noted that this process is a valuable solution to eliminate residues: vacuum residues,
cracked residues, asphalts, etc. rich in metals, sulfur and other impurities and that it allows to convert
them in clean fuel gas.

K36
Several projects, called IGCC (Integrated Gasification Combined Cycle) are underway in differents
refineries. Total investments are in the range of 500 - 1,000 millions USD.
IGCC project scheme is shown below:
GASIFICATION - DIFFERENT OPTIONS
Other air
constituents
Air
Air
separation
Oxygen
Synthesis gas ELECTRICITY

Cogeneration
Steam Gasification STEAM
CO + H2
or
Partial Steam
CO conversion
oxidation
an hydrogen HYDROGEN
purification
Petroleum
residues
(or any Ashes Sulfur
petroleum
D PCD 345 C
cut)
In case of 800 000 t/year residue treatment, the table below gives following possible productions
according to selection:
1 2 3 4
270,000
Synthesis gas
to
CO + H2 (Nm3 /h) 300,000
Hydrogen (Nm 3 /h) 210,000 to

130,000
260,000
Cogeneration
Electricity 210 MW 150 MW
Steam 350 t/h 350 t/h

K37
3- VACUUM RESIDUE HYDROTREATMENT AND HYDROCONVERSION
a - Process objectives
These processes are often referred to as deep upgrading processes The heavy feedstocks contain
large amounts of asphaltenes, metals, sulfur and other impurities and have to be transformed into
purified cuts that are converted to a greater or lesser extent and can be processed and upgraded in
conventional manufacturing units.
The chief problem with these processes is not the actual conversion but the Hydrodemetallization
(HDM) of the residues. The degree of difficulty depends on the nature of the original crude oil and the
characteristics of the residues processed.
The properties of the hydrotreatment catalysts used enable hydrodesulfurization (HDS) to be

performed simultaneously with HDM. If the operation involves only HDM + HDS and not conversion, it
produces an excellent basestock for manufacturing low sulfur fuel oil. The purified heavy cuts
produced can also be used as feedstock for the refinery's conventional conversion units.
Sour gas
Vacuum
residue
HYDROTREATMENT Light cuts
HDM
H2
HDS Heavy cuts to:
D PCD 346 B
- conventional conversion
- LS fuel oil
The initial hydrotreatment operation may be followed by hydroconversion, that is hydrocracking of the
heavy cuts produced. This operation implies the use of specific catalysts and produces a range of
product streams that are integrated into the refining scheme. With this type of process the rate of
conversion of the feed into lighter products may be as high as 60-70%.
Sour gas
Vacuum
residue HYDROTREATMENT Light cuts
HDM - HDS
H2 + Intermediate cuts
D PCD 347 B
PARTIAL CONVERSION
BY HYDROCRACKING Heavy cuts
Whatever the objective, the chief problem in this type of operation is the metal content of the feed.
Moreover it is the parameter that determines the type of technology to be used.
b - Main types of process
All vacuum residue hydrotreatment and hydroconversion processes are characterized by severe
operating conditions:
- temperature 400°C
- pressure 200 bar
- large amounts of catalyst (100 to 300 tons to process 100 t/h of feed)

K38
They differ in the way in which the catalyst is used in the reactor as a function of the metal content of
the feed. The most commonly used techniques are:
• FIXED BED PROCESSES (low to medium metal content)
• EBULLIENT BED PROCESSES (high metal content)
• MOVING BED PROCESSES (high metal content)
FIXED BED PROCESSES
In this type of process the catalyst is placed in several reactors in series. If the feed requires
substantial demetallisation the first reactor that the feed encounters may be duplicated. This enables
operation by cycle, with one reactor operating while the other is shut down, emptied and refilled with
fresh catalyst.
This system allows continuous operation and is used in the HYVAHL process. The process flow
scheme is shown in Figure 10. An example of the results, based on a Kirkuk residue, is shown below.
HYVAHL
%
0
Gas – H2S
10 Gasoline
20
Kerosene/Gas oil
30
Kirkuk
FEEDSTOCK
vacuum 40
PRODUCTS
residue 50
Distillate/VGO
S% = 5.23
Metals = 190 g/t 60
70
80
Residue
90
D PCD 348 B
100 102
Conversion of the feed exceeds 60% and yields relatively high quality products. Different units
operates in the USA and South Korea.

K39
EBULLIENT BED PROCESSES
This type of process is suited to heavy feeds with a higher metal content. The catalyst is maintained in
suspension in a liquid phase based on the following principle.
FRESH
CATALYST EFFLUENTS
MAKE-UP
Catalyst
in suspension
FEED
+ HYDROGEN
Recirculation
D PCD 349 B
pump SPENT
CATALYST
Several reactors are used in series. They are large in size, with a diameter of up to 4.5 m and a height
of up to 30 m.
These processes can be used to process feeds with a very high metal content without risk of plugging
and without loss of catalyst activity since the catalyst can be removed from the reactor and replaced by
fresh catalyst. The rate of conversion is high but product quality is lower than that achieved with fixed
bed processes.
The two main processes that use this technology are LC Fining developed by Lummus and H-Oil by
Hydrocarbon Research Inc. (HRI).
The flow scheme of the LC Fining process is shown in Figure 12.

K40
Fresh
MOVING BED PROCESSES catalyst
FEED
+
This type of process is suited to feeds with
a high metal content but is not yet much HYDROGEN
used. It involves catalyst movement within
the reactors.
Operation is continuous as in the

previously described processes, with
removal of the spent catalyst and
replacement by fresh catalyst.
The scheme of the bunker reactor used in

the Shell HYCON process is shown
opposite.
In addition to the moving bed reactor, the

conversion process also includes fixed
bed reactors as shown in Figure 13. A
typical example of the results obtained is
shown below. EFFLUENTS
D PCD 350 B
Spent
catalyst
HYCON
%
0
Gas + gasoline
10
20 Kerosene/Gas oil +
30
VACUUM
FEEDSTOCK
PRODUCTS
40
RESIDUE 50 Distillate/VGO +
60
560°C+ CUT
70
80
+
Residue
D PCD 351 B
90
100 102.3
The quality of the products obtained is relatively high. The highest yield is a heavy distillate (VGO type),
which constitutes an excellent FCC feedstock, and the residue can be used to produce LS fuel oil.

14 - K Overview Conversion

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Refining-Petrochemicals-Chemicals-Engineering

S.C. PETROTEL-LUKOIL S.A.

REFINING PROCESSES AND PETROLEUM PRODUCTS

K - OVERVIEW OF CONVERSION PROCESSES

I - ORIGINS AND CHARACTERISTICS OF CONVERSION UNIT FEEDS .................................. 2

II - HEAVY FEED CONVERSION PROCESSES ........................................................................... 6

1 - Cracking techniques of heavy hydrocarbons ............................................................................... 6

III - THERMAL CRACKING PROCESSES .................................................................................... 10

1 - Visbreaking of vacuum residue .................................................................................................. 10

IV - HEAVY FEED CONVERSION BY CATALYTIC CRACKING WITHOUT HYDROGEN .......... 16

V - CONVERSION OF HEAVY FEEDS BY HYDROCRACKING.................................................. 31

RA CON - 00012_A_A - Rev. 12 11/05/2007

 2007 ENSPM Formation Industrie - IFP Training

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

I- ORIGINS AND CHARACTERISTICS OF CONVERSION UNIT FEEDS

CRUDE ATMOSPHERIC KEROSENE

These feeds consist chiefly of:

- atmospheric residue which is more or less equivalent to a 380°C+ cut

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

PRINCIPLE OF DEASPHALTING Deasphalting solvent

Vacuum residue Oil

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

ARABIAN LIGHT CRUDE

Atmospheric VGO/ VGO/

15 0.962 0.912 0.943 1.031 0.973 >1

wt% S 3.1 2.2 2.8 4.2 3.65 6.2

• High sulfur and nitrogen content on HS crude

• High Conradson carbon residue

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

TIA JUANA HEAVY

15 0.962 0.995 1.017

wt% S 3.1 4.4 3.18

Conradson carbon wt% 10.8 15.3 15.5

Asphaltenes wt % 2.6 7.0 7.2

Ni + V (wt ppm) 42 125 550

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

II - HEAVY FEED CONVERSION PROCESSES

1- CRACKING TECHNIQUES OF HEAVY HYDROCARBONS

Three main techniques can be distinguished:

Cracking techniques Parameters

THERMAL CRACKING Temperature

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

GASOLINE - GAS OIL - VGO

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

2- HEAVY FEED CRACKING PROCESSES

THERMAL PROCESS • Low-selectivity processes: producting a lot of gas

• Poor quality products, rich in olefins and diolefins

CATALYTIC CRACKING • More selective cracking

HYDROCRACKING • Very high cracking selectivity

• Vacuum distillate Hydrocracking • No coke production thanks to hydrogen

• Vacuum residue Hydrotreating and • High hydrogen consumption requiring an hydrogen

HYCON (SHELL) residues with appropriate complex technologies

00012_A_A © 2007 ENSPM Formation Industrie - IFP Training

North America 290.0 10.6 94..3 77.9 18.8

Latin America 76.6 32.2 15.6 4.1 1.3

Western Europe 103.6 75.4 15.7 31.1 6.0

Africa 9.3 4.0 0.8 1.3 0.6

Middle East 13.7 17.3 3.9 25.1 13.4

Japan 38.9 – 4.0 6.5 21.5

Others Asia-Oceania 83.7 19.2 21.1 25.7 12.8

Total 615.8 158.7 155.4 171.7 74.4

Source: Oil and Gas Journal - December 22, 1997

Atmospheric Vacuum Conversion capacity/