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ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS

Block 2, Forum 10 paper


ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION
OF OLEFINS
Derek Lawler, Stone & Webster
Warren Letzsch, Stone & Webster
Fakhri Dhaidan, Stone & Webster
Abstract:
Ethylene (20 Wt%) and Propylene (25 wt%) from Fuel Oil is now a reality using advanced
Fluid Catalytic Cracking Unit (FCCU) technology. Integrated sites with FCCU and Steam
Cracking maximise the conversion of crude oil to petrochemicals.
This paper describes the advances made in:
FCCU, (Fluid Catalytic Cracking Unit)
Steam Cracking,
Site Integration,
Types of feed that are suitable for this process,
Preparation of feeds
Shaw Stone & Webster in combination with Total, Axens and Sinopec have developed world
leading technology for the production of Olefins
Introduction
Ethylene and Propylene are light olefins that form the primary building blocks for many
modern plastic materials including polymers such as Polyethylene and Polypropylene. The
market for plastics and polymers is forecast to grow at or ahead of world GDP. Oil and Gas
are the primary raw materials to make olefins and converting them into plastics is an
economic alternative to producing road fuels. Natural gas contains Ethane and a number of
companies, particularly in the Middle East, are currently investing in significant additional
capacity to convert Ethane to Ethylene. Crude Oil and Condensate are the primary sources of
Naphtha that is a traditional feed for conversion to Ethylene and Propylene. Fuel Oil in oil
refineries is converted into Propylene using Fluid Catalytic Cracking Units (FCCU). There is a
trend to use lower cost Ethane and Fuel Oil as feeds to produce olefins as Naphtha is
increasingly expensive. The continued growth in the production of olefins and the
diversification of feedstocks is supported by technology advances in Fluid Catalytic Cracking
Units (FCCU) and Steam Cracking (SC).
Background
Currently the most widespread method of producing olefins uses Steam Cracker technology
where paraffins are heated inside tubes in a furnace to above 800 deg C in the presence of
steam where they thermally crack.
There are two main types of Steam Cracker, Naphtha and Ethane:
Naphtha is a mixture of hydrocarbons in the C3 to C10 range and is a by-product of
oil refining or is sourced from Condensate from gas and oil fields. Naphtha cracks to
produce olefins and aromatics. Naphtha is also in demand to produce Gasoline and
the price of Naphtha is closely linked to that of Gasoline. There are times when it is
not economic to crack Naphtha.
Ethane is co-produced with LNG and as such its availability is growing. Converting
Ethane to Ethylene is a cost effective upgrade route that is being adopted in the
Middle East where several new large Ethane Steam Cracker projects are being
implemented. The product of cracking Ethane is predominantly Ethylene not
Propylene
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
Increased Ethylene demand is forecast to be met from cracking Ethane, but this will not meet
the forecast demand for Propylene. There are several technologies other than Naphtha
cracking for producing Propylene including Propane De-hydrogenation but the most common
production route is Fluid Catalytic Cracking.
Approximately one third of the worlds propylene for chemicals is currently produced as a by-
product in Fluid Catalytic Cracking (FCC) units in oil refineries. In this process heavy fuel oil is
suitably prepared and cracked on a circulating catalyst at above 520 degC. This produces a
range of cracked components including Gasoline and Propylene. Advances in FCC
technology have allowed greater flexibility to make increased quantities of Propylene. Recent
advances allow FCC Units to be designed and built to produce 25% Propylene from suitable
feeds. Further advances show that the technology can produce both Propylene and 20%
Ethylene from Fuel Oil.
1. FCCU ADVANCES
1.1 OVERVIEW OF FLUID CATALYTIC CRACKING
FCC Flow Scheme
Hot Catalyst Flows under gravity from the Regenerator to the Riser
Feed and Steam are Injected in the Riser
Feed Vaporizes and Cracks and Lifts Catalyst Into the Reactor Separator
At the Top of the Riser the Products and Catalyst are Separated
Product Vapours go to a Fractionator
Catalyst Falls into a Steam Stripper
Spent Catalyst Returns to the Regenerator
Regenerator Burns Coke on Catalyst and Heats it to approximately 720C
Catalyst Re-circulates at 30 to 100 Tonnes per Minute
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
FCCU Schematic
FCCU was developed in the 1930s and 40s to produce high octane aviation gasoline and is
now a standard process in oil refineries with over three hundred units throughout the world.
The primary product from FCC is gasoline but the FCC is used to make a range of products
from Diesel to Ethylene. The process uses a circulating catalyst that is fine enough to be
fluidized. The catalyst particle sizes in an FCCU are like a very fine sand and typically range
from 20 to 100 microns with an average size around 70 microns. FCCUs have been built with
a capacity range from 60 to 600 M3/H. The process is continuous with the catalyst being
regenerated as part of the process. The feed for most FCC units is Vacuum Gasoil that is
produced from Fuel Oil by Vacuum Distillation. Recently the trend is to crack whole Fuel Oils
in Residue FCC Units to convert the bottom of the barrel into higher value components.
Developments in these technologies by the licensors and catalyst companies make this an
economic way to upgrade fuel oil residues.
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
S&W / Axens Residue FCC with Two Stage Regenerator
By adjusting the operating parameters and the catalyst FCCU technology produces a wide
range of products.
Products and Operating Conditions
Reactor Temperature Catalyst Properties
Gasoline/Diesel 510 - 520C Mod ACT
Gasoline 520 - 545C High. ACT
Propylene 525 - 565C Low ACT
Pentasil
Petrochemicals 540 - 650C Low ACT
Modified Activity
Second Stage
Regenerator
Riser Separator RS
First Stage
Regenerator
Reactor / Disengager
Stripper / Packing
Reactor Riser
Feed Injection
Withdrawal Well
Combustion Air Ring
Combustion Air Ring
Lift Air
MTC Injection
Coupled to cyclones
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
1.2 FEED INJECTION
Feed for the FCCU is pumped to the feed injectors, atomised with steam and injected into the
hot catalyst. The Feed is typically at 200 deg C and the catalyst is typically at 720 deg C.
Good contact between the feed and the catalyst in the mix-zone is essential for efficient
cracking. The feed vaporizes and cracks on the hot catalyst. The steam and vaporized feed
lift the catalyst up the riser. Residence time in the riser is 1 3 seconds.
There are a number of different technologies for Feed Injection that aim to provide good
mixing with the catalyst to vaporize the feed. One of the most effective technologies uses a
well developed design that is more commonly applied to make artificial snow. In the snow-
maker, water is injected through a shaped orifice onto a target bolt where it splashes; air
under pressure is blown across the bolt and shears the water into very fine filaments that are
atomised by the tip to form a fine mist that blows into the cold atmosphere to make artificial
snow. The droplet size is determined by the ratio of water to air, the velocity of the water and
air, the angle of incidence and by the physical properties, density, surface tension and
viscosity. The relationship is described by Mugele and Evans
1
and applied extensively by
Spray Systems Inc. For the FCCU the liquid is oil and the gas is steam.
Stone & Webster Feed Injector
There are over seventy FCCUs using these feed nozzles in operation throughout the world
giving trouble free operation. Several nozzles have been in service for ten years without
replacement or loss of performance.
FCC catalyst is highly porous with a large surface area. Only vapour molecules are able to
enter the pores of the catalyst to crack on the active sites. Fuel Oil requires high temperature
and low partial pressure to vaporize the heavy molecules in it. The excellent performance of
the S&W feed injector is because the droplet size of the oil is very small, similar to the particle
size of the catalyst giving excellent heat and mass transfer and the steam lowers the partial
pressure.
FCC licensors continue to develop Feed Injection technology because it is the heart of the
FCC process. Recent developments for the highly successful S&W Feed Injectors are to
improve the shape of the slot and to reduce fabrication costs.
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
1.3 MIX-ZONE TEMPERATURE CONTROL (MTC)
The mix-zone is an area of the riser just after the feed injection. In an FCCU during normal
operation the catalyst circulates in a ratio of 7:1 with the feed, for every tonne of feed there
will be approximately seven tonnes of circulating catalyst. The catalyst from the regenerator is
at approximately 700 - 720
O
C. To ensure good vaporization of heavy feed it is important to
have a high temperature in the mix-zone but this may lead to more cracking and light
products than are required. To achieve a high mix-zone temperature and lower riser
temperature Stone & Webster licenses a technology that quenches the catalyst and products
in the riser. This is called mix-zone temperature control and has been successfully
implemented in FCCUs where there is a requirement to run more residue feeds.
S&W / Axens MTC Technology
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
1.4 RISER TERMINATION
When the feed meets the catalyst it vaporizes and the cracking reactions are fast, producing
intermediate cracked compounds in the vapour phase. These intermediate compounds enter
the pores of the catalyst and are further cracked to Gasoline and Propylene. If the vapour
remains in contact with the catalyst it is further cracked to coke and fuel gas.
In a modern FCCU all the valuable cracking reactions take place in the riser and it is
important to rapidly separate the products from the catalyst at the end of the riser. The
principle separating mechanism used to disengage the solid catalyst from the vapour product
uses some form of ballistic or centrifugal force such as a cyclone. The product vapours and
steam leave the reactor through second stage cyclones that remove the remaining catalyst.
The catalyst drops to the bottom of the reactor into the stripper.
Riser Termination Devices have evolved from a basic tee to more sophisticated proprietary
disengaging devices that all try to achieve the following:
Rapid Separation of Products and Catalyst
Compact Design
Easy Start-up and Operation
Efficient Catalyst Removal
Reduces Dry Gas
Reduces Coke
Sealed or Open Operation
Stone & Webster RS
2
Separator
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
1.5 PACKED STRIPPER
The stripper removes hydrocarbons from the catalyst by stripping it with steam before it
returns to the Regenerator. In the reactor stripper the ratio of catalyst to oil is very high and
prolonged contact results in all the hydrocarbons cracking to coke and gas. FCC Coke
consists of heavy aromatic and multi ring compounds. A measure of the effectiveness of a
stripper is the Hydrogen on Coke and this is reduced by good stripping or by excessive
contact time.
To be effective in stripping hydrocarbons from the catalyst, the steam has to be well
dispersed. A steam ring with nozzles jets the steam into the catalyst and is very effective in
stripping. Within 0.5m of the steam ring the steam velocity reduces and bubbles of steam and
hydrocarbon form. These bubbles have to rise against the catalyst descending. The larger the
bubble the faster it ascends and the less effective it is in stripping. In traditional disc and
donut or shed deck stripper designs, part of the available cross section is blocked. At these
constrictions the velocity of the descending catalyst increases and the size of steam bubble
able to flow against it has to increase.
Total of France developed the use of packing in strippers in the 1990s. Koch-Glitsch further
developed the materials and design and its use has been widely licensed for use in revamps
and new FCC units. In a Packed Stripper 95% the whole area is open to flow and the
stripping is more effective. Increasing the flow area is particularly valuable in revamping
existing units to increase catalyst circulation and capacity.
Total / Stone & Webster / Koch-Glitsch Stripper Packing
.
1.6 COLD WALL CONSTRUCTION
Cold Wall construction allows the use of Carbon Steel for the construction of the FCC. The
internals of the vessels and transfer lines are covered in insulating and abrasion resistant
refractory. Advances in refractory and anchoring technologies have made this design very
reliable. The move to Cold Wall design removes metallurgical limits from the operating
window of the FCC and it is these advances that Stone & Webster has developed to make
high temperature, high Olefins FCC a reality.
Robust Construction
Improved Operation
Reduces Coke to the
Regenerator
Good Start-up Characteristics
Minimises Steam Usage
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
High Olefins FCC Technology increases the yields of Propylene and Ethylene from FCCs.
These valuable products are then recovered and purified using the techniques developed in
Steam Cracking.
2.0 HIGH OLEFINS FCC
FCCUs currently produce approximately 30% of the Propylene used in the Chemical Industry.
This figure is likely to increase as Refiners with FCCUs recover more Propylene from their
existing units and build new FCCU that maximise Propylene production. FCC produces
Propylene by cracking heavy molecules to light gasoline molecules and then cracking these
molecules further to Propylene.
Conventional FCC catalyst produces Propylene rather than Ethylene because the active
catalyst sites are Bronsted Acid sites that promote proton addition reactions resulting in
carbenium ions and Beta Scission. The fundamental mechanism of catalytic cracking, -
scission, leads to high yields of C
3
and C
4
olefins. This is because the hydrocarbon molecule
in the presence of an acid site tends to form a carbenium ion at the secondary or tertiary
carbon atom. The cracking actually occurs at the position relative to the carbenium ion.
This type of a reaction mechanism always results in the production of a C
3
or C
4
olefin. In
addition the process is operated such as to minimize secondary hydrogen transfer reactions
which compromise the olefin yield.
RIPP in China has recently developed catalysts that produce Ethylene. These catalysts have
active Lewis acid sites that promote electron removal and the formation of free radicals.
Details of the catalyst development are given by Wang Xieqing et al
2
.
By utilising the properties of these catalysts and the advances in FCC design S&W can offer
more opportunities to produce light olefins from heavy feeds.
2.1 ZSM-5 FCC ADDITIVE
A form of zeolite, named ZSM-5 by its licensors at Mobil, is the most widely used technology
to increase the yield of Propylene from existing FCC units. When molecules of FCC Naphtha
enter the zeolite structure they are preferentially cracked to Propylene and Butylene by a
catalytic action initiated the Bronsted Acid sites. Because Paraffins are cracked by ZSM-5 it
also has an advantage as it increases the Octane of FCC Gasoline.
The normal yield of Propylene in FCCs is approximately 3% Using ZSM-5 and temperatures
up to 540 C and can increase Propylene yield to approximately 6%.
2.2 DEEP CATALYTIC CRACKING (DCC)
RIPP in China produce an FCC catalyst that contains a Pentasil zeolite they have developed.
This catalyst operates up to temperatures up to 565 C and can produce a yield of Propylene
of 15% to 20%. This catalyst is used in a successful development of the FCC called DCC.
DCC uses well proven FCC technology and applies it to the different operating conditions
required for the production of Propylene. This includes more steam and lower operating
pressures. DCC has been in successful operation for several years at units in China and in
Thailand. A new 92,000 Barrel Per Day DCC unit is licensed for construction in Saudi Arabia
and will produce approximately 900,000 Tonnes per year of Propylene.
2.3 CATALYTIC PYROLYSIS (CPP)
RIPP has developed a new catalyst and demonstrated it in a unit that operates at up to 650
C. A new commercial unit for his process is under construction in China. As well as Bronsted
Acid sites, the new catalyst contains Lewis Acid sites that produce Ethylene. The CPP can
produce a mix of Ethylene and Propylene and this provides a route to produce light olefins
from Fuel Oil. The production from a CPP unit compares well to that of a Steam Cracker.
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
CPP is essentially a Chemicals Unit because the recovery systems required to purify the
Propylene and Ethylene are those required on a Steam Cracker. The light olefins are made
by cracking the Gasoline components in the FCC. The paraffins and olefins crack and leave a
Naphtha that is highly aromatic.
Table 2.1 Comparative Yields
Cracking to produce light olefins requires higher temperatures, lower pressures and more
steam.
Reactor Temp. C
Reactor Pressure, Bar Gauge
Residence Time, Secs
Catalyst to Oil Ratio, wt/wt
Dispersion Steam, wt% Feed
Cracking Environment
FCC
500 - 550
1-3
1-5
4-8
1-3
Riser
DCC
530 - 590
1-2
1-10
10-15
5-30
Riser & Bed
CPP
560 - 670
1
1-3
15-25
30-50
Riser
SC
760 - 870
1
0.1 0.2
-
30 - 80
Coil
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
Table 2.2 Naphtha Compositions
BTX in Naphtha wt% DCC CPP SC
Benzene 1.6 4.6 37.8
Toluene 5.7 16.6 14.9
Xylene 10.0 23.7 2.9
Steam cracking produces an aromatic naphtha rich in Benzene and catalytic cracking
produces an aromatic naphtha rich in Xylene.
3.0 STEAM CRACKING
Steam Cracking is an established technology for converting Paraffins into Olefins. There are
two types of Steam Cracking facility, gas and liquid. A gas cracker converts ethane to
ethylene with few other products. A liquid cracker converts LPG, Naphtha or Gasoil to
Ethylene, Propylene, Naphtha (Pyrolysis Gasoline) and fuel oil.
Stone & Webster Twin Cell Steam Cracking Furnace
Steam Cracking is a thermal cracking process with a free radical mechanism requiring
elevated temperatures of approximately 800
O
C, low pressures and steam. Following the
cracking the products are quenched to prevent unwanted reactions. Ethylene is normally
stored and as a low temperature liquid. Recovery of the Ethylene from lighter gases and
Propylene requires cryogenic techniques that are continuously improving to reduce energy
and equipment costs.
Fresh
Feed
To
Quench
HP Steam
Fuel
Gas
Dilution
Steam
USC Cracking
SLE
Furnace
Preheated
BF Water
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
Significant advances have been made to improve the performance, reliability and
environmental impact of Steam Crackers. There are now single furnaces producing 250,000
TPA of Ethylene and furnaces 50% larger are being planned. Furnace designers continue to
seek improved coil designs to minimize coking and enhance run lengths using advanced
tubing materials including current trials using ceramic tubes. Advanced burner designs
increase efficiency and reduce NOx emissions.
4 SITE INTEGRATION
Integrating an oil refinery with petrochemicals is a proven way to optimize the return on
investment and many of the major oil companies follow this strategy. Integration reduces
overall investment costs because infrastructure and utilities are shared, tankage and transport
are minimized and units are sized to be complementary. Low value streams from the
petrochemical plant such as fuel gas and C4 olefins are valuable intermediates in the refinery
to provide Hydrogen and Alkylate. Low value streams from the refinery such as FCC off-gas
and propylene are suitable as feed streams in the petrochemical plant. Integration can include
a cogeneration facility to generate electricity using low value fuel and co-product streams and
to reduce energy costs.
S&W has evaluated many scenarios and has seen repeatedly that integration of refining and
petrochemicals shows a good return. As well as integrating the refinery and olefins
production, integrating olefin production and the first line derivative products can achieve
optimum recovery, minimise investment costs and achieve high returns. In most scenarios
integrated sites are more profitable than merchant facilities producing polymer grade
monomers for sale.
4.1 Refinery/Olefins Plant Integration
A simple integrated refinery/olefins plant utilises Naphtha from the Crude Distillation Unit as
feed to a Steam Cracker. This configuration is used successfully in North Africa where a
Hydroskimming refinery processes light sweet crude oil to produce Naphtha, Kero, Diesel and
Fuel Oil. In the case of North African crude the Fuel Oil is a Low Sulphur Waxy Residue and
is sold at a premium as a supplementary feed for FCCU. The Naphtha is converted to
Ethylene and Propylene. The Ethylene is converted to Polyethylene and the Propylene is
exported.
A more complex integrated refinery/olefins plant incorporates an FCC that converts part of the
Fuel Oil to Gasoline and Propylene. This configuration is used in Middle Europe. The
Ethylene is converted to Polyethylene and other derivatives such as Ethyl Benzene.
Propylene is typically converted to Polypropylene or Cumene. FCCU gases that contain C2s
and C3s are used to supplement the feed to Steam Crackers. A Spanish refinery has
integrated a Hydrocracker with Naphtha Steam Cracking to produce high quality Diesel and
Chemicals.
In the USA and Europe there are several complexes that are highly integrated and convert
crude oil into range of high value products including Polymers, Chemicals, road fuels and
Lube Oils. Typically these facilities have no fuel oil production because they either convert the
final residue to Coke or to Electricity.
4.2 Revamp of Existing Facilities
There is currently more activity in revamping existing refineries and olefins plants to increase
capacity and yields than there is building grass root units. In developed countries it is easier
to obtain permission to expand and existing facility than it is to build on a new site.
Due to advances in Steam Cracker technology the economics are attractive to replace old
Steam Cracking furnaces with fewer, larger new furnaces capable of cracking a wider range
of liquids. An alternative option that some companies are looking at is the DCC/CPP process
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
to replace old furnaces and take advantage of lower cost feeds. A DCC/CPP unit occupies
approximately the same plot space as two furnaces and utilises the same recovery facilities.
An FCCU is typically a refinery unit that produces Propylene and some Ethylene that can be
converted to polymers and chemicals. There are many existing locations where Refineries,
Petrochemical and Chemical plants are adjacent to each other. Often they are integrated by
interchanging products and the trend is towards more integration.
FCCUs are producing more C2s and C3s.
In countries that are developing their Petrochemical industries the infrastructure and expertise
is often centred on existing refinery facilities.
There is a trend towards mega sites to take advantage of the economies of scale and there
are a series of investment currently taking place to install the largest capacity Steam Crackers
and largest capacity High-Olefin FCCU. As well as separate recent development
Many medium sized refinery/petrochemical sites are looking at modernising and improving
their profitability by processing lower cost feeds.
An ultimate configuration is for a design where Crude Oil is converted completely into
Plastics, Chemicals and Energy.
Light Crude Oil Petrochemical Refinery
L Li ig gh ht t
C Cr ru ud de e
E Et th hy yl le en ne e
P Pr ro op py yl le en ne e
B BT TX X
G Ga as s O Oi il ls s t to o F Fu ue el l
G Ga as s t to o F Fu ue el l
N Na ap ph ht th ha a
A AG GO O
A AT TB B
L Li ig gh ht t
R Re ec cy yc cl le e
C Ca at ta al ly yt ti ic c
R Re es si id d. . F FC CC C
D DC CC C
C CP PP P
P Py yr ro ol ly ys si is s
C Co oi il l
Q QC C
R Re ec co ov ve er ry y
H He ea av vy y
R Re ec cy yc cl le es s
C Cr ru ud de e
D Di is st t n n
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
FEEDSTOCKS
FCCU is a very versatile technology for producing Olefins as it accommodates a wide range
of feeds. As is shown in the Crude to Chemicals refinery, potentially all the Crude Oil is
converted to Chemicals and power.
The FCCU process obtains the heat it requires for the heat of cracking by burning the coke on
the re-circulating catalyst. Feed to the FCCU has to contain material that will form coke and
this is mostly found in heavy residue feeds. It is feasible to process whole crudes through the
FCCU but more typically the residue from the atmospheric crude distillation unit is used as
feed to the FCCU either directly or after being further processed. Crude distillation residue is
traditionally sold as Fuel Oil and so has a relatively low cost as a feedstock.
Traditional FCCUs convert Fuel Oil to gasoline and the technology is well proven. Fuel Oil is a
low cost feedstock and is available in many forms and qualities. The desirable properties for
FCCU are that the Fuel Oil contains a high level of paraffinic compounds that crack and that it
is low in contaminants. Residue from crude oil that is low in metals and contaminants is
used directly as feed for the FCCU. Residues containing high metals are further processed as
described in the next section of this paper.
FCCU concentrates any non-volatile or non-crackable components in the feed on the catalyst.
Contaminants such as metals build up on the catalyst. To keep the catalyst active a portion of
the catalyst is replaced on a continuous basis by purging. An FCCU on low metals feed
typically uses 1-4 Tonne of catalyst a day. An FCCU on high metals feed can use up to 30
Tonnes a day. The spent catalyst is usually returned to the supplier for re-use or safe
disposal. Feedstocks that are high in metals (above 20ppm) use more catalyst to purge the
metals from the system. At levels above 50ppm metals in feed it is no longer economic to
replace so much catalyst.
Many African crude oils such as those from Algeria, Libya and Angola are low enough in
metals to be attractive as feeds for RFCC.
The quantity of metals in the feed determines the feasibility to process the residue without
further processing. The Paraffinicity of the feed determines how much of it will crack to light
olefins. Paraffins and Naphthenes in crude oil will crack to form light Olefins but Aromatics
and Asphaltenes will not crack.
In many cases the crude oils that are low in metals are also low in aromatics and are the most
suitable feeds for RFCC.
Steam Cracker feed has to be low in residue components to minimise coking, Coke is formed
during Steam Cracking but it is not a useful by-product and has to be removed from the
process. A particular advantage of the FCCU is its capability to process heavier feeds than
Steam Cracking and these are typically less expensive.
6 PREPARATION OF FEEDS
Low metal paraffinic residues are ideal feeds for FCCU to produce Olefins. Crude Oils from
Algeria, Angola and Libya as well as China and Vietnam meet these requirements. Other
crude oils such as Arab Light and Arab Heavy are paraffinic but contain too many
contaminants to be economically cracked directly. To process feeds that contain a lot of
metals and asphaltenes the feed has to be treated to remove the contaminants. The primary
technologies used are Atmospheric Reside Hydrotreating, Vacuum Distillation and Solvent
De-Asphalting.
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
Integrated Fuels / Petrochemical Refinery
Atmospheric Residue Hydrotreating
This process takes the residue from the atmospheric distillation and processes it in the
presence of Hydrogen over a series of catalysts that remove the contaminant metals and
coke precursors as well as Sulphur and Nitrogen that are other contaminants. The resultant
residue product is an excellent feed for the FCCU. The main disadvantage of this process is
that has a relatively high capital cost.
Vacuum Distillation
The most widely used process to prepare FCCU feed is by Vacuum distilling the fuel oil
residue formed during atmospheric distillation of Crude Oil to produce Vacuum Gasoil Oil
(VGO). Vacuum distillation concentrates the Asphaltenes and metals in the Vacuum Residue
and the VGO distillate is relatively free of them. Between 60 and 70 percent of the
Atmospheric residue is recovered as VGO. The remaining vacuum residue is either burnt as
fuel or further processed. Coking converts the vacuum residue to lighter hydrocarbons and
coke. Solvent De-asphalting of the residue extracts more feed for the FCCU.
Solvent De-Asphalting
Heavy paraffin components in residue will dissolve in light paraffin liquids such as Propane
and Butane. This solvent action is used in Solvent De-Asphalting (SDA) to separate out more
feed for the FCCU. SDA recovers material from the vacuum residue that can be cracked in
the FCC. The FCCU feed is De-Asphalted Oil (DAO) and is low in metals and asphaltenes.
The quantity and quality of the DAO is determined by the residue feed and the solvent.
Propane extracts less DAO than Butane but it is higher quality. Butane extraction typically
extracts 60 percent of the Vacuum residue. The SDA residue is very heavy and contains most
of the metals that were in the crude oil. While disposal of this material is troublesome, it
makes a good feedstock for gasification.
Recovering the solvent in SDA is usually achieved by heating the solvent under pressure to
its supercritical phase where the heavy oils are no longer soluble. Solvent in the residue is
recovered by distillation.
H He ea av vy y C Cr ru ud de e
N Na ap ph ht th ha a
A AG GO O
A AT TB B
G Ga as so ol li in ne e
D Di ie es se el l
O Ol le ef fi in ns s & & B BT TX X
P Po ow we er r
H Hy yd dr ro og ge en n
L Li iq qu ui id d
P Pr ro od du uc ct ts s
Crude
Distlln
Resid Processing
Coking or Deasphalting
plus
Hydroprocessing
Reforming
Hydrotreating
Cracking
Pyrolysis
FCC
DCC/CPP
Aromatics Recovery
Gasifier
Power Generation
Syn Gas Processing
Copyright World Petroleum Congress all rights reserved
ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS
Block 2, Forum 10 paper
References
1. Mugele, R. and Evans, H. D., Droplet Size Distributions in Sprays, Ind. Eng. Chem., Vol. 43, No. 6,
pp. 1317-1324, 1951
2. Wang Xieqing, Shi Wenyuan, Xie Chaogang, Li Zaiting Research Institute of Petroleum Processing,
SINOPEC, Catalytic Pyrolysis Process (CPP)-An Upswing of RFCC for Ethylene and Propylene
Production, AIChE National Spring Meeting, session T5a01 Advances in Catalytic Cracking, March
10 to 14 2002,New Orlean, LA
Copyright World Petroleum Congress all rights reserved

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