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

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 byproduct 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.
1.1

FCCU ADVANCES
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

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.

ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS Block 2, Forum 10 paper
S&W / Axens Residue FCC with Two Stage Regenerator

Coupled to cyclones Second Stage Regenerator Riser Separator RS Reactor / Disengager Withdrawal Well Combustion

Air Ring

Stripper / Packing

First Stage Regenerator Combustion Air Ring

Reactor Riser MTC Injection

Lift Air

Feed Injection

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

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 snowmaker, 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.

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 OC. 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

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 RS2 Separator

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

Robust Construction Improved Operation Reduces Coke to the Regenerator Good Start-up Characteristics Minimises Steam Usage

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.

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 C3 and C4 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 C3 or C4 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.

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

FCC Reactor Temp. C Reactor Pressure, Bar Gauge Residence Time, Secs Catalyst to Oil Ratio, wt/wt Dispersion Steam, wt% Feed Cracking Environment 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

Cracking to produce light olefins requires higher temperatures, lower pressures and more steam.

ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS Block 2, Forum 10 paper
Table 2.2 Naphtha Compositions

BTX in Naphtha wt% Benzene Toluene Xylene

DCC 1.6 5.7 10.0

CPP 4.6 16.6 23.7

SC 37.8 14.9 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

Dilution Steam

BF Water Preheated Fresh Feed HP Steam SLE

USC Cracking Furnace

Fuel Gas

To Quench

Steam Cracking is a thermal cracking process with a free radical mechanism requiring elevated temperatures of approximately 800 OC, 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.

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.

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

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
Crude Distn

Pyrolysis
Naphtha AGO
Coil QC

Recovery

Gas to Fuel Ethylene

Light Crude

Light Recycle

Propylene BTX Gas Oils to Fuel

Catalytic
ATB
Resid. FCC DCC CPP

Heavy Recycles

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.

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.

ADVANCES IN FCCU TECHNOLOGY FOR THE PRODUCTION OF OLEFINS Block 2, Forum 10 paper
Integrated Fuels / Petrochemical Refinery
Crude Distlln Naphtha Gasoline

Reforming

AGO Hydrotreating

Diesel

Heavy Crude

Cracking Pyrolysis FCC DCC/CPP Aromatics Recovery Olefins & BTX

ATB Resid Processing Coking or Deasphalting plus Hydroprocessing

Power Gasifier Power Generation Syn Gas Processing Hydrogen Liquid Products

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.

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