PETROLEUM TECHNOLOGY- Part III

THE PROCESS & TECHNOLOGY OF CRACKING

Introduction: In context to refinery processes for petroleum, cracking is defined as decomposition induced by elevated temperatures (>350 C, >660 F), whereby the higher molecular weight constituents of petroleum are converted to lower molecular weight products. Cracking reactions involve carboncarbon bond rupture & are thermodynamically favored at high temperatures. Although cracking basically involves converting large oil molecules into low boiling materials, during the actual process some smaller molecules may combine to give a product of higher molecular weight. A number of products may be formed during cracking of the petroleum feedstock such as gasoline, coke & fuel oil. Some material obtained during cracking & having a boiling range intermediate between gasoline & fuel oil is referred to as recycle stock, which is recycled back into the cracking equipment until conversion is complete. Chemistry of Cracking: Two general types of reaction occur during cracking: 1. The decomposition of large molecules into small molecules (primary reactions): CH3 CH2 CH2 CH3 Butane Or CH3 CH2 CH2 CH3 CH3 CH3 + CH2=CH2 CH4 + CH3 CH=CH2 methane propene

Butane ethane ethylene 2. Reactions by which some of the primary products react to form higher molecular weight materials (secondary reactions): CH2=CH2 Or R CH= CH2 + R CH= CH2

CH2=CH2

CH3 CH2 CH=CH2 butene

Ethylene

tar, heavy oil, coke, etc.

Methodology of cracking: There are several methods of performing cracking reactions & are described below: 1. Thermal Cracking: This involves the noncatalytic conversion of higher-boiling petroleum stocks into lower-boiling products by application of temperatures above 350 C. From the reaction point of view thermal cracking is a free radical chain reaction, a free radical being defined as an atom or group of atoms with an unpaired electron. For free radical reactions of various kinds involving hydrocarbons, refer page 255-257 of The Chemistry & Technology of Petroleum by James G. Speight or any standard organic chemistry textbook. 2 Catalytic Cracking : This is nothing but thermal decomposition similar to thermal cracking except that the cracking process occurs in the presence of a catalyst, which is not (in theory) consumed in the process & directs the course of the cracking reactions to produce more of the desired higher-octane hydrocarbon products. Nowadays most gasoline fractions are produced by this method superseding the older thermal cracking process. The chemistry of catalytic cracking is an ionic process involving carbonium ions which are hydrocarbon ions having a positive charge on a carbon atom. For details of chemical reactions involving

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PETROLEUM TECHNOLOGY- Part III

THE PROCESS & TECHNOLOGY OF CRACKING
catalytic cracking, refer page 255-257 of The Chemistry & Technology of Petroleum by James G. Speight or any standard organic chemistry textbook. 3. Visbreaking: Viscosity breaking or visbreaking is a mild thermal cracking operation used to reduce the viscosity & pour point of residual or asphaltic feed stocks. This operation produces a large amount of partially cracked gas oil which could then be processed in a conventional catalytic cracking plant.

4. Coking : Coking is again a variation of the thermal cracking process in which the time of cracking is so long that coke is produced as the bottom product. It is used for the continuous conversion of heavy, low-grade oils into lower products. The feedstock can be material such as reduced crude, straight-run residua, or cracked residua, & the products are gases, naphtha, fuel oil, gas oil, & coke. The coke obtained is usually used as fuel, but also finds specialty uses such as electrode manufacture, production of chemicals, & metallurgical coke, thus increasing its value. 5. Hydrocracking: This is an advancement in catalytic cracking process (>350 C) in which hydrogenation accompanies cracking. It is characterized by the cleavage of carbon-to-carbon linkages accompanied by hydrogen saturation of the fragments to produce lower-boiling products. Relatively high hydrogen pressures (100 to 2000 psi) are required to minimize polymerizations & condensations leading to coke formation. 6. Hydrotreating : This is again a variation of the catalytic cracking process, except that, although catalysts are employed for hydrotreating, there is very little cracking involved & the process actually is used for selective hydrogen addition to olefins & aromatics in order to saturate them. Another important purpose of hydrotreating is removal of sulfur & nitrogen compounds present in the feedstock by selective hydrogenation. The temperatures & pressures employed are generally moderate compared to hydrocracking. Description of Cracking processes: 1. Thermal Cracking: Thermal cracking of higher-boiling materials to motor or high-octane gasoline is now becoming an obsolete process, since these days the requirement of highoctane & low levels of deleterious sulfur & nitrogen compounds has proved to be a serious limitation for this process. New units are now practically not installed & many of the older operating refineries have either shutdown these units or have gone for revamping the older units to the more modern catalytic processes. Nevertheless a brief description of the commercial thermal cracking processes is given for better understanding The Dubbs Process: This is a typical application of the thermal cracking process. The feedstock (reduced crude) is preheated by direct exchange with the cracked products in the fractionating columns. Cracked gasoline & heating oil are removed from the upper section of the column. Light & heavy distillate fractions are removed from the lower section & are pumped to separate heaters. Higher temperatures are used to crack the more refractory light distillate fraction. The streams from the heaters are combined & sent to a reaction chamber where a certain residence time allows the cracking reactions to be completed. The cracked products are then separated in a low-pressure flash chamber where a heavy fuel oil is removed as bottoms. The remaining cracked products are sent to the fractionating column. Low pressures (<100 psi) & temperatures of 500 C or greater, produce low molecular weight hydrocarbons than those produced at higher pressures (400-1000 psi) & at temperatures below 500 C. The reaction time is also important; light feeds (gas oils) & recycle oils require longer reaction times than the readily-cracked heavy residues. Mild cracking conditions, with a low conversion per cycle, favor a high yield of gasoline components, with low gas & coke production, but the gasoline quality is not high, whereas more severe conditions give increased gas & coke production & reduced gasoline yield (but of higher quality).

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Gas

Feedstock (topped crude) Gasoline

Reaction chamber

Heater

Flasher

Fractionator

Furnace Oil Residuum Recycle

Mixed-Phase Cracking: Mixed-phase cracking (also called liquid-phase cracking) is a continuous thermal decomposition process for the conversion of heavy feedstocks to products boiling in the gasoline range. The process generally employs rapid heating of the feedstock (kerosene, gas oil, reduced crude, or even whole crude), after which it is passed to a reaction chamber & then to a separator where the vapors are cooled. Overhead products from the flash chamber are fractionated to gasoline components & recycle stock, while flash chamber bottoms are withdrawn as a heavy fuel oil. Coke formation, which may be considerable at the process temperatures (400 to 480 C), is minimized by use of pressures in excess of 350 psi.

Gas

Gasoline

Reaction Chamber

Feed Stock

Heater

Residuum Mixed-phase thermal cracking

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Fractionator

Flasher

PETROLEUM TECHNOLOGY- Part III

THE PROCESS & TECHNOLOGY OF CRACKING
Vapor-Phase Cracking: Vapor-phase cracking is a high temperature (545 to 595 C), lowpressure (< 50 psi) thermal conversion process which favors dehydrogenation of feedstock (gaseous hydrocarbons to gas oils) to olefins & aromatics. Coke is often deposited in heater tubes causing shutdowns - relatively large reactors are required for these units. Gas

Gasoline

Reaction chamber

Heater

Flasher

Feed Stock

Heater

Fractionator

Heavy fuel oil Recycle Vapor-phase thermal cracking Selective Cracking: This is a thermal conversion process, which utilizes optimum conditions of temperature & pressure for maximum product yield solely depending on the nature of the feedstock. For example, heavy oil might be cracked at 495 to 515 C & 300 to 500 psi, while lighter gas oil may be cracked at 510 to 530 C & 500 to 700 psi. It eliminates the accumulation of stable low-boiling material in the recycle stock & also minimizes coke formation from hightemperature cracking of the higher-boiling material. The end result is the production of fairly high yields of gasoline, middle distillates, & olefinic gases. Gas

Feedstock (topped crude) Gasoline

Reaction chamber

Heater

Flasher

Fractionator

Middle Distillate

Residuum Light oil (recycle) Heavy oil (recycle)

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Naphtha Cracking: The thermal cracking of naphtha involves the upgrading of low-octane fractions of catalytic naphtha to higher-quality material. The process is designed for upgrading heavier portions of naphtha, which contain uncracked virgin feedstock & to remove napthenes, as well as paraffins. During the process, small quantities of heavier aromatics are formed by condensation reactions, & the product stream contains substantial quantities of olefins.

2. Catalytic Cracking: As mentioned earlier, catalytic cracking differs from thermal cracking by use of catalyst & also is a much more efficient process compared to the non-catalytic thermal cracking. The catalytic & thermal methods are compared in the table below: Sr. No. 1 2 Catalytic Cracking The gasoline produced by this method has a higher octane number. The gasoline produced consists largely of isoparaffins & aromatics, which contribute to the higher octane number & also are chemically more stable. Catalytic cracking produces substantial quantities of olefinic gases suitable for polymer gasoline manufacture along with small amounts of methane, ethane, & ethylene. Catalytic cracking is a more selective cracking process & gives lesser end products. Gives a more economically salable coke. It has greater capability to accept highsulfur feedstock. Also gasoline produced by this method has a lower sulfur content. Thermal Cracking Comparatively lower octane number gasoline produced. Gasoline contains more mono-olefins & diolefins which are relatively less stable.

Quantity of olefinic gases is smaller in thermal cracking.

Not a very selective process & end products are more. Coke quality is not very high. High-sulfur feedstocks can prove to be a limitation.

5 6

Catalytic cracking, as a commercial process thus involves contacting a gas oil fraction with an active catalyst under suitable conditions of temperature, pressure, & residence time so that a substantial part (> 50%) of the gas oil is converted into gasoline & lower-boiling products, usually in a single pass operation. A limitation of the catalytic cracking process is the deposition of carbonaceous material on the catalyst, reducing the catalyst activity. The removal of the coke or carbonaceous deposit is therefore an important factor in the design of such units, one method being the burning of the catalyst bed or layer in the presence of air for regenerating the catalyst. A brief description of the various commercial catalytic cracking processes including the early ones is given below for better understanding: a. Houdry Fixed-Bed Catalytic Cracking: This was the first of the modern catalytic processes & went into commercial operation in 1936. In this fixed-bed process, the catalyst in the form of small lumps or pellets was made up of layers or beds in several (four or more) catalystcontaining drums called converters. Feedstock vaporized at about 450C & under 7 to 15-psi pressure passed through one of the converters where the cracking reactions took place. After a short time, deposition of coke on the catalyst rendered it ineffective, and, using a synchronized valve system, the feed stream was diverted to the adjacent converter while the

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catalyst in the first converter was regenerated by carefully burning the coke deposits with air. After about 10 minutes, the catalyst was ready to go on stream again. In the present age, fixed-bed processes have been replaced with the more versatile movingbed or fluid-bed processes.

Product fractionation Flue Gas

Air Feedstock (heated) Houdry fixed-bed catalytic cracking

b. Fluid-bed Catalytic Cracking: This is presently the most widely used catalytic cracking process & is characterized by the use of a finely divided silica/alumina based catalyst, which is moved through the processing unit. The catalyst particles are of such a size that when aerated with air, or hydrocarbon vapor, the catalyst behaves like a liquid & can be moved through pipes. Thus, vaporized feedstock & fluidized catalyst flow together into a reaction chamber where the catalyst, still dispersed in the hydrocarbon vapors, forms beds in the reaction chamber & the cracking reactions take place. Because of the even flow distribution of the catalyst & because of its high specific heat in relation to the vapors reacting, the entire reaction can be maintained at a remarkably constant temperature. The cracked vapors pass through cyclones located in the top of the reaction chamber, thereby removing the catalyst from the vapors by centrifugal action. The cracked vapors out of the reaction chamber enter the fractionating towers where fractionation into light- & heavy-cracked gas oils, cracked gasoline, & cracked gases takes place. Due to the contamination of the catalyst in the reaction chamber with coke, its activity is reduced, & it has to be regenerated. Thus the separated spent catalyst flows via steam fluidization from the reaction chamber to the regenerator vessel, where the coke is removed by controlled burning. In the course of burning the coke, a large amount of heat is liberated. Most of this heat of combustion is absorbed by the regenerated catalyst, & is sufficient to vaporize the fresh feed entering the reaction chamber. The fluid-bed catalytic cracking units abbreviated as FCCU are large-scale processes & unit throughputs are typically in the range of about 10,000 to 130,000 barrels per day which corresponds to catalyst circulation rates of 7 to 130 tons per minute. The large circulation rates of hot, abrasive catalyst constitute a very significant challenge to the mechanical integrity of the reactor, the regenerator & their associated internal equipment.

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Gases & gasoline Flue gas Steam Water

Products

Light gas Oil Fractionator Reactor

Fresh Catalyst

Regenerator

Reactor

Heavy gas Oil Bottoms

Catalyst make-up Air

Steam Regenerated catalyst Spent catalyst

Feedstock Flowsheet for fluid-bed catalytic cracking c. Model IV Fluid-Bed Catalytic Cracking Unit: This unit involves a process in which the catalyst is transferred between the reactor & regenerator by means of U-bends, & the catalyst flow rate can be varied in relation to the amount of air injected into the spent-catalyst U-bend. Regeneration air, other than that used to control circulation, enters the regenerator through a grid, & the reactor & regenerator are mounted side by side. This design was preceded by the Model III balanced pressure design, the Model II downflow design, & the original Model I upflow design. Flue gas Product fractionation

Regenerator

Feedstock

Regenerated catalyst Air Spent Catalyst Flowsheet for Model IV fluid-bed catalytic cracking

Steam

d. Orthoflow Fluid-Bed Catalytic Cracking: This process uses the unitary vessel design, which provides straight-line flow of catalyst & thereby minimizes erosion encountered in pipe-bends.

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Commercial Orthoflow designs are of three types: Models A & C, with the regenerator beneath the reactor, & model B, with the regenerator above the reactor. In all cases the catalyststripping section is located between the reactor & the regenerator; all designs employ the heat- balanced principle incorporating fresh feedrecycle feed cracking. Flue gas

Regenerator

Air Product fractionation

Recycle

Reactor

Steam Feedstock Air Model B Orthoflow fluid-bed catalytic cracking process Product fractionation

Reactor

Steam

Air Feedstock Recycle

Model C Orthoflow fluid-bed catalytic cracking unit

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Regenerator

Flue gas

PETROLEUM TECHNOLOGY- Part III

THE PROCESS & TECHNOLOGY OF CRACKING
e. Universal Oil Products (UOP) Fluid-bed Catalytic Cracking: This process is adaptable to the needs of both large & small refineries, & its important distinguishing features include 1) elimination of the air riser with its attendant large expansion joints, 2) elimination of considerable structural steel supports, & 3) reduction in regenerator & in air-line through use of 15 to 18 psi pressure operation. Product fractionation Reactor Flue gas Regenerator

Catalyst stripper

Steam

Air Feedstock Flowsheet for UOP fluid-bed catalytic cracking f. Shell Two-Stage Fluid-Bed Catalytic Cracking: This two-stage fluid catalytic process allows greater flexibility in shifting product when dictated by demand. Thus, virgin feedstock is first contacted with cracking catalyst in a riser reactor, that is, a pipe in which fluidized catalyst & vaporized oil flow concurrently upward, & the total contact time in this first stage is of the order of seconds. Light products Light products

Middle distillate

Fractionator

Fractionator

Heavy distillate Stripper Air Regenerator

Separator

Reactor

Reactor

Steam

Regenerated catalyst Feedstock Flowsheet for Shell two-stage catalytic cracking

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High temperatures 470 to 565 C are employed to reduce undesirable coke lay-down on catalyst without destruction of gasoline by secondary cracking. Other operating conditions in the first stage are a pressure of 16 psi & catalyst-oil ratio of 3:1 to 50:1, & volume conversion ranges between 20 & 70% have been recorded. All or part of the unconverted or partially converted gas-oil product from the first stage is then cracked further in the second-stage fluid-bed reactor. Operating conditions are 480 to 540 C & 16 psi with a catalyst-oil ratio of 2 to 12/1. Conversion in the second stage varies between 15 & 70% with an overall conversion range of 50 to 80%. g. Airlift Thermofor Catalytic Cracking (Socony Airlift TCC process) : This process is a moving-bed, reactor-over-generator continuous process for conversion of heavy gas oils into lighter high-quality gasoline & middle distillate fuel oils. Feed preparation may consist of flashing in a tar separator to get vapor feed, & the tar separator bottoms may be sent to a vacuum tower from which the liquid feed is produced. The gas-oil vapor-liquid flows downward through the reactor concurrently with the regenerated synthetic bead catalyst. The catalyst is purged by steam at the base of the reactor, & gravitates into the kiln or regeneration is done by the use of air injected into the kiln. Approximately 70% of the carbon on the catalyst is burned in the upper kiln burning zone & the remainder in the bottom burning zone. Regenerated, cooled catalyst enters the lift pot, where low-pressure air transports it to the surge hopper above the reactor for reuse.

(liquid) Feedstock (vapor) Steam Reactor

Surge hopper

Regenerated catalyst

Product fractionation

Flue gas

Kiln

Kiln

Air (hot)

Air (lift)

Flowsheet for airlift thermofor catalytic cracking

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h. Houdriflow Catalytic Cracking: This is a continuous, moving-bed process employing an integrated single vessel for the reactor & regenerator kiln. The charge stock, sweet or sour, can be any fraction of the crude boiling between naphtha & soft asphalt. The catalyst is transported from the bottom of the unit to the top in a gas lift employing compressed flue gas & steam. The reactor feed & catalyst pass concurrently through the reactor zone to a disengager section, in which vapors are separated & directed to a conventional fractionation system. The spent catalyst, which has been steam purged of residual oil, flows to the kiln for regeneration, after which steam & flue gas are used to transport the catalyst to the reactor.

Feedstock Steam

Products Flue gas Reactor

Catalyst Lift Kiln

Air Flowsheet for Houdriflow catalytic cracking i. Houdresid Catalytic cracking: Houdresid catalytic cracking is a process that uses a variation of the continuous-moving catalyst bed designed to get high yields of high-octane gasoline & light distillate from reduced crude charge. Residuum cuts ranging from crude tower bottoms to vacuum bottoms, including residua high in sulfur or nitrogen can be employed as the feedstock, & the catalyst is synthetic or natural. Though the equipment employed is similar in many respects to that used in Houdriflow units, novel process features modify or eliminate the adverse effects on catalyst & product selectivity usually resulting when heavy metals iron, nickel, copper, & vanadium are present in the fuel. The Houdresid catalytic reactor & catalyst-regenerating kiln are contained in a single vessel. Fresh feed plus recycled gas oil are charged to top of the unit in a partially vaporized state & mixed with steam. Refer flowsheet below:

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Catalyst storage

PETROLEUM TECHNOLOGY- Part III

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Light products Houdresid unit

Fractionator

Feedstock

Redu ced crude

Fractionator

Middle distillates

Fuel stocks Recycle

Flowsheet for Houdresid catalytic cracking

j.

Suspensoid Catalytic Cracking: This was developed from the thermal cracking process carried out in tube & tank units. Small amounts of powdered catalyst or a mixture with the feedstock & the mixture are pumped through a cracking coil furnace. Cracking temperatures are 550 to 610 C with pressures of 200 to 500 psi. After leaving the furnace, the cracked material enters a bubble tower where they are separated into two parts, gas oil & pressure distillate. The latter is separated into gasoline & gases. The spent catalyst is filtered from the tar, which is used as a heavy-industry fuel oil. The process is a compromise between catalytic & thermal cracking. Here the catalyst allows a higher cracking temperature & assists mechanically in keeping coke from accumulating on the walls of the tubes. The normal catalyst employed is spent clay obtained from the contact filtration of lubricating oils (2 to 10 lb. per barrel of feed).

Products (gasoline, gases)

Catalyst Fractionator

Feedstock

Heater

Filter

Heavy fuel oil Catalyst

Flowsheet for Suspensoid catalytic cracking

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3. Visbreaking: As explained earlier visbreaking is a mild thermal cracking operation employed for viscosity reduction of residual or asphaltic feed stocks. Visbreaking conditions range from 455 to 510C & from 50 to 300 psi at the heating-coil outlet. Liquid-phase cracking takes place at these low-severity conditions. Besides fuel oil (major product), material in the gas oil & gasoline boiling range is also produced. The gas oil produced may be diverted to catalytic cracking units or used as heating oil. Thus, a crude oil residuum is passed through a furnace where it is heated to a temperature of 480C, the outlet pressure controlled at about 100 psi. The furnace is designed in a manner such that it contains a soaking section of low heat density, where the charge can be held until the visbreaking reactions are completed. The cracked products are then passed into a flashdistillation chamber. The overhead material from this chamber is then fractionated to produce a low-quality gasoline as an overhead product & light gas oil as bottoms. The liquid products from the flash chamber are cooled with a gas oil flux & then sent to a vacuum fractionator. This yields a heavy gas oil distillate & a residual tar of reduced viscosity. Gasoline Feedstock Heavy gas oil Vacuum fractionator

Flasher

Fractionator

Reactor

Tar Light gas oil Flowsheet for Visbreaking operations 4. Coking: As mentioned earlier coking processes generally utilize longer reaction times than thermal cracking processes. To accomplish this, drums or chambers (reaction vessels) are employed. Normally two or more such vessels are provided, in order to simultaneously decoke the off-line vessel without interrupting the semicontinuous type of process. The various type of coking processes are described below: a. Delayed Coking: This is a semicontinuous process in which the heated charge is transferred to large soaking (or coking) drums, which provide the long residence time needed to allow the cracking reactions to be completed. The feed to these units is normally an atmospheric residuum although cracked tars & heavy catalytic oils may also be used. The process flow is as follows: The feedstock enters the product fractionator where it is heated & lighter fractions are removed as side streams. The fractionator bottoms, including a recycle stream of heavy product, are then heated in a furnace whose outlet temperature varies from 480 to 515C. The heated material enters one of a pair of coking drums where the cracking reactions are completed. The cracked products leave as overheads, & coke deposits form on the the inner surface of the drum. Two drums allow for continuous operation, with one on stream while the other is being cleaned. The temperature in the coke drum ranges from 415 to 450C

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at pressures from 15 to 90 psi. The overheads from the coking drum go to the fractionator, where naphtha & heating oil fractions are recovered. The heavy recycle material is material is combined with preheated fresh feed & returned to the reactor. The coke drum is usually on stream for about 24 hours before becoming filled with porous coke, & the following procedure is used to remove the coke: 1) the coke deposit is cooled with water; 2) one of the heads of the coking drum is removed to permit the drilling of a hole through the center of the deposit; & 3) a hydraulic cutting device, which uses multiple high -pressure jets, is inserted into the hole, & the wet coke is removed from the drum. These cleaning operations normally require 24 hours before the drum can be put into reuse. Gas Gasoline (naphtha) Gas oil

Feedstock Fractionator Coking drum (soaker) Coking drum (soaker)

Coke

Operative

Nonoperative

Flowsheet for Delayed coking b. Fluid Coking: Fluid coking is a continuous process, which uses the fluidized-solids technique to convert residua, including vacuum pitches, to more valuable products. The residuum is coked by being sprayed into a fluidized bed of hot, fine coke particles, which permit the coking reactions to be conducted at higher temperatures & shorter contact times than can be employed in delayed coking. Moreover, these conditions result in decreased yields of coke with greater quantity of more valuable liquid product being recovered. Fluid coking uses two vessels, a reactor & a burner; coke particles are circulated between these to transfer heat (generated by burning a portion of the coke) to the reactor. The reactor holds a bed of fluidized coke particles, & steam is introduced at the bottom of the reactor to fluidize the bed. The pitch feed at, for example 260 to 370C is injected directly into the reactor. The temperature in the coking vessel ranges from 480 to 565C, & the pressure nearly atmospheric causing the incoming feed to partly vaporize & partly deposit on the fluidized coke particles. The material on the particle surface then cracks & vaporizes, leaving a residue, which dries to form coke. The vapor products pass through cyclones, which remove most of the entrained coke. The vapor is discharged into the bottom of a scrubber where the products are cooled to condense a heavy tar, which contains substantial quantity of coke dust & is recycled back to the reactor. The upper part of the scrubber tower is a fractionating zone from which coker gas

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oil is withdrawn for feeding to a catalytic cracking unit. The naphtha & gas from the fractionating zone are taken overhead to condensers. In the reactor, the coke particles flow down through the vessel into a stripping zone at the bottom. Steam displaces the product vapors between the particles & the coke then flows into a riser, which leads to the burner. Steam is added to the riser to reduce the solids loading & induce upward flow. The average bed temperature in the burner is 590 to 650C, & air is added as needed to maintain the temperature by burning part of the product coke. The pressure in the burner may range from 5 to 25 psi. Flue gases from the burner pass through cyclones & discharge to the stack. Hot coke from the bed is returned to the reactor through a second riser assembly. Coke is one of the products of the process, & it must be withdrawn from the system in order to keep the solids inventory from increasing. The net coke produced is removed from the burner bed through a quench elutriator drum, where water is added for cooling & cooled coke is withdrawn & sent to storage. During the course of the coking reaction the particles tend to grow in size. The size of the coke particles remaining in the system is controlled by a grinding system within the reactor. Fuel gas Cracked gasoline

Fractionator

Gas oil

Flue gas

Coke

Burner

By-product coke Reactor Feedstock Air

Coke

Steam Flowsheet for Fluid coking c. Decarbonizing: The decarbonizing thermal process is designed to minimize coke & gasoline yields but, at the same time, to give maximum yield of gas oil. The process is essentially the

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same as the delayed coking process, but lower temperatures & pressures are employed. For example, pressures range from 10 to 25 psi while heater outlet temperatures maybe 485C & coke drum top temperatures maybe of the order of 415C. Gas

Gasoline Gas oil Fractionator

Coke drum

Feedstock

Flowsheet for Decarbonizing d. Low-Pressure Coking: Low-pressure coking is a process designed for a once-through, low pressure operation. The process is similar to delayed coking except that recycling is not practiced & the coke chamber operating conditions are 435C, 25 psi. Excessive coking is inhibited by the addition of water to the feedstock. Gas and gasoline

Coke chamber

Coke chamber

Coke drum Fractionator Flasher

Gas oil

Feedstock Fuel oil Flowsheet for Low-pressure coking e. High-Temperature Coking: This is a semicontinuous thermal conversion process designed for high-melting asphaltic residua which yield coke & gas oil as the primary products. The coke may further be treated to remove sulfur to produce a low-sulfur coke ( 5%), even though the feedstock could have as much as 5% wt/wt sulfur. The process flow is as follows:

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The feedstock is fed into the pitch accumulator, then to the heater (370C, 30 psi), & finally to the coke oven where temperatures may be as high as 980 to 1095C. Volatile materials are fractionated, and, after the cycle is complete, coke is collected for sulfur removal & quenching prior to storage.

Gas Gasoline Pitch accumulator

Coke oven

Gas oil

Coke Flowsheet for High-temperature coking

5. Hydrocracking: Hydrocracking is similar to catalytic cracking, with hydrogenation superimposed & with the reactions taking place simultaneously or sequentially. The purpose hydrocracking is to convert high-boiling feedstocks to lower-boiling products by cracking the hydrocarbons in the feed & hydrogenating the unsaturated materials in the product streams. The polycyclic aromatics are first partially hydrogenated before cracking of the aromatic nucleus takes place. Also the majority of sulfur & nitrogen is converted to hydrogen sulfide & ammonia. The reaction rates are facilitated by use of catalysts. Large quantities of hydrogen sulfide & ammonia are formed when using high sulfur & nitrogen feedstocks for hydrocracking units. These are removed by the injection of water in which, under the high pressure conditions employed, both hydrogen sulfide & ammonia are very soluble compared with hydrogen & hydrocarbon gases. 6. Hydrotreating: The purpose of the process is the removal of sulfur & nitrogen compounds without appreciable alteration in the boiling range or in other words it is selective hydrogenation of the feedstock for removal of sulfur & nitrogen with very little cracking involved. Hydrotreating catalysts are usually cobalt plus molybdenum or nickel plus molybdenum in the sulfide forms, impregnated on an alumina base. The operating conditions of 1000 to 2000 psi hydrogen pressures & 370C temperatures are such that appreciable hydrogenation of aromatics will not occur. Commercial Processes for Hydrocracking & Hydrotreating : Since commercial processes for hydrocracking & hydrotreating operate essentially in the same manner i.e. feedstock is passed along with hydrogen gas into a tower or reactor filled with catalyst pellets the commercial processes have not been classified separately as hydrocracking & hydrotreating. The processing conditions i.e. the temperature & pressures decide whether a lot of cracking reactions are taking place along with the hydrogenation or just removal of nitrogen & sulfur is taking place. Hydrofining: This process can be applied to lubricating oils, naphthas, & gas oils. The feedstock is heated in a furnace & passed with hydrogen through a reactor containing a

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suitable metal oxide catalyst, such as cobalt & molybdenum oxides on alumina. Reactor operating conditions range from 205 to 425C & from 50 to 800 psi, depending on the feedstock & the degree of treating required.. Higher-boiling feedstocks, high sulfur content, & maximum sulfur removal require higher temperatures & pressures. After passing through the reactor, the treated oils cooled & separated from the excess hydrogen, which is recycled through the reactor. The treated oil is pumped to a stripper tower where hydrogen sulfide, formed by the hydrogenation reaction, is remove by steam, vacuum, or flue gas, & the finished product leaves the bottom of the stripper tower. In this process the catalyst is usually not regenerated & is replaced after about a year s use. This process is used to upgrade low-quality, high-sulfur naphthas. The sulfur content of kerosenes can be reduced with improved color, odor, & wick-char characteristics. The tendency of kerosene to form smoke is not affected since aromatics, which cause smoke., are not affected by the mild hydrofining conditions. Cracked gas oils with high sulfur content can be converted to excellent furnace fuel oils & diesel fuel oils by reduction in sulfur content & by removal of components that form gum & carbon residues.

Hydrogen

Water (vapor) Furnace Reactor Stripper

Feedstock

Drier

Product stream Hydrogen Flowsheet for Hydrofining

Unifining: This is regenerative, fixed-bed, catalytic process to desulfurize & hydrogenate refinery distillates of any boiling range. Contaminating metals, nitrogen compounds, & oxygen compounds are eliminated, along with sulfur. The catalyst is a cobalt molybdenum-alumina type which may be regenerated in situ with steam & air. Ultrafining: It is a regenerative, fixed-bed, catalytic process to desulfurize & hydrogenate refinery stocks from naphthas through lube stocks. The catalyst is cobalt-molybdenum on alumina & may be regenerated in situ using an air-stream mixture. Regeneration requires 10 to 20 hours & may be repeated 50 to 100 times for a given batch of catalyst; catalyst life is 2 to 5 years depending on the feedstock.

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Autofining: The autofining process differs from other hydrorefining processes in that an external source of hydrogen is not required. Sufficient hydrogen to convert sulfur to hydrogen sulfide is obtained by dehydrogenation of naphthenes in the feedstock. The processing equipment is similar to that used in Hydrofining. The catalyst is cobalt & molybdenum oxides on alumina, & operating conditions are usually 340 to 425C at pressures of 100 to 200 psi. Hydrogen formed by dehydrogenation of naphthenes in the reactor, is separated from the treated oil & is then recycled through the reactor. The catalyst is regenerated with steam & air at 200 to 1000 hour intervals, depending on whether light or heavy feedstocks have been processed. The process is used for the same purpose, as Hydrofining but is limited to fractions with end points not higher than 370C. Feedstock (preheated) Flue gas

Accumulator

Knockout drum

Fractionator

Reactor

Product stream

Heavy fuel oil Flowsheet for Autofining Isomax: The Isomax process is a two-stage, fixed-bed catalyst system which operates under hydrogen pressures from 500 to 1500 psig in a temperature range of 205 to 370C, for example with middle distillate feedstocks. Exact conditions depend on the feedstock & product requirements, & hydrogen consumption is of the order of 1000 to 1600 SCF per barrel of feed processed. Each stage has a separate hydrogen recycle system. Conversion may be balanced to provide products for variable requirements, & recycle can be taken to extinction if necessary. Fractionation can also be handled in a number of ways to yield desired products. Recycle hydrogen

Hydrogen Fuel gas Feedstock recycle Reactor

Fuel gas Fuel gas Butanes Stabilizer

Reactor

Light gasoline Heavy gasoline Diesel fuel Bottoms

Feedstock recycle Flowsheet for Isomax hydrocracking process

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H-Oil: The H-Oil process is basically a catalytic hydrogenation technique in which, during the reaction, considerable hydrocracking takes place. The process is used to upgrade heavy sulfurcontaining crudes & residual stocks to high-quality sweet distillates, thereby reducing fuel oil yield. A modification of H-Oil called Hy-C cracking will convert heavy distillates to middle distillates & kerosene. Oil & hydrogen are fed upward through the reactors as a liquid-gas mixture at a velocity such that catalyst is in continuous motion. Catalyst of small particle size can be used, giving efficient contact among gas, liquid, and solid with good mass & heat transfer. Part of the reactor effluent is recycled back through the reactors for temperature control & to maintain the requisite liquid velocity. The entire bed is held within a narrow temperature range, which provides essentially an isothermal operation with an exothermic process. Because of the movement of catalyst particles in the liquid-gas medium, deposition of tar & coke is minimized, & fine solids entrained in the feed will not lead to reactor plugging. The can also be added & withdrawn from the reactor without interrupting the continuity of the process. The reactor effluent is cooled by exchange & separates into vapor & liquid. After scrubbing in a lean-oil absorber, hydrogen is recycled, and the liquid product is either stored directly or fractionated prior to storage & blending. Hydrogen recycle

Gas

Hydrogen recycle

Lean oil Reactor Reactor Separator Absorber Flasher Rich oil Distillate Product stream

Feedstock

Hydrogen make-up Flowsheet for H-Oil Process

Unicracking-JHC: This is a fixed-bed catalytic process that employs a high-activity catalyst with a high tolerance for sulfur & nitrogen compounds & can be regenerated. The design is based upon a single-stage or a two-stage system with provisions to recycle to extinction. A two-stage reactor system receives untreated feed, make-up hydrogen, and a recycle gas at the first stage in which gasoline conversion may be as high as 60% by volume. The reactor effluent is separated to recycle gas, liquid product, and unconverted oil. The second-stage oil may be either once through or recycle cracking; feed to the second stage is a mixture of unconverted first-stage oil & second-stage recycle.

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Hydrogen make-up Feedstock Hydrogen recycle Flasher (s) Reactor Reactor Gasoline Fractionator Gas and light gasoline

Diesel fuel

Feedstock recycle Flowsheet for Unicracking-JHC process Gulf HDS: This is a regenerative fixed-be process to upgrade petroleum residues by catalytic hydrogenation to refined fuel oils or to high-quality catalytic charge stocks. Desulfurization & quality improvement are the primary purposes of the process, but if the operating conditions & catalysts are varied, light distillates can be produced & the viscosity of heavy material can be lowered. Long on-stream cycles are maintained by reducing random hydrocracking reactions to a minimum, and whole crudes, virgin, or cracked residua may serve as feedstock. The catalyst is a metallic compound supported on pelleted alumina & may be regenerated in situ with air & steam or flue gas through a temperature cycle of 400 to 650C. On-stream cycles of 4 to 5 months can be obtained at desulfurization levels of 65 to 75% & catalyst life may be as long as 2 years. Hydrogen make-up Hydrogen recycle Lean Absorber Gas Diethanolamine Rich Gas Separator (low press.) Light gasoline Heavy naphtha Light gas oil Heavy gas oil Light bottoms Heavy bottoms Flowsheet for Gulf HDS process Feedstock

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Separator (high press.)

Reactor

Reactor

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H-G Hydrocracking: This process may be designed with either a single- or a two-stage reactor system for conversion of light & heavy gas oils to lower-boiling fractions. The feedstock is mixed with recycle gas oil, make-up hydrogen, and hydrogen-rich recycle gas, and then heated & charged to the reactor. The reactor effluent is cooled & sent to a high-pressure separator where hydrogen-rich gas is flashed off, scrubbed, then recycled to the reactor. Separator liquid passes to a stabilizer for removal of butanes & lighter products, & the bottoms are taken to a fractionator for separation; any unconverted material is recycled to the reactor. C2 gases Feedstock (Heavy gas oil) (Recycle) Separator Stabilizer Hydrogen (Make-up) Reactor Fractionator Fuel Gas Filter Stripper/vacuum drier Hydrogen recycle C3, C4 gases Gasoline Product Stream

Feedstock recycle Flowsheet for H-G hydrocracking process Ferrofining: The mild hydrogen-treating process was developed to treat distilled & solvent-refined lubricating oils. The process eliminates the need for acid & clay treatment. The catalyst is a threecomponent material on alumina base with low hydrogen consumption & life expectancy of 2 years or more. Process operations include heating the hydrogen-oil mixture & charging to a downflow catalyst-filled reactor. Separation of oil & gas is a two-stage operation whereby gas is removed to the fuel system. The oil is then stripped to control the flash point, dried in vacuum, & a final filtering step removes the catalyst fines. Hydrogen Feedstock Gas and steam

Separator (high press.)

Separator (low press.)

Reactor

Product Flowsheet for Ferrofining process

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List of know-how suppliers for Cracking Processes: Most oil majors have developed & modified technologies to suit their own particular requirements. There have been many modifications to the older technologies & many of these processes are patented with the patents owned by the worlds leading refining companies. Some of the major technology licensors are: Universal Oil Products (UOP): They are one of the leading technology licensors & provide integrated refinery solutions including catalytic cracking, hydroprocessing & reforming. Reliance Petroleum Ltd., the largest single-stream refinery in Asia has major processing units designed by UOP. Shell Development Company (Shell): Shell is a leading company providing technology for visbreaking units & crackers. ABB-Lummus Global/Chevron: They are among the top technology & engineering solutions provider for FCC units, Hydrocrackers & Hydrotreaters. Stone & Webster Engineering Corporation (S & W): They specialize in FCC units & have a major share of the world market. Institut Francais Petole (IFP): IFP is recognized the world over for its Hydrotreating technologies for light distillates & majority of new installations are opting for IFP technology. One of their specialties is a new selective hydrotreating technology named Prime G for ultra low sulfur gasoline. Haldor Topsoe AS (Topsoe): They are leading contenders for supply of Hydrotreating technology. Kellogg, Brown & Root Inc. (KBR): Most of the older FCC units in North America were designed by KBR & they are doing a lot of revamp/ technology upgradation jobs on their older units. BASF: BASF is a Germany based multinational & they have developed certain commercial Hydroprocessing technologies. ExxonMobil: They have developed new selective hydrotreating technologies for ultra low sulfur gasolines called Scanfining, Octgain 125 & Octgain 220 which shall become very relevant when international norms for sulfur content in motor fuels are brought down to 50 ppm. Some other companies offering Cracking & Hydroprocessing technologies include CD tech, Petrobras (Brazil), Akzo, Criterion (mainly catalyst suppliers) etc. It is important to note that of the various technologies available, the selection has to be made based basically on three factors: a) feedstock to be processed b) end-product or its mix required & c) economics of a particular process vis--vis its competitive technology. List of reference books: 1. The Chemistry and Technology of Petroleum James G. Speight Publisher: Marcel Dekker, Inc. 2. Petroleum Refinery Engineering W. L. Nelson Publisher: McGraw-Hill Kogakusha, Ltd. 3. Chemical Process Industries R. Norris Shreve & Joseph A. Brink, Jr. Publisher: McGraw-Hill International Book Company

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