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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PETROLEUM TECHNOLOGY. after which it is passed to a reaction chamber & then to a separator where the vapors are cooled.Part III THE PROCESS & TECHNOLOGY OF CRACKING 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. reduced crude. Coke formation. The process generally employs rapid heating of the feedstock (kerosene. gas oil. or even whole crude). is minimized by use of pressures in excess of 350 psi. while flash chamber bottoms are withdrawn as a heavy fuel oil. Gas Gasoline Reaction Chamber Feed Stock Heater Residuum Mixed-phase thermal cracking Page 3 of 23 Fractionator Flasher . which may be considerable at the process temperatures (400 to 480° C). Overhead products from the flash chamber are fractionated to gasoline components & recycle stock.

which utilizes optimum conditions of temperature & pressure for maximum product yield solely depending on the nature of the feedstock.PETROLEUM TECHNOLOGY. The end result is the production of fairly high yields of gasoline. Coke is often deposited in heater tubes causing shutdowns . 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. 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. lowpressure (< 50 psi) thermal conversion process which favors dehydrogenation of feedstock (gaseous hydrocarbons to gas oils) to olefins & aromatics.Part III THE PROCESS & TECHNOLOGY OF CRACKING Vapor-Phase Cracking: Vapor-phase cracking is a high temperature (545 to 595° C). middle distillates. & olefinic gases.relatively large reactors are required for these units. For example. while lighter gas oil may be cracked at 510 to 530° C & 500 to 700 psi. Gas Feedstock (topped crude) Gasoline Reaction chamber Heater Flasher Fractionator Middle Distillate Residuum Light oil (recycle) Heavy oil (recycle) Page 4 of 23 . heavy oil might be cracked at 495 to 515° C & 300 to 500 psi.

using a synchronized valve system. The process is designed for upgrading heavier portions of naphtha. 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 gasoline produced consists largely of isoparaffins & aromatics. ethane. It has greater capability to accept highsulfur feedstock. 3 Quantity of olefinic gases is smaller in thermal cracking. the feed stream was diverted to the adjacent converter while the Page 5 of 23 .PETROLEUM TECHNOLOGY. Gives a more economically salable coke. & residence time so that a substantial part (> 50%) of the gas oil is converted into gasoline & lower-boiling products. No. The catalytic & thermal methods are compared in the table below: Sr.Part III THE PROCESS & TECHNOLOGY OF CRACKING Naphtha Cracking: The thermal cracking of naphtha involves the upgrading of low-octane fractions of catalytic naphtha to higher-quality material. as well as paraffins. which contribute to the higher octane number & also are chemically more stable. High-sulfur feedstocks can prove to be a limitation. A brief description of the various commercial catalytic cracking processes including the early ones is given below for better understanding: a. & the product stream contains substantial quantities of olefins. Catalytic Cracking: As mentioned earlier. A limitation of the catalytic cracking process is the deposition of carbonaceous material on the catalyst. Thermal Cracking Comparatively lower octane number gasoline produced. small quantities of heavier aromatics are formed by condensation reactions. as a commercial process thus involves contacting a gas oil fraction with an active catalyst under suitable conditions of temperature. and. 2. Feedstock vaporized at about 450°C & under 7 to 15-psi pressure passed through one of the converters where the cracking reactions took place. pressure. The removal of the coke or carbonaceous deposit is therefore an important factor in the design of such units. After a short time. 5 6 Catalytic cracking. which contain uncracked virgin feedstock & to remove napthenes. usually in a single pass operation. Gasoline contains more mono-olefins & diolefins which are relatively less stable. Houdry Fixed-Bed Catalytic Cracking: This was the first of the modern catalytic processes & went into commercial operation in 1936. 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. Catalytic cracking is a more selective cracking process & gives lesser end products. & ethylene. Catalytic cracking produces substantial quantities of olefinic gases suitable for polymer gasoline manufacture along with small amounts of methane. 4 Not a very selective process & end products are more. deposition of coke on the catalyst rendered it ineffective. In this fixed-bed process. 1 2 Catalytic Cracking The gasoline produced by this method has a higher octane number. Coke quality is not very high. reducing the catalyst activity. Also gasoline produced by this method has a lower sulfur content. During the process. one method being the burning of the catalyst bed or layer in the presence of air for regenerating the catalyst.

Page 6 of 23 . still dispersed in the hydrocarbon vapors. thereby removing the catalyst from the vapors by centrifugal action. a large amount of heat is liberated. which is moved through the processing unit. In the present age. or hydrocarbon vapor. Product fractionation Flue Gas Air Feedstock (heated) Houdry fixed-bed catalytic cracking b. abrasive catalyst constitute a very significant challenge to the mechanical integrity of the reactor. vaporized feedstock & fluidized catalyst flow together into a reaction chamber where the catalyst. & cracked gases takes place. the entire reaction can be maintained at a remarkably constant temperature. Because of the even flow distribution of the catalyst & because of its high specific heat in relation to the vapors reacting. In the course of burning the coke. Due to the contamination of the catalyst in the reaction chamber with coke. where the coke is removed by controlled burning. 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. The cracked vapors pass through cyclones located in the top of the reaction chamber. cracked gasoline.000 barrels per day which corresponds to catalyst circulation rates of 7 to 130 tons per minute. The catalyst particles are of such a size that when “aerated” with air. Thus.Part III THE PROCESS & TECHNOLOGY OF CRACKING catalyst in the first converter was regenerated by carefully burning the coke deposits with air. & it has to be regenerated. Thus the separated spent catalyst flows via steam fluidization from the reaction chamber to the regenerator vessel. & is sufficient to vaporize the fresh feed entering the reaction chamber.PETROLEUM TECHNOLOGY. After about 10 minutes. the catalyst behaves like a liquid & can be moved through pipes. forms beds in the reaction chamber & the cracking reactions take place. fixed-bed processes have been replaced with the more versatile movingbed or fluid-bed processes. Most of this heat of combustion is absorbed by the regenerated catalyst. its activity is reduced. The cracked vapors out of the reaction chamber enter the fractionating towers where fractionation into light.000 to 130.& heavy-cracked gas oils. the catalyst was ready to go on stream again. The fluid-bed catalytic cracking units abbreviated as “FCCU” are large-scale processes & unit throughputs are typically in the range of about 10. The large circulation rates of hot. the regenerator & their associated internal equipment.

PETROLEUM TECHNOLOGY. 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. which provides straight-line flow of catalyst & thereby minimizes erosion encountered in pipe-bends. Page 7 of 23 . & the catalyst flow rate can be varied in relation to the amount of air injected into the spent-catalyst U-bend. Regeneration air. enters the regenerator through a grid. & the original Model I upflow design. Orthoflow Fluid-Bed Catalytic Cracking: This process uses the unitary vessel design. the Model II downflow design.Part III THE PROCESS & TECHNOLOGY OF CRACKING 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. other than that used to control circulation. This design was preceded by the Model III balanced pressure design. Flue gas Product fractionation Regenerator Feedstock Regenerated catalyst Air Spent Catalyst Flowsheet for Model IV fluid-bed catalytic cracking Steam d. & the reactor & regenerator are mounted side by side.

& model B. all designs employ the heat. with the regenerator above the reactor. In all cases the catalyststripping section is located between the reactor & the regenerator. with the regenerator beneath the reactor. 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 Page 8 of 23 Regenerator Flue gas .PETROLEUM TECHNOLOGY.balanced principle incorporating fresh feed–recycle feed cracking.Part III THE PROCESS & TECHNOLOGY OF CRACKING Commercial Orthoflow designs are of three types: Models A & C.

& its important distinguishing features include 1) elimination of the air riser with its attendant large expansion joints. 2) elimination of considerable structural steel supports. Product fractionation Reactor Flue gas Regenerator Catalyst stripper Steam Air Feedstock Flowsheet for UOP fluid-bed catalytic cracking f.Part III THE PROCESS & TECHNOLOGY OF CRACKING e. a pipe in which fluidized catalyst & vaporized oil flow concurrently upward. virgin feedstock is first contacted with cracking catalyst in a riser reactor. that is.PETROLEUM TECHNOLOGY. & 3) reduction in regenerator & in air-line through use of 15 to 18 psi pressure operation. Universal Oil Products (UOP) Fluid-bed Catalytic Cracking: This process is adaptable to the needs of both large & small refineries. 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 Page 9 of 23 . & the total contact time in this first stage is of the order of seconds. Shell Two-Stage Fluid-Bed Catalytic Cracking: This two-stage fluid catalytic process allows greater flexibility in shifting product when dictated by demand. Thus.

Operating conditions are 480 to 540° C & 16 psi with a catalyst-oil ratio of 2 to 12/1. Other operating conditions in the first stage are a pressure of 16 psi & catalyst-oil ratio of 3:1 to 50:1. Airlift Thermofor Catalytic Cracking (Socony Airlift TCC process) : This process is a moving-bed. cooled catalyst enters the lift pot. Conversion in the second stage varies between 15 & 70% with an overall conversion range of 50 to 80%. & the tar separator bottoms may be sent to a vacuum tower from which the liquid feed is produced. (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 Page 10 of 23 . 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. The gas-oil vapor-liquid flows downward through the reactor concurrently with the regenerated synthetic bead catalyst. & volume conversion ranges between 20 & 70% have been recorded. where low-pressure air transports it to the surge hopper above the reactor for reuse. Feed preparation may consist of flashing in a tar separator to get vapor feed. Approximately 70% of the carbon on the catalyst is burned in the upper kiln burning zone & the remainder in the bottom burning zone. The catalyst is purged by steam at the base of the reactor.Part III THE PROCESS & TECHNOLOGY OF CRACKING High temperatures 470 to 565° C are employed to reduce undesirable coke lay-down on catalyst without destruction of gasoline by secondary cracking. g. & gravitates into the kiln or regeneration is done by the use of air injected into the kiln.PETROLEUM TECHNOLOGY. reactor-over-generator continuous process for conversion of heavy gas oils into lighter high-quality gasoline & middle distillate fuel oils. Regenerated.

novel process features modify or eliminate the adverse effects on catalyst & product selectivity usually resulting when heavy metals –iron.PETROLEUM TECHNOLOGY. nickel. Though the equipment employed is similar in many respects to that used in Houdriflow units. flows to the kiln for regeneration. The spent catalyst. sweet or sour. The reactor feed & catalyst pass concurrently through the reactor zone to a disengager section. Houdriflow Catalytic Cracking: This is a continuous. including residua high in sulfur or nitrogen can be employed as the feedstock. The catalyst is transported from the bottom of the unit to the top in a gas lift employing compressed flue gas & steam. in which vapors are separated & directed to a conventional fractionation system. The Houdresid catalytic reactor & catalyst-regenerating kiln are contained in a single vessel. Refer flowsheet below: Page 11 of 23 Catalyst storage . after which steam & flue gas are used to transport the catalyst to the reactor. The charge stock.Part III THE PROCESS & TECHNOLOGY OF CRACKING h. can be any fraction of the crude boiling between naphtha & soft asphalt. moving-bed process employing an integrated single vessel for the reactor & regenerator kiln. & the catalyst is synthetic or natural. & vanadium – are present in the fuel. copper. Fresh feed plus recycled gas oil are charged to top of the unit in a partially vaporized state & mixed with steam. 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. which has been steam purged of residual oil. Residuum cuts ranging from crude tower bottoms to vacuum bottoms.

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 spent catalyst is filtered from the tar. Suspensoid Catalytic Cracking: This was developed from the thermal cracking process carried out in tube & tank units. After leaving the furnace. The latter is separated into gasoline & gases. per barrel of feed). the cracked material enters a bubble tower where they are separated into two parts. Cracking temperatures are 550 to 610° C with pressures of 200 to 500 psi.Part III THE PROCESS & TECHNOLOGY OF CRACKING Light products Houdresid unit Fractionator Feedstock Redu ced crude Fractionator Middle distillates Fuel stocks Recycle Flowsheet for Houdresid catalytic cracking j. The normal catalyst employed is spent clay obtained from the contact filtration of lubricating oils (2 to 10 lb. Small amounts of powdered catalyst or a mixture with the feedstock & the mixture are pumped through a cracking coil furnace. gases) Catalyst Fractionator Feedstock Heater Filter Heavy fuel oil Catalyst Flowsheet for Suspensoid catalytic cracking Page 12 of 23 .PETROLEUM TECHNOLOGY. which is used as a heavy-industry fuel oil. gas oil & pressure distillate. Products (gasoline.

The cracked products leave as overheads. The liquid products from the flash chamber are cooled with a gas oil flux & then sent to a vacuum fractionator. The heated material enters one of a pair of coking drums where the cracking reactions are completed. material in the gas oil & gasoline boiling range is also produced. The temperature in the coke drum ranges from 415 to 450°C Page 13 of 23 . The gas oil produced may be diverted to catalytic cracking units or used as heating oil. Visbreaking conditions range from 455 to 510°C & from 50 to 300 psi at the heating-coil outlet. Liquid-phase cracking takes place at these low-severity conditions. are then heated in a furnace whose outlet temperature varies from 480 to 515°C. with one on stream while the other is being cleaned. which provide the long residence time needed to allow the cracking reactions to be completed. Besides fuel oil (major product). The feed to these units is normally an atmospheric residuum although cracked tars & heavy catalytic oils may also be used. The furnace is designed in a manner such that it contains a soaking section of low heat density. 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 outlet pressure controlled at about 100 psi. The fractionator bottoms. 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. Thus. where the charge can be held until the visbreaking reactions are completed. including a recycle stream of heavy product. drums or chambers (reaction vessels) are employed.Part III THE PROCESS & TECHNOLOGY OF CRACKING 3. a crude oil residuum is passed through a furnace where it is heated to a temperature of 480°C. in order to simultaneously decoke the off-line vessel without interrupting the semicontinuous type of process. Gasoline Feedstock Heavy gas oil Vacuum fractionator Flasher Fractionator Reactor Tar Light gas oil Flowsheet for Visbreaking operations 4. Two drums allow for continuous operation. Normally two or more such vessels are provided. Coking: As mentioned earlier coking processes generally utilize longer reaction times than thermal cracking processes. This yields a heavy gas oil distillate & a residual tar of reduced viscosity. To accomplish this.PETROLEUM TECHNOLOGY. & coke deposits form on the the inner surface of the drum. The cracked products are then passed into a flashdistillation chamber. The process flow is as follows: The feedstock enters the product fractionator where it is heated & lighter fractions are removed as side streams. Visbreaking: As explained earlier visbreaking is a mild thermal cracking operation employed for viscosity reduction of residual or asphaltic feed stocks.

The vapor products pass through cyclones. Fluid Coking: Fluid coking is a continuous process. & the wet coke is removed from the drum. & the pressure nearly atmospheric causing the incoming feed to partly vaporize & partly deposit on the fluidized coke particles. The temperature in the coking vessel ranges from 480 to 565°C. & steam is introduced at the bottom of the reactor to fluidize the bed. 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. which contains substantial quantity of coke dust & is recycled back to the reactor.Part III THE PROCESS & TECHNOLOGY OF CRACKING at pressures from 15 to 90 psi. These cleaning operations normally require 24 hours before the drum can be put into reuse. The vapor is discharged into the bottom of a scrubber where the products are cooled to condense a heavy tar. The overheads from the coking drum go to the fractionator. which remove most of the entrained coke.PETROLEUM TECHNOLOGY. for example 260 to 370°C is injected directly into the reactor. & 3) a hydraulic cutting device. The heavy recycle material is material is combined with preheated fresh feed & returned to the reactor. 2) one of the heads of the coking drum is removed to permit the drilling of a hole through the center of the deposit. leaving a residue. The pitch feed at. including vacuum pitches. fine coke particles. coke particles are circulated between these to transfer heat (generated by burning a portion of the coke) to the reactor. The residuum is coked by being sprayed into a fluidized bed of hot. which uses multiple high -pressure jets. which permit the coking reactions to be conducted at higher temperatures & shorter contact times than can be employed in delayed coking. Fluid coking uses two vessels. a reactor & a burner. to more valuable products. is inserted into the hole. which dries to form coke. Gas Gasoline (naphtha) Gas oil Feedstock Fractionator Coking drum (soaker) Coking drum (soaker) Coke Operative Nonoperative Flowsheet for Delayed coking b. these conditions result in decreased yields of coke with greater quantity of more valuable liquid product being recovered. The upper part of the scrubber tower is a fractionating zone from which coker gas Page 14 of 23 . The reactor holds a bed of fluidized coke particles. which uses the fluidized-solids technique to convert residua. where naphtha & heating oil fractions are recovered. The material on the particle surface then cracks & vaporizes. Moreover.

the coke particles flow down through the vessel into a stripping zone at the bottom. The net coke produced is removed from the burner bed through a quench elutriator drum. The average bed temperature in the burner is 590 to 650°C. Flue gases from the burner pass through cyclones & discharge to the stack.Part III THE PROCESS & TECHNOLOGY OF CRACKING oil is withdrawn for feeding to a catalytic cracking unit. Steam is added to the riser to reduce the solids loading & induce upward flow. at the same time. The size of the coke particles remaining in the system is controlled by a grinding system within the reactor. The process is essentially the Page 15 of 23 . Steam displaces the product vapors between the particles & the coke then flows into a riser. Coke is one of the products of the process. Hot coke from the bed is returned to the reactor through a second riser assembly. where water is added for cooling & cooled coke is withdrawn & sent to storage. The pressure in the burner may range from 5 to 25 psi. In the reactor. which leads to the burner. Decarbonizing: The decarbonizing thermal process is designed to minimize coke & gasoline yields but. to give maximum yield of gas oil.PETROLEUM TECHNOLOGY. During the course of the coking reaction the particles tend to grow in size. Fuel gas Cracked gasoline Fractionator Gas oil Flue gas Coke Burner By-product coke Reactor Feedstock Air Coke Steam Flowsheet for Fluid coking c. & air is added as needed to maintain the temperature by burning part of the product coke. The naphtha & gas from the fractionating zone are taken overhead to condensers. & it must be withdrawn from the system in order to keep the solids inventory from increasing.

For example. pressures range from 10 to 25 psi while heater outlet temperatures maybe 485°C & coke drum top temperatures maybe of the order of 415°C. 25 psi. The coke may further be treated to remove sulfur to produce a low-sulfur coke ( 5%).PETROLEUM TECHNOLOGY. Gas Gasoline Gas oil Fractionator Coke drum Feedstock Flowsheet for Decarbonizing d. Gas and gasoline Coke chamber Coke chamber Coke drum Fractionator Flasher Gas oil Feedstock Fuel oil Flowsheet for Low-pressure coking e. Excessive coking is inhibited by the addition of water to the feedstock. even though the feedstock could have as much as 5% wt/wt sulfur. 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. Low-Pressure Coking: Low-pressure coking is a process designed for a once-through. The process flow is as follows: Page 16 of 23 . but lower temperatures & pressures are employed. low pressure operation.Part III THE PROCESS & TECHNOLOGY OF CRACKING same as the delayed coking process. The process is similar to delayed coking except that recycling is not practiced & the coke chamber operating conditions are 435°C.

& gas oils. The processing conditions i.Part III THE PROCESS & TECHNOLOGY OF CRACKING The feedstock is fed into the pitch accumulator. Commercial Processes for Hydrocracking & Hydrotreating : Since commercial processes for hydrocracking & hydrotreating operate essentially in the same manner i. both hydrogen sulfide & ammonia are very soluble compared with hydrogen & hydrocarbon gases. impregnated on an alumina base. 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. under the high pressure conditions employed. 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 reaction rates are facilitated by use of catalysts. then to the heater (370°C. Hydrofining: This process can be applied to lubricating oils.e. 6. These are removed by the injection of water in which.PETROLEUM TECHNOLOGY. Large quantities of hydrogen sulfide & ammonia are formed when using high sulfur & nitrogen feedstocks for hydrocracking units. with hydrogenation superimposed & with the reactions taking place simultaneously or sequentially. Volatile materials are fractionated. Hydrocracking: Hydrocracking is similar to catalytic cracking. naphthas. The feedstock is heated in a furnace & passed with hydrogen through a reactor containing a Page 17 of 23 . 30 psi).e. 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. The polycyclic aromatics are first partially hydrogenated before cracking of the aromatic nucleus takes place. Hydrotreating catalysts are usually cobalt plus molybdenum or nickel plus molybdenum in the sulfide forms. Also the majority of sulfur & nitrogen is converted to hydrogen sulfide & ammonia. The operating conditions of 1000 to 2000 psi hydrogen pressures & 370°C temperatures are such that appreciable hydrogenation of aromatics will not occur. and. after the cycle is complete. Gas Gasoline Pitch accumulator Coke oven Gas oil Coke Flowsheet for High-temperature coking 5. coke is collected for sulfur removal & quenching prior to storage. 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. & finally to the coke oven where temperatures may be as high as 980 to 1095°C.

& maximum sulfur removal require higher temperatures & pressures. 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. Regeneration requires 10 to 20 hours & may be repeated 50 to 100 times for a given batch of catalyst. Hydrogen Water (vapor) Furnace Reactor Stripper Feedstock Drier Product stream Hydrogen Flowsheet for Hydrofining Unifining: This is regenerative. The catalyst is a cobalt –molybdenum-alumina type which may be regenerated in situ with steam & air. This process is used to upgrade low-quality. & wick-char characteristics. which cause smoke. Contaminating metals. The catalyst is cobalt-molybdenum on alumina & may be regenerated in situ using an air-stream mixture. nitrogen compounds. Ultrafining: It is a regenerative. depending on the feedstock & the degree of treating required.. or flue gas. Reactor operating conditions range from 205 to 425°C & from 50 to 800 psi. Higher-boiling feedstocks. high-sulfur naphthas. fixed-bed. catalyst life is 2 to 5 years depending on the feedstock.PETROLEUM TECHNOLOGY.Part III THE PROCESS & TECHNOLOGY OF CRACKING suitable metal oxide catalyst. The treated oil is pumped to a stripper tower where hydrogen sulfide. Page 18 of 23 . the treated oils cooled & separated from the excess hydrogen. formed by the hydrogenation reaction. After passing through the reactor. is remove by steam. catalytic process to desulfurize & hydrogenate refinery distillates of any boiling range. catalytic process to desulfurize & hydrogenate refinery stocks from naphthas through lube stocks. high sulfur content. such as cobalt & molybdenum oxides on alumina. fixed-bed. along with sulfur.. The tendency of kerosene to form smoke is not affected since aromatics. odor. vacuum. are not affected by the mild hydrofining conditions. The sulfur content of kerosenes can be reduced with improved color. which is recycled through the reactor. In this process the catalyst is usually not regenerated & is replaced after about a year ’s use. & oxygen compounds are eliminated. & the finished product leaves the bottom of the stripper tower.

Conversion may be balanced to provide products for variable requirements. Each stage has a separate hydrogen recycle system. for example with middle distillate feedstocks. The catalyst is regenerated with steam & air at 200 to 1000 hour intervals. The process is used for the same purpose. 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 Page 19 of 23 . depending on whether light or heavy feedstocks have been processed.PETROLEUM TECHNOLOGY. Exact conditions depend on the feedstock & product requirements. fixed-bed catalyst system which operates under hydrogen pressures from 500 to 1500 psig in a temperature range of 205 to 370°C. Sufficient hydrogen to convert sulfur to hydrogen sulfide is obtained by dehydrogenation of naphthenes in the feedstock. Fractionation can also be handled in a number of ways to yield desired products. The processing equipment is similar to that used in Hydrofining.Part III THE PROCESS & TECHNOLOGY OF CRACKING Autofining: The autofining process differs from other hydrorefining processes in that an external source of hydrogen is not required. & hydrogen consumption is of the order of 1000 to 1600 SCF per barrel of feed processed. is separated from the treated oil & is then recycled through the reactor. 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. Hydrogen formed by dehydrogenation of naphthenes in the reactor. The catalyst is cobalt & molybdenum oxides on alumina. as Hydrofining but is limited to fractions with end points not higher than 370°C. & recycle can be taken to extinction if necessary. & operating conditions are usually 340 to 425°C at pressures of 100 to 200 psi.

Page 20 of 23 . liquid. deposition of tar & coke is minimized. The design is based upon a single-stage or a two-stage system with provisions to recycle to extinction. & fine solids entrained in the feed will not lead to reactor plugging. hydrogen is recycled. considerable hydrocracking takes place. make-up hydrogen. feed to the second stage is a mixture of unconverted first-stage oil & second-stage recycle. A two-stage reactor system receives untreated feed. liquid product. 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. Part of the reactor effluent is recycled back through the reactors for temperature control & to maintain the requisite liquid velocity. and the liquid product is either stored directly or fractionated prior to storage & blending. The reactor effluent is cooled by exchange & separates into vapor & liquid. After scrubbing in a lean-oil absorber. which provides essentially an isothermal operation with an exothermic process. The second-stage oil may be either once through or recycle cracking. giving efficient contact among gas. during the reaction. The entire bed is held within a narrow temperature range.Part III THE PROCESS & TECHNOLOGY OF CRACKING H-Oil: The H-Oil process is basically a catalytic hydrogenation technique in which. Oil & hydrogen are fed upward through the reactors as a liquid-gas mixture at a velocity such that catalyst is in continuous motion. The reactor effluent is separated to recycle gas. A modification of H-Oil called Hy-C cracking will convert heavy distillates to middle distillates & kerosene. The can also be added & withdrawn from the reactor without interrupting the continuity of the process. and solid with good mass & heat transfer. Catalyst of small particle size can be used. thereby reducing fuel oil yield. Because of the movement of catalyst particles in the liquid-gas medium. and unconverted oil. and a recycle gas at the first stage in which gasoline conversion may be as high as 60% by volume. The process is used to upgrade heavy sulfurcontaining crudes & residual stocks to high-quality sweet distillates.PETROLEUM TECHNOLOGY.

Part III THE PROCESS & TECHNOLOGY OF CRACKING 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.) Light gasoline Heavy naphtha Light gas oil Heavy gas oil “Light” bottoms “Heavy” bottoms Flowsheet for Gulf HDS process Feedstock Page 21 of 23 Separator (high press. Long on-stream cycles are maintained by reducing random hydrocracking reactions to a minimum.PETROLEUM TECHNOLOGY. virgin.) Reactor Reactor . Hydrogen make-up Hydrogen recycle Lean Absorber Gas Diethanolamine Rich Gas Separator (low press. but if the operating conditions & catalysts are varied. Desulfurization & quality improvement are the primary purposes of the process. light distillates can be produced & the viscosity of heavy material can be lowered. 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. and whole crudes. 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 650°C. or cracked residua may serve as feedstock.

make-up hydrogen. and hydrogen-rich recycle gas. The feedstock is mixed with recycle gas oil. & a final filtering step removes the catalyst fines.PETROLEUM TECHNOLOGY. The catalyst is a threecomponent material on alumina base with low hydrogen consumption & life expectancy of 2 years or more. The oil is then stripped to control the flash point. The reactor effluent is cooled & sent to a high-pressure separator where hydrogen-rich gas is flashed off.) Reactor Product Flowsheet for Ferrofining process Page 22 of 23 . & the bottoms are taken to a fractionator for separation. C2 gases Feedstock (Heavy gas oil) (Recycle) Separator Stabilizer Hydrogen (Make-up) Reactor Fractionator Fuel Gas Filter Stripper/vacuum drier Hydrogen recycle C3. 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.) Separator (low press. scrubbed. Separator liquid passes to a stabilizer for removal of butanes & lighter products.or a two-stage reactor system for conversion of light & heavy gas oils to lower-boiling fractions. Hydrogen Feedstock Gas and steam Separator (high press. dried in vacuum. and then heated & charged to the reactor. 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. any unconverted material is recycled to the reactor. then recycled to the reactor.Part III THE PROCESS & TECHNOLOGY OF CRACKING H-G Hydrocracking: This process may be designed with either a single.

ABB-Lummus Global/Chevron: They are among the top technology & engineering solutions provider for FCC units. Haldor Topsoe AS (Topsoe): They are leading contenders for supply of Hydrotreating technology. Kellogg. The Chemistry and Technology of Petroleum – James G. BASF: BASF is a Germany based multinational & they have developed certain commercial Hydroprocessing technologies. “Reliance Petroleum Ltd. Brink. Speight Publisher: Marcel Dekker.PETROLEUM TECHNOLOGY. Some other companies offering Cracking & Hydroprocessing technologies include CD tech. Brown & Root Inc. One of their specialties is a new selective hydrotreating technology named “Prime G” for ultra low sulfur gasoline.Part III THE PROCESS & TECHNOLOGY OF CRACKING List of know-how suppliers for Cracking Processes: Most oil majors have developed & modified technologies to suit their own particular requirements. “Octgain 125” & “Octgain 220” which shall become very relevant when international norms for sulfur content in motor fuels are brought down to 50 ppm. Inc. 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-à-vis its competitive technology. Norris Shreve & Joseph A. Ltd. 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. Jr. 2. It is important to note that of the various technologies available. (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.”. 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. the largest single-stream refinery in Asia has major processing units designed by UOP. Hydrocrackers & Hydrotreaters. 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. Petrobras (Brazil). Petroleum Refinery Engineering – W. List of reference books: 1. ExxonMobil: They have developed new selective hydrotreating technologies for ultra low sulfur gasolines called “Scanfining”. Shell Development Company (Shell): Shell is a leading company providing technology for visbreaking units & crackers. hydroprocessing & reforming. Chemical Process Industries – R. Akzo. L. 3. Nelson Publisher: McGraw-Hill Kogakusha. Stone & Webster Engineering Corporation (S & W): They specialize in FCC units & have a major share of the world market. Criterion (mainly catalyst suppliers) etc. Publisher: McGraw-Hill International Book Company Page 23 of 23 .