5

THERMAL CONVERSION PROCESSES

.

offered by ExxonMobil Research and Engineering. A discussion of Fluid Coking and Flexicoking is provided in section 5. Fluid Coking and Flexicoking. such as the Burton process. are designed to process special feeds and to produce high value anode grade coke or needle coke.1. These units are normally of small capacity. developed by Standard Oil of Indiana. The feed is heated to the reaction temperature in a direct fired heater. such as an atmospheric or vacuum residue. the oil often underwent thermal decomposition. refiners began to utilize the thermal conversion of VOLUME II / REFINING AND PETROCHEMICALS 213 . the coke removal. handling and disposal are carried out in a batch manner. A by-product of this process was petroleum coke. Coke accumulated in the vessel and was removed manually. 5. Since the temperature of the batch still and the residence time were not well controlled. paved the way for the basic delayed coking process. the coke drums operate in pairs such that one drum is in filling mode.4. Most modern units today are designed and operated to maximize the yield of distillate products and produce fuel grade coke as a by-product. was used to produce gasoline from gas oil.1 Introduction Coking is a thermal cracking process in which a low value residual oil. This type of coker represents the majority of coker installations. and subsequently transferred to the coke drums. Though the coking process is continuous. while the other is off-line for decoking. The coking reaction is delayed until the heated feed is transferred into the coke drums where the residence time is long enough for the coking reactions to go to completion. Coke is removed from the drum by taking the drum off-line. consist of a class of coking processes that are less widely practiced compared to delayed coking. development of continuous distillation processes and improved thermal cracking processes. particularly the needle cokers.1 Coking 5. Later developments included use of multiple stills in series to produce different boiling range products. is converted into valuable distillate products.1.2 Evolution of the coking process and its role in the refinery The delayed coking process represents a natural evolution from earlier thermal cracking processes. The Burton process. off-gas and petroleum coke. Two different classes of coking processes are implemented commercially: delayed coking and fluid coking. Coke accumulated in the first still and was removed using manual techniques. During the late Nineteenth century.5. Delayed coking is a semi-continuous process. refineries employed batch distillation techniques. In order to achieve near steady state unit operation. Some specialized plants. and enters the downstream fractionator. During the 1920s. Coke is deposited in the drum and the cracked vapour product exits the drum from the top. Coking allows the refiner to significantly reduce the production of low value fuel oil. As demand for gasoline in the United States increased and demand for heavy fuel oil (essentially atmospheric reduced crude) decreased. Delayed coking represents the largest combined capacity and is the most widely encountered process.1. the first still was operated at the highest temperature to flash the majority of the crude oil. on the other hand. In this arrangement.

Coke drums downstream of the reaction furnace were employed to collect the increased yield of petroleum coke. decreased decoking cycle time. manual decoking methods were employed. In the early stages. Light Vacuum Gas Oil. in which one was filled and the other emptied at the same time. The term ‘delayed’ was attributed to the fact that the coking reaction is delayed until after the heated feed is transferred into the coke drums where adequate residence time is provided for the coking reactions to reach completion.THERMAL CONVERSION PROCESSES these residue fractions. 214 ENCYCLOPAEDIA OF HYDROCARBONS . it was possible to operate in a semi-continuous fashion. Improvements to the delayed coking process are still being made. Using a two-drum system. LVGO. Heavy Vacuum Gas Oil. HVGO. The delayed coking process was commercially demonstrated by Standard Oil of Indiana at the Whiting refinery in 1929. The growth in demand for motor gasoline from the 1950s through the 1970s saw an increase in the number of delayed coking units constructed that allowed the refiner to convert residual fuel oil stocks into gasoline and gas oil. Early developments included the use of drilling bits and high pressure hydraulic cutting nozzles to remove coke. Residual conversion refinery based on delayed coking. Residual conversion refinery The economics of a refinery can be considerably improved by the addition of a residual light naphtha isomerate C3-C4 LPG crude oil heavy naphtha reformate kerosene diesel kerosene/jet fuel gasoline diesel LVGO HVGO naphtha diesel jet fuel gas oil coker naphtha LCGO HCGO coke C3-C4 olefins light gasoline alkylate diesel heavy gasoline light cycle oil slurry oil Fig. Development of hydraulic decoking methods began in the 1930s and continues to the present day. 1. Process improvements are offered to allow the processing of very heavy residues and to increase liquid yields. The gas oil provided an additional feed to the fluid catalytic crackers which had become the predominant gasoline production units in the refinery. These improvements are offered by various process licensors and specialized equipment suppliers. improved operator safety and advances to allow for larger diameter coke drums and increased capacity. Improvements of the mechanical type generally address increased furnace run length.

• Thermal cracking of heavy stocks proceeds stepwise through a series of progressively lower molecular-weight products. in which the carbon to hydrogen ratio is very high. • With further heating and increased interfacial forces.. The principal reactions can be summarized as follows: • Decomposition of large molecules into smaller molecules. The ratio increases to well over 1. The coker produces a wide range of products. 5. simple chemical compound. 1 (see also Chapter 1. • The other secondary reactions occurring in coking are polymerization and condensation. react with other hydrocarbons.1. In addition.6 – 142 (liquid volume %) 4. During the coking process. Cokers producing needle coke operate at even higher pressures and temperatures. a precise explanation of the reaction mechanism is difficult.1). the state is called the mesophase (or liquid crystal state). or decompose further to olefins and smaller radicals. which are highly reactive and short-lived species. Petroleum coke is a by-product from the coker unit.5 53. which must be processed further in the refinery along with the other intermediate streams. Coker design Table 1. designed to operate at low pressures and low recycle ratios in order to maximize liquid product yields.2 34. and Cϩ 5 naphtha products.075 224 The design features of the coker vary depending on the type of coke to be produced.COKING conversion unit. The vacuum residue is processed in a delayed coker rather than blending into fuel oil.3 Process chemistry Coking reactions Delayed coking is a thermal cracking process.1 0. heavy gas oil to light gas oil to gasoline to gas with reactions occurring simultaneously.0 4. including free radicals. The delayed coker converts the vacuum residue into more valuable lighter products and petroleum coke. When these planar compounds rearrange and become stacked in a fixed direction. It can be described as an impure mixture of elemental carbon and hydrogen compounds. Overall refinery yields based on 50:50 Light Arabian and Heavy Arabian crude mix (100. the recycle amount is also generally high (typically greater than 50%).9 26.8 44. 1981). Ballard et al. and so on. etc. C3-C4 LPG. A schematic diagram of a residual conversion refinery is shown in Fig.000 when the coke is calcined. for example. 1971. often in excess of 20 by weight.000 bbl/d crude rate) Overall Overall refinery refinery yields yields (without coker) (with coker) Product C3 components C4 components Gasoline Jet fuel Diesel Fuel oil Coke (t/d) Sulphur (t/d) (liquid volume %) 3.9 2. The Heavy Coker Gas Oil (HCGO) is hydrotreated as feedstock to the FCC (Fluid Catalytic Cracking) unit while the Light Coker Gas Oil (LCGO) is hydrotreated and blended into the diesel pool.4 5. mesophase spheres form and grow into droplets dispersed in the oil. The decomposition and polymerization reactions result in the formation of polycondensed aromatic compounds. many different chemical reactions occur simultaneously. The spheres continue to grow and coalesce into bulk mesophase. combine with other free radicals resulting in termination. The overall yields from a residual conversion refinery that processes a blend of 50:50 Arabian Light and Arabian Heavy compared to the yields from a refinery without a coker are presented in Table 1. • Free radicals. The coke structure can be related to the chemical and molecular VOLUME II / REFINING AND PETROCHEMICALS 215 . • Further heating results either in ‘mosaic’ or fibrous coke formation.3 19.0 1. Thus. Petroleum coke does not consist of a single. such as a delayed coker. high-pressure jet pumps. They typically include smaller diameter coke drums. nor is it a form of pure elemental carbon. Current designs are mostly fuel grade cokers. The off-gas and the un-stabilized naphtha are further processed in the vapour recovery unit to produce fuel gas.3 1. Cokers producing anode coke are usually subjected to more severe temperature and pressure conditions. with complete conversion of the vacuum residue to solid petroleum coke and hydrocarbon products that are lighter than the feed. although it approaches the latter (SRI Consulting.

the feed is partially vaporized and mildly cracked. given the temperature and residence time in the coke drum. In addition.4 Coking processes Delayed coking Delayed coking represents the largest number of commercial coking units. ϪH) influences its chemical Fig. In contrast to resin and asphaltene molecules. residence time and gas-flow rate. Coking Fresh feed (residue) is delivered into the bottom of the fractionator where it is mixed with the Simplified delayed coking flow scheme. vapours to recovery off-gas LPG water slop oil water naphtha sour water fractionation tower coke drums steam LCGO HCGO make-up water steam coke BFW steam pumparound BFW residue feed coker heating 216 ENCYCLOPAEDIA OF HYDROCARBONS .) may be present in both the side chains and the ring structures. the reaction mechanism of delayed coking is complex. b) fractionation. not of individual members capable of being broken up on heating. A simplified flow diagram of the delayed coking process is shown in Fig. The coke produced is more crystalline in appearance than asphaltic coke obtained from conventional vacuum residues. in the coke drum. BFW. 2. etc. but of condensed polycyclic nuclei having short methyl and other side chains. polymerized and condensed to coke.THERMAL CONVERSION PROCESSES composition of the feedstocks. Needle coke formation mainly involves the polymerization and condensation of the aromatics to such a degree that coke is eventually formed. d ) closed blowdown. Petroleum cokes have an unordered crystalline structure. ϪSH. The delayed coking flow scheme can be divided into the following sections: a) coking. c) vapour recovery. In summary. Structure of petroleum coke reactivity. the structural model of the carbenes and carboids that constitute most of petroleum coke probably consist. Main process sections Numerous studies have been performed to explain the formation and the structure of a coke. 2. but three distinct steps occur in the entire coking process: in the furnace. etc. Boiler Feed Water. The dimensions and ordering of the coke crystals are the principal factors in determining its physical properties (thermal conductivity. density. The most critical operational factors are the temperature.). and the heavy liquid feed. S. is simultaneously cracked to vapour. which have an effect on coke calcining technology.1. N. Heterocompounds are present in very small amounts and play only a small role in the coking mechanism. Heterocompounds (with O. 5. coke contains 2-10% of adsorbed intermediate decomposition products. electrical conductivity. the vapours crack as they pass through the drum. while the type of side chains (ϪCH3. and e) coke removal.

Gas oil is injected into the coke drum overhead line to quench the product vapours and minimize coking in the line. Vapour recovery flow scheme. while the hydrocarbon vapours exit the drum at the top and are sent to the bottom of the fractionator. With low recycle designs. The heavier portion of the coke-drum vapours condenses in the wash section to form the recycle. reduce residence time and thus minimize coking in the heater tubes. 3. Coke accumulates in the coke drums as it forms over the period of the coking cycle. Coking reactions occur in the coke drum producing coke and light hydrocarbon vapours. The uncondensed vapour is separated in the overhead drum and sent to the vapour recovery section for LPG (Liquefied Petroleum Gas) recovery. The coker gas oil pumparound heat is typically used to preheat fresh feed. which is mixed with the fresh feed and returned to the heater. An open spray chamber design is commonly employed in such designs. the internals near the bottom of the tower are minimized due to the potential for coking deriving from the low wash oil rates. cooled and sent to storage. 3. A portion of the coker gas oil is pumped back to the wash section below as wash oil. The fractionator wash water fractionator overhead liquid sponge absorber fuel gas to treating light gas oil rich light gas oil fuel gas wet gas compressor fractionator vapour sour water primary absorber LPG to treating stripper wash water naphtha to hydrotreating sour water Fig. A part of the condensed liquid is returned as reflux to the top of the fractionator and the remaining overhead liquid is sent to the vapour recovery section for stabilization. Fractionation The most conventional fractionator design has shed decks above the feed zone with a trayed wash section immediately above the decks. Vapour recovery A simplified flow scheme of the vapour recovery is shown in Fig. Heavy Coker Gas Oil (HCGO) is withdrawn as a total draw-off. High pressure steam or condensate is injected into the heater tubes in order to maintain a minimum fluid velocity. the feed is rapidly heated to the coking temperature and sent to the coke drums. The total feed is then pumped from the fractionator bottom to the coker heater. provide reboil heat in the vapour recovery towers and to generate steam. The next side-draw product. A portion of the unstripped LCGO is used as lean sponge oil in the secondary absorber of the vapour recovery section. In the heater. Sour water collected in the overhead drum is sent off-site for treating. The coke drum vapours pass through the shed decks. is steam stripped in a side stripper to remove the light ends. debutanizer VOLUME II / REFINING AND PETROCHEMICALS 217 . wash section and enter the gas oil fractionation section where a circulating gas oil pumparound is used to remove heat and to condense the gas oil vapours. Light Coker Gas Oil (LCGO).COKING recycle material from the wash section. Rich sponge oil is returned to the fractionator for recovery of the absorbed hydrocarbons. The fractionator overhead vapours are partially condensed in an overhead condenser.

shown in Fig. steam stripped. and therefore a portion of the stabilized naphtha from the downstream debutanizer is cooled and recycled to the top of the absorber as supplemental lean oil. is used to separate and recover hydrocarbon and steam vapours generated during the coke drum steaming and cooling operations. and Cϩ 5 as bottom product. this lean oil is insufficient to achieve the desired LPG recovery. is condensed in the overhead condenser before entering the blowdown drum. The vapours generated during steaming and quenching are routed to the blowdown scrubber for condenser blowdown drum to vapour recovery blowdown scrubber slop oil to reprocessing slop oil tank to sour water flash drum coke handling return water water make-up coke drum blowdown LCGO make-up heavy oil to fractionator jet water to coke drums quench water to coke drums quench water tank 218 ENCYCLOPAEDIA OF HYDROCARBONS . etc. The net bottoms from the blowdown scrubber. The overhead gas from the absorber containing mostly C2 and lighter and some unrecovered C3s is fed to the bottom of the sponge absorber where it comes into contact with lean sponge oil. mostly steam and light hydrocarbon vapours. and sent for further processing. light oil is separated from the steam condensate and pumped to the refinery slops system. Any C5 and heavier hydrocarbons present in the absorber off-gas are recovered in the sponge absorber and returned to the fractionator as rich sponge oil. The bottoms from the stripper.. initially for further treating in a sour water stripper and later sent to the clear water tank for reuse in coke cutting. and quenched by water. mercaptans. 4. Closed blowdown The closed blowdown system. are removed and returned either to the fractionator or sent to the refinery slops system. Normally. containing wax tailings. including hydrogen sulphide. and the resulting vapour and liquid streams are fed to an absorber-stripper. flows to the debutanizer where LPG is recovered as an overhead liquid product.THERMAL CONVERSION PROCESSES overhead vapour is compressed and cooled. The vent gas from the blowdown water separator is returned to the wet gas compressor or other suitable refinery hydrocarbon recovery systems. The Cϩ product is cooled and sent 5 to storage. Coke removal The coke drum filled with coke is taken offline. 4. containing C3s and heavier. The coke drum blowdown vapours are condensed in the blowdown scrubber by contact with circulating oil drawn from the bottom of the blowdown scrubber. The overhead C3-C4 LPG is further treated to remove sulphur compounds. Fig. The vapour is fed to the bottom of the absorber while the liquid is fed to the top of the stripper. The uncondensed vapour. while the recovered water is pumped off-site. Closed blowdown system. In the blowdown drum. The fractionator overhead liquid stream is introduced into the top of the absorber as lean oil. The sponge absorber overhead off-gas is finally treated with an amine solution to remove hydrogen sulphide before discharging into the refinery fuel gas system.

Coke drums of about 9 m diameter are currently in commercial use.COKING Fig.8 double-fired type peak flux average ϭ1. which. The actual outage is determined based on the type and origin of feedstock. while the cycle time sets the drum volume. thin flames hydrocarbon and steam recovery. direct rail car and hydraulic coke handling. The vapour velocity typically determines the drum diameter. New designs employ steel alloys containing 9% Cr and 347 SS tubes. Coke drum Coke drum sizing is governed by the superficial vapour velocity. single-fired type peak flux average ϭ1.8 to 2. The coke drum shell is fabricated from alloy steel (typically 1-Cr and 0. which is indicative of the progress of coking in the drum and preparation for the drum switching. The allowable drum vapour velocity is a function of the vapour density and the foaming tendency of the feedstock. The coke drum level. which is the disengaging height between the top tangent line and the maximum coke level in the drum. Modern designs and retrofits use shorter cycle time of the order of 14-18 hours. thereby greatly reducing the residence time and the potential for coking in the heater tubes. and the average radiant heat flux is approximately 43. although some units run at velocities higher than 0.5Mo) with a stainless steel (410S. coke pad loading. is monitored by a nuclear backscatter level instrument mounted on the outside of the coke drums. Various coke handling methods are in use. is common in modern cokers. cycle time and the allowable outage. resulting in lower peak temperatures and shorter residence time. Heater tube metallurgy is also being enhanced.1 to 0.2 m/s. Single-fired vs. usually a four-way ball valve. in which the heat input is from both sides of the tube. The foaming in the drum is controlled by the addition of anti-foam chemicals (generally as a mixture with a distillate fluid) during the last few hours of the fill cycle. The switch valve also allows the drum to be bypassed during unit start-up and shutdown. for a given drum diameter. These are also used to detect the foam levels as the drum fills up.2 outlet old burners bushy flames outlet outlet outlet modern low NOx burners long. The most commonly used methods are coke pit and coke pad handling. 11-13 Cr) cladding. 5. including coke pit loading. cokers were designed with coking cycle times of 20 to 24 hours (overall drum cycle of 40-48 hours). There are two principal types of heater design in use today: single-fired heaters or a double-fired heaters (Fig. The drum outage.2 m/s. Steam injection in the radiant section. This arrangement allows higher average heat flux. Major design considerations Coker heater The coker heater provides the necessary heat to the feed in order to reach the coking reaction temperature. is typically in the range of 4 to 6 m. A switch valve. Coke is removed from the drum by hydraulic decoking. The cycle time schedule sets the total volume required for the coke drum. which permit higher skin temperatures and allow longer run lengths to be achieved. Steam is injected in order to increase the fluid velocity. In modern cokers the double-fired heater designs are mainly used. particularly when processing heavy feeds. VOLUME II / REFINING AND PETROCHEMICALS 219 . double-fired coker heater. Typical drum vapour velocities are in the range of 0.000 W/m2. essentially sets the overall dimensions for the coke drum. The cold-oil velocities vary from 1. located at the drum inlet is used to switch the feed between the drums. its foaming tendency and the operating conditions.4 m/s. 5). In the past.

220 ENCYCLOPAEDIA OF HYDROCARBONS . The hydrocarbon conversion reactions occur in the reactor. A slotted standpipe in the bottom of the fractionator is used for collecting the coke particles and to provide passage to the heater charge pump. LCGO. including wet gas. up to the HCGO draw-off pan. are in commercial use. feed net coke hot coke air steam cold coke Fig. where maximizing liquid yields is the primary objective. is employed in order to remove the accumulated coke from the bottom of the fractionator to minimize unit downtime. Modern designs therefore minimize tower internals at the bottom of the fractionating tower. vapour recovery and coke-handling systems are similar to those used in the delayed coking process. Also. 6. and reaction product vapours fluidize the bed as they rise toward the reactor cyclone and scrubber. overhead condenser.. Blowdown scrubber A generic flow diagram of the Fluid Coking process is shown in Fig. Fluidized coking processes are a specialized class of coking processes that consume part of the coke produced to supply the necessary endothermic heat of reaction for thermal cracking. Cokers with recycle less than 5% are considered ultra-low recycle operations. New coke produced from the cracking reactions is deposited on the coke particles in the reactor bed. A demulsifying agent is added to the blowdown overhead water separator to aid the oil/water separation. The bottom section of the fractionator. Recycle is produced at the fractionator bottom by condensing the heavier portion of the coker gas oil. water separator.THERMAL CONVERSION PROCESSES Coker fractionator Other coking processes Delayed coking represents the largest number of commercially practised coking units. Higher recycle produces more coke at the expense of gas oil yields. 2003). is highly prone to coking due to the entrained coke particles as well as the high-temperature vapourphase coking. bottom heater and the associated pumps. however the HCGO end point decreases. The fractionation. Stripping steam is injected at the bottom of the reactor. preheats the fresh feed. 6. Another significant function of the blowdown system is to handle the coke drum emergency relief discharge during any drum overpressure event. Simplified Fluid Coking scheme. Below 150°C. cools the reactor effluent vapours. Coker recycle Coker recycle is one of the key operating variables in a coker to control the HCGO end point as well as to reduce the coking propensity of the heavy feed in the heater tubes. A scrubber. and other impurities like Conradson Carbon Residue (CCR) and metals are also reduced. circulating oil cooler. low to ultra-low recycles are used. Feed enters the reactor into the fluidized bed of coke. removes coke particles entrained by the vapours. The drum blowdown temperature varies from a maximum of 450°C at the start of the cooling cycle to about 150°C near the end of the cycle. with some designs using an open spray chamber below the HCGO pan. the drum effluent bypasses the scrubber and is sent directly to the blowdown overhead condenser. a separate coke removal system. consisting of a circulating pump and coke filters. and condenses the heavy recycle stream. gasoline. The reaction section entails two primary vessels: a coking reactor and a heater. In fuel grade cokers. licensed by ExxonMobil Research and Engineering (EMRE). and HCGO. The blowdown system includes a blowdown scrubber. In product to fractionator flue gas to CO boiler The blowdown scrubber recovers and provides primary separation of the hydrocarbons and the steam that are generated during the coke drum steaming and cooling operations. located on top of the reactor. which is then mixed with the fresh feed and sent to the heater. Detailed information on these technologies and their applications can be found in an article by EMRE (Hammond et al. Fluid Coking The coker fractionator separates the coke drum vapours into various products. The Fluid Coking and Flexicoking processes. This figure and the description that follows apply to the Fluid Coking reactor system only.

The gasifier is also used to heat the circulating coke and supply the heat required for the coking reaction. Fluid Coking and Flexicoking processes are similar. The net coke produced by the process exits the heater.4 wt% carbon residue feedstock) Product yields Butanes and lighter (wt%) C5 . Fig. To provide bed level control in the reactor.5-4. Flexicoking Table 2. 7. treated to remove coke fines and processed to remove H2S.1 65. This gas is normally cooled. Typical yields from Fluid Coking and Flexicoking (4. and a vertical riser.4°API and 24.6 18. The gross coke quantities produced from delayed coking. The heat input required to achieve thermal conversion is also similar among the processes. Heat required to support the coking reaction is obtained by partially combusting a portion of the gross coke produced in the reactor. The Flexicoking process produces a large quantity of low heating-value gas. About 90-97% of the gross coke produced is consumed by the Flexicoking process. an angle riser. hot fluidized coke is circulated from the heater to the top of the reactor through the hot coke line. The Flexicoking process consumes additional coke to produce a synthetic gas product.7 0.510 °C (vol%) Gross coke (wt%) Net coke (wt%) Low BTU gas (FOE-vol%) FOE. Fuel Oil Equivalent Fluid Coking 13.8 The objective of the Flexicoking process is to further reduce the amount of net coke produced in the reactor by utilizing a gasifier to convert the net coke to a synthetic gas. The flue gas. A flow diagram showing the Flexicoking process is provided in Fig. 7.9 – Flexicoking 13.1 30. The net coke low BTU gas Flexicoking scheme. cold coke from the bottom of the reactor stripper section is circulated back to the heater through the cold coke line. The cold coke from the reactor is heated by direct contact with hot gas. 3. Typical yields for processing an Arabian vacuum residue provided by the process licensor (ExxonMobil Research and Engineering) are shown in Table 2. sulphur oxides (SOx) and inerts. Fluid Coking consumes about 20% of the gross coke produced to supply heat required for the coking reaction. The yield of liquid product and gross coke production are the same.1 30.8 MJ/m3). Each of the transfer lines consists of a standpipe. The heater normally operates at about 500-600ºC and slightly above atmospheric pressure. Simplified All coking processes are severe thermal conversion processes and accomplish that conversion using much the same reaction mechanisms. The gas can be utilized in burners designed to handle low heating-value gas (approx. product to fractionator steam Venturi scrubber feed tertiary cyclones dry coke fines ejector wet coke fines purge coke steam air steam VOLUME II / REFINING AND PETROCHEMICALS 221 .COKING order to supply heat and maintain reactor temperature.7 24. a sharp angle bend. can be utilized in a CO-boiler. which contains mostly carbon monoxide (CO).1 65.

aromatic extracts from lube operations.1. The major utility cost for a fluid coker or flexicoker is associated with the air blower. depending on the overall economic objectives.37 – – 222 ENCYCLOPAEDIA OF HYDROCARBONS . The conditions vary significantly between the three types of coking operations. reduces liquid yields and reduces the gas oil end point. The operating conditions are selected depending on the feedstock quality and the process objectives.0 161 46 Slurry oil FCC 1. and pyrolysis tars from ethylene plants.041 4.1 8. metals and asphaltenes. a variety of other refinery residual feedstocks and intermediate products can also be processed in the delayed coker. and coke drum temperature. Feedstocks Heavy aromatic stocks such as the decant or slurry oil produced from FCC units. Coke drum pressure The reference pressure at which coking reactions take place is generally considered to be the operating pressure at the top of the coke drum. Increasing coke drum pressure also increases gas and gasoline yields. from the distillation processes and asphaltenes produced from deasphalting.21 –1. On the other hand. Table 3.01 9.5 Process variables This section provides a description of coker feedstocks.5 5. The three primary operating variables that affect product yield and quality are: coke drum pressure.22 – – Needle coke Thermal tar Thermal cracker 1. While the typical feedstock to a coker is a straight-run vacuum residue. These properties determine the quality of coke produced as well as the entire slate of the coker products. product yields and quality of the various coker products and the variables that affect the yields and product qualities. The ability of a coker to handle a variety of feedstocks is demonstrated by the range of the gravity (Ϫ5 to ϩ15°API) and carbon residue (4 to 40 wt%) of the materials it can process. The above feedstock classification leads to different qualities of the by-product coke produced.0 0. Operating variables Delayed cokers can process practically any heavy oil material in the refinery.5 25.9 0.0 5. Capital costs for a fluid coker are approximately the same as those for a delayed coker. the feedstock properties that affect the yields and product quality are: the specific gravity. CCR. and the content of sulphur. such as the atmospheric and vacuum tower bottoms. Increasing coke drum (coking) pressure increases coke yields. The properties of some typical feedstocks are summarized in Table 3. slop oils.9 39 89 Fuel grade coke Vacuum residue 50:50 Light/Heavy Arabian Mix 1.6 0. The feedstocks to a coker can be classified into the following main categories: • Straight-run residual material. • 5. Typical coker feedstock characteristics Anode coke Feedstock Feedstock source Specific gravity at 15°C API gravity Conradson carbon (wt%) Sulphur (wt%) Vanadium (ppm) Nickel (ppm) Vacuum residue African crude 1. In addition to the origin and upstream treatment. the capital costs for a flexicoker are greater (30-40%) than for a fluid coker because of the need for an additional gasifier vessel. • Other materials such as visbroken tars.2 18. thermal tars from thermal cracking units. recycle ratio.THERMAL CONVERSION PROCESSES produced using the Flexicoking process for the same feedstock is substantially reduced compared to the Fluid Coking process. gas clean-up and the requirement for a larger air blower. etc. tank sludge bottoms. The pressure is actually controlled at the reflux drum near the top of the coker fractionator. and coal tar pitches.052 3.

Table 5. needle cokers often run with recycle ratios of 50 to 80%. While anode cokers are typically limited to recycle ratios of 25 to 30%. As the recycle ratio is increased. the narrow range of furnace outlet temperatures at which a given feed must be run is critical for the smooth operation of the unit and the maintenance of reasonable furnace run lengths.5% carbon residue feedstock) Past designs Drum pressure (bar) Recycle ratio (vol%) Coke yield (wt%) C5 plus liquid yield (vol%) 2. the range of coker operating conditions can vary significantly. hydrocracking and fluidized catalytic cracking technologies. Table 4 shows the effects of drum operating pressure and recycle on delayed coker yields at a given drum temperature (Sloan et al. plant operability and hardware limitations. While drum temperatures for anode cokers are only slightly higher (5°C). and a lower gas oil end point. Recycle ratio The recycle ratio represents the amount of recycle material (typically 540°C plus) produced at the bottom of the coker fractionator and recycled back (along with the fresh feed) to the heater and coke drum for additional cracking. valves up to the quench point) may be subject to excessive coking which could lead to increased unit downtime. 1992.5 5-10 435-440 Anode coke 1. To produce anode grade or needle coke. with advances in hydrotreating.5-3. 4 to 6 bar. it is not uncommon to operate needle cokers at much higher pressures..1 69. as limited by the capability of the Coke drum temperature is a key operating variable in a delayed coker. reduced liquid yield. Too low a furnace outlet temperature leads to incomplete coking reactions in the drum. higher operating pressures are employed and generally justified because of the higher value coke produced from those units. the drum overhead system (overhead piping. reducing the drum pressure and recycle can potentially contribute to shot coke formation. Bansal et al. produces a hard coke that would be difficult to remove from the coke drum.0-7. A higher drum temperature can only be achieved through a higher furnace outlet temperature. With heavier feeds containing high CCR and asphaltenes. It should be recalled that fuel grade cokers typically run at a drum temperature of about 435-440°C. Effect of low pressure and low recycle on coking yields (20.0 25-30 440-445 Needle coke 4. While anode cokers are typically limited to 2 to 3 bar pressures.. cokers are being designed and revamped to operate at pressures as low as 1 bar. Range of coker operating conditions Fuel grade Drum pressure (bar) Recycle ratio (vol%) Drum temperature ( °C) 1. With anode or needle grade coke production. with many operated at recycle rates of 2 to 3%.COKING Table 4. while today. which results in the production of soft coke.7 72. The higher coke yield leads to more gas and gasoline yields also. which could result in excessive furnace tube coking and the need for frequent tube cleaning. as shown in Table 5. Coke drum temperature In old designs. in the 450 to 460°C range. Today.1 10 32.0 50-80 450-455 VOLUME II / REFINING AND PETROCHEMICALS 223 . greater amounts of HCGO contaminants can be tolerated and cokers are designed with recycle ratios of 5% or lower. Although the drum temperature is not directly controlled. The optimum temperature at which the drum must be operated for a given feed is a compromise between the yield benefits. higher recycle ratios are commonly used and justified because of the higher value coke produced. Also. drum operating pressures of 2 bar were common for sponge coke production. needle cokers typically run at much higher drum temperatures.0-1. on the other hand.7 Current trend 1. carbon residue and metals. A very high temperature. higher drum temperatures are required to produce a coke with the required properties.0 5 29. With these key operating variables in mind. Higher recycle rates produce cleaner HCGO with lower end point.6 downstream units to handle contaminants. When producing anode or needle grade coke. 1993). the resulting effects are an increased coke yield. In the past. conventional cokers were designed with recycle ratios of 10 to 15% in order to produce cleaner gas oils.

Essentially all feed metals are retained by the coke.6 20.0 10.9 100.0 30.6 18.8 7.7 35.4 100.8 0. 224 ENCYCLOPAEDIA OF HYDROCARBONS .5 39.857 33.0 8. These yield estimates are developed using the KBR (Kellogg Brown and Root) yield models.2 0.09 60 – LCGO 0.0 Slurry Oil FCC Needle coke Thermal Tar Thermal Cracker Table 7. PONAs.2 26. Research Octane Number.9 32. Delayed coker product properties based on 50:50 light Arabian and heavy Arabian crude mix Coker naphtha Specific gravity at 15°C API gravity Sulphur (wt%) Nitrogen (wt%) Bromine number Cetane index RON Carbon residue (wt%) PONAs (vol%) Paraffins Olefins Naphthenes Aromatics 45.5 2.0 8.9 46. The estimated properties for various coker products are summarized in Table 7 for the Arabian crude feed blend. Included in the table are the following yield cases: low sulphur and low CCR residue feedstocks suitable for anode grade production. In general.3 44.0 100. which is indicative of the degree of olefinicity.0 9.3 RON. product specifications. Typical delayed coker yields Anode coke Feedstock Feedstock source Dry gas C3-C4 components Gasoline (C5-205°C) LCGO HCGO Coke Total Vacuum Residue African crude 4. and highly aromatic feedstocks that produce needle coke.3 4.14 30 40 – – HCGO 0.65 0.946 18.8 20.5 0. all coker products are highly olefinic.0 3.THERMAL CONVERSION PROCESSES Table 6. The sulphur and nitrogen are distributed among the various products with coke retaining a major portion of the feed sulphur and nitrogen. The bromine number. Coker product properties Coker products are set primarily by the refinery product slate.40 12 – – 0.6 100.9 31.0 – – – – – – – – 80 0. The product treatment steps and the end usage are summarized in Table 8. high sulphur and high CCR residue feed with high metals that produce a fuel grade coke.740 59.5 7.0 Fuel grade coke Vacuum Residue Arabian mix Yields (wt%) 6. ranges between 10 and 70.0 15. and the ability of the refinery process units to handle their further processing.1 15. Paraffin Olefin Naphtenes Aromatics Product yields Typical coker yields for conventional residual oils as well as those for needle coker feedstocks are summarized in Table 6.0 4.

Typical anode coke specifications Specification (wt%) Moisture Volatile Combustible Material (VCM) Sulphur Silicon Iron Green coke 8-12 8-12 1. the feed sulphur and metals content need to be sufficiently low so that the produced coke can meet the desired specifications.0 6.02 0. and ethylene. ultimately. Typically.02 0. Generally. Coke quality paraffinic or asphaltic materials. Heavy coker gas oil is also sent for hydrotreating or hydrocracking along with the virgin vacuum gas oil and is ultimately sent as feed to the FCC unit. widely used in the aluminium industry for the manufacture of electrodes (also called anode coke). ethane.06 Many delayed cokers produce a regular grade coke also known as anode coke. is porous and exhibits structural consistency.02 0.25 0.02 0. used primarily in power and cement plants as fuel. There are essentially three grades of coke currently being produced in the petroleum industry: regular grade sponge coke.02 0. Light coker gas oil is typically blended with other diesel range materials from other refinery units and sent for further hydrotreating for low sulphur (Ͻ500 ppm) or ultra-low sulphur (Ͻ10 ppm) diesel production. containing most of the coker LPG and some heavier hydrocarbons and must be processed in a Vapour Recovery Unit (VRU) to recover LPG and a gasoline product.0-3. This coke has a sponge-like structure.5 1. The quality of coke produced can vary significantly depending on the residue feed being processed.000 10-12 141 489 880 The coke quality not only determines the unit economics but also influences its operability. and fuel grade coke. a small amount of hydrogen produced is present in the dry gas. Also. Regular (anode) coke Table 10.0-3. Typical specifications for the anode coke are shown in Table 10.03 0. high grade needle coke.02 (kg/m3) (g/cm3) 720-800 – Calcined coke 0. for catalytic reforming for octane improvement before blending with the finished gasoline product. Coker gasoline is recovered and stabilized in the VRU and sent for hydrotreating and.5 0. Table 9.03 720-800 2.3 0. a premium coke used to manufacture electrodes for the steel industry. reliability. This gas is usually produced as ‘wet’ gas from the gas separator. Typical coke properties are summarized in Table 9. operations. Typical coke properties Property Sulphur (wt%) Nitrogen (ppm) Volatile material (wt%) Vanadium (ppm) Nickel (ppm) Bulk density (kg/m3) Value 7. The anode coke is generally produced from Nickel Ash Vanadium Bulk density Real density VOLUME II / REFINING AND PETROCHEMICALS 225 . anode grade coke has less than 3 wt% sulphur and no more than 350 ppm by weight total metals.COKING Table 8.5 0. Coker product treating steps and end use Product C3-C4 olefins Light naphtha Heavy naphtha LCGO HCGO Treating step Mercaptan extraction Mercaptan extraction Hydrodesulphurization Hydrodesulphurization Hydrodesulphurization Hydrocracking LPG Alkylation feed Gasoline blending Isomerization feed Reforming feed Gasoline blending Diesel blending FCC feed End use Coker gas includes hydrocarbons such as methane. maintenance and safety.04 0.

the green coke is calcined in a rotary kiln. This coke is thus referred to as fuel grade.1 720-800 – – Calcined coke 0.69 1. All premium needle cokes have a low CTE. Typical needle coke specifications are shown in Table 11. residence time and rate of cooling. In addition.5 0. Coke calcining With the current trend in refineries to process heavy crude oils.5 0. • Quench water management. pyrolysis tars from ethylene plants and some coal tar pitches are considered potential coker feeds for needle coke production.25 226 ENCYCLOPAEDIA OF HYDROCARBONS . Process heat is supplied through a fuel burner. It is used primarily for the production of electrodes for the steel industry (electric arc furnaces). Many new and existing cokers have switched to processing heavy crude oils in order to achieve improved refining economic margins. From the kiln. such as rate of heating. Due to very high sulphur. either anode or needle coke. Cokes with varying amounts of the volatile matter can be burned in the kiln. Petroleum coke (green coke).11 5. metals and other impurities present in the heavy feedstocks. low Coefficient of Thermal Expansion (CTE). Typical specifications of green coke vs. Fuel grade coke are essentially mechanical and are too specific for the purposes of this work. aromatic extracts from lube operations. sulphur and metals. In the following section we will briefly describe the coke calcining process.2-0. such processes are frequently performed outside the petroleum refinery. Calcined anode coke is used mostly in the manufacture of anodes for the aluminium industry. In a typical coke calcining plant.1 670-720 1-5и10Ϫ7 2. In addition.5 1. the Table 11. calcined coke are presented in Table 10 and Table 11.1. The other operations CTE (°C) Real density (g/cm3) Table 12.5 0. is calcined in rotary kilns. • Automated drum unheading (removal of the top and bottom heads). This change results in the production of poorer quality coke that is not suitable for anode production. Needle coke production requires a special feedstock.8 0. Usage of calcined coke User industry Aluminium Silicone carbide Phosphorous Calcium carbide Graphite Calcined coke usage (kg/kg) 0. Typical needle coke specifications Specification (wt%) Moisture Volatile Combustible Material (VCM) Sulphur Ash Bulk density (kg/m3) Green coke 6-10 4-7 0. the industry continues to see a major shift in terms of coke quality. • Coke receiving and water drainage.THERMAL CONVERSION PROCESSES Needle coke This form of coke is the most valuable of all the various petroleum cokes produced. The characteristics of the calcined coke depend primarily on the properties of the green coke fed to the calciner as well as the major operating variables. The coke is uniquely characterized by properties such as its low sulphur and metals content. hot zone (calcining) temperature. the coke produced is only suitable for fuel purposes. which is typically high in aromatics.1 0.2-0. its needle like crystalline structure and high electrical conductivity. either in power plants or the cement industry.4 1. and low in asphaltenes.6 Support process operations The support (auxiliary) operations include some of the key mechanical operations associated with the delayed cokers and the coke calcining processes: • Decoking operation (removal of coke from coke drums). Typical feedstocks include slurry or decant oil from FCC units or thermal tars from gas oil thermal cracking units. • Coke calcining. the coker unit must be operated at conditions that will provide the best premium needle coke quality. Another source of the process heat is the volatiles which are released in the kiln. • Hydraulic decoking by high pressure water jets. Consumption of calcined coke in specific user industries varies considerably as shown in Table 12.

30 March-3 April. (1981) Thermal cracking. Northup Rao Uppala Kellogg. Bharat B. Bansal B.G. XIII.COKING calcined coke is discharged into a rotary cooler where it is quenched with direct water sprays at the cooler inlet. Sloan H. References Ballard W. in: Proceedings of the National Petroleum Refiners Association annual meeting. the calcined coke is conveyed to storage silos. (1992) Delayed coking has a role in clean fuels environment. New Orleans (LA). Bansal Joseph A. Texas. «Fuels Reformulation». Fruchtbaum Aldrich H. et al. in: Proceedings of the American Institute of Chemical Engineers Spring national meeting. Additional cooling is accomplished by pulling a stream of ambient air through the cooler. New York. San Antonio (TX). in: McKetta J. 21-23 March. USA VOLUME II / REFINING AND PETROCHEMICALS 227 . From the discharge of the cooler.P.D. v.J. Process Economics Program Report 72. et al. (editor in chief) Encyclopaedia of chemical processing and design. et al.B. et al. (2003) Review of fluid coking and flexicoking technologies. (1993) Design and economics for low pressure delayed coking. Hammond D. Marcel Dekker.. 1976. Brown & Root Houston. July-August. SRI Consulting (1971) Petroleum coke.

Sign up to vote on this title
UsefulNot useful