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• After desalting and dehydration, crude is separated into fractions by distillation. • The distilled fractions can not be used directly. • The reason for such a complex set of processes is the difference between the crude oil properties and the needs of the market. • Another reason for complexity is environmental. Legislation demands cleaner products and is the major drive for process improvement and development of novel processes.
Flow scheme of a typical refinery
Physical and chemical processes
Distillation Solvent extraction Propane deasphalting Solvent dewaxing Blending
Chemical Thermal Catalytic
Visbreaking Delayed coking Flexicoking Hydrotreating Catalytic reforming Catalytic cracking Hydrocracking Catalytic dewaxing Alkylation Polymerization Isomerization
Coking Coking is a severe method of thermal cracking used to upgrade heavy residuals ("bottom-of. Coke can be formed from the condensation of polynuclear aromatics (such as nbutylnapthalene) .the-barrel”) into lighter products or distillates.
Some thermodynamics .
For reaction 3 .
Delayed Coking • Coking is a severe method of thermal cracking used to upgrade heavy residuals ("bottom-of. • It is the process mostly used today – other processes compared with delayed coking • First developed in 1928. in early refineries extensive thermal cracking would result in deposit of unwanted coke in the heaters.the-barrel”) into lighter products or distillates. .
Coking • Solution: raise rapidly the temperature of the residue above the coking point without depositing the coke in the heater itself. but before subsequent processing. which doubled the run length and led to the development of the art of switching coke drums while still maintaining operation . • The next step was to add a second coke drum.In the early 1930s the drums were limited in size to 10 ft in diameter. Provision of an insulated surge drum downstream of the heater so that the coking took place after the heater. Coke drums as large as 30 ft in diameter have recently been installed .
Delayed Coking .
Delayed Coking .
where the charge is rapidly heated to the desired temperature level for coke formation in the coke drums.Coking section • Reduced-crude or vacuum-residue fresh feed is preheated by exchange against gas oil products before entering the coker-fractionator bottom surge zone. • The fresh feed is mixed with recycle condensed in the bottom section of the fractionator and is pumped by the heater charge pump through the coker heater. .
• The total vapors rise upward through the drum and leave overhead. where the trapped liquid is converted to coke and light-hydrocarbon vapors.Coking Section • Steam is often injected into each of the heater coils to maintain the required minimum velocity and residence time and to suppress the formation of coke in the heater tubes. which it converts to coke and gas while the other drum is being decoked. • The vapor-liquid mixture leaving the furnace enters the coke drum. . • A minimum of two drums is required for operation. One drum receives the furnace effluent.
These operations clean and cool the effluent-product vapors and condense a recycle stream at the same time. • The coke-drum effluent vapors are often "quenched" and "washed" with hot gas oil pumped back to the trayed wash section above the sheds. is pumped from the coker fractionator to the coking furnace . • This recycle stream.Fractionation Section • The coke-drum overhead vapors flow to the coker fractionator and enter below the shed section. together with the flesh feed.
Delayed coker maximum drum size US Coking plant statistics .
Sulphur and metal content are usually retained in the coke produced. Recycle ratio is used to control the endpoint of the coker gas oil. • However. These include mode of operation. • Feedstock variables are the characterization factor and the Conradson carbon which affect yield production. Units are operating at a recycle ratio as low as 3%.Effect of process variables • Increasing pressure will increase coke formation and slightly increase gas yield. . a pressure of 150 psig is required. refinery economics require operating at minimum coke formation. Engineering variables also affect the process performance.4 bar gauge (35 psig). while existing units work at 2. In a case of production of needle coke. coke removal and handling equipment. capacity. New units are built to work at 1 bar gauge (15 psig). It has the same effect as pressure.
The steam generated during cooling is condensed in the blowdown system. • Unheading: The top and bottom heads are removed in preparation for coke removal. This mixture of steam and hydrocarbon is sent first to the fractionator and later to the coker blowdown system. where the hydrocarbons (wax tailings) are recovered.Decoking Scedule • Steaming: The full coke drum is steamed out to remove any residual-oil liquid. • Cooling: The coke drum is water-filled. allowing it to cool below 93°C. • Draining: The cooling water is drained from the drum and recovered for reuse. .
Condensed hydrocarbons are sent to either the coker fractionator or the blowdown drum. and pressure-tested. the drum is tightened. • Heading and testing: After the heads have been replaced. purged. High-pressure water jets are used to cut the coke from the coke drum. and the cycle is repeated for the other drum. • Coking: The heated coke drum is placed on stream. • Heating up: Steam and vapors from the hot coke drum are used to heat up the cold coke drum. . The water is separated from the coke fines and reused. Condensed water is sent to the blowdown drum.Decoking Schedule • Decoking: Hydraulic decoking is the most common cutting method.
put by filling the coke drums faster (14-16 typically) . It allows the refiner to increase the unit through." which have cycle times less than the design cycle. they are often referred to as 18-hour cycles. This has an operating advantage. • Refiners sometimes operate on "short cycles.Decoking schedule • Cycles are typically 36-hour coking cycles. composed of 18 hours of coking and 18 hours of decoking.
For special applications in which high-quality needle coke is desired. certain highly aromatic heavy oils or blends of such heavy oils may be used instead .Feedstocks • Heavy residues such as vacuum residue or occasionally atmospheric residue are the feedstocks which are most commonly used in delayed coking.
Predicting yields • Because the correlations used to predict coking yields are. relatively little information is given in the published literature on how to predict coking yields . considered to be proprietary information to the companies which have developed these correlations. in general.
6 * (wt% CCR) .’’ Marcel Dekker.. (2001).144*(wt%CCR) Naphtha wt% = 11...Prediction yields Gas(C4-) wt% = 7. and Handwerk. New York.E. G. Gary. ‘‘Petroleum Refining.8 + 0. . J.29 + 0343 * (wt% CCR) Coke wt% = 1.H.
Empirical correlations The two impurities in the products from delayed coking which are of greatest concern are sulfur and metals .
(2–5 cm) in diameter are produced.2 in. It is used to make expensive graphite electrodes for the steel industry. It is produced from feeds having low to moderate asphaltene content. It is produced as green coke which requires calcination to remove the volatiles as fuel product.1–0. Green coke can also be used as fuel. Discrete mini-balls of 0. . Needle coke: This coke has a needle-like structure and is made from feed having no asphaltene contents such as decant oils from FCC. Shot coke: This coke is an undesirable product and is produced when feedstock asphaltene content is high and/or when the drum temperature is too high.Types of coke produced Coke amount can be up to 30 wt% in delayed coking. The most common types of coke are: Sponge coke: Sponge coke is named for its sponge-like appearance.
Regular-Grade Coke Production • Virgin petroleum feedstocks have a large number of cross-linkages with less than 6 carbon atoms. These feedstocks tend to produce isotropic or amorphous cokes and when they are visibly very porous they are called sponge coke • Sponge coke derived from a petroleum feedstock that shows abundant pore structure • electrodes for the aluminuium industry • fuel .
is low in sulfur and low in metal is needed Polymerization and condensation of a large number of aromatic compounds with a low concentration of impurities leads to the formation of coke containing fewer cross-linkages and has a more crystalline appearance . and low metal content. good mechanical strength at high temperatures. low coefficient of thermal expansion. It owes this application to its excellent electrical conductivity. in addition. A heavy feedstock which is highly aromatic and.Needle Coke Production Used in the manufacture of high-quality graphite electrodes for the steel industry. low sulfur content.
in a more desirable aluminum-grade coke. .0 wt %. • In general produce coke is produced with a VCM ranging between 6. if structure and impurity levels are acceptable.Temperature • Temperature is used to control the volatile combustible material (VCM) content of the coke product.OPERATING VARIABLES . • At constant pressure and recycle ratio the coke yield decreases as the drum temperature increases. • This results in a harder coke and.0 and 8.
• Typical Temperatures 460-525oC. . • Higher temperatures also increase the potential of coking the furnace tubes and/or transfer line. • If the temperature is too low. the coking reaction does not proceed far enough and pitch or softcoke formation occurs • If temperature is too high the coke formed is very hard and difficult to remove from the coke drum with hydraulic decoking equipment.Temperature • The furnace supplies all the necessary heat to promote the coking reaction.
stock which produces fuel-grade coke having a market value 15 to 30 percent of that for aluminumgrade coke drives design economics to the absolute minimum coke yield. • As a result. • This increases the coke yield and slightly increases the gas yield while decreasing the pentane and heavier liquid-product yield. units are currently being designed with coke-drum pressures as low as 150 lb/in2. • The use of a heavier coker feed.Pressure • Increasing pressure is to retain more of the heavy hydrocarbons are retained in the coke drum. even though it results in an increased expense for vaporhandling capacity. . • The trend in the design of delayed cokers which maximize the yield of clean liquid products is to design for marginally lower operating pressures. • Typical values of pressure used is 15-35 lb/in2.
• The recycle ratio is used primarily to control the endpoint of the coker gas oil.Recycle Ratio • As the recycle ratio is increased. the coke and gas yields increase while the pentane and heavier liquid yield decreases. Units operating at recycle ratios as low as 3 percent have been reported . The same economics which are forcing the operation of cokers to lower operating pressures are also at work on recycle ratios.
.000 to $95. it is often necessary when carrying out economic evaluations to develop a rough. preliminary budget-type estimate. This type of estimate typically has an accuracy of 30%. This cost excludes the vaporrecovery unit and is based on the following assumptions. • For a delayed coker a cost in the range $45.000/(short ton-day) of coke produced may be used for preliminary evaluations. • Although a highly accurate investment cost for a delayed coker can be determined only by a detailed definitive estimate.Estimated Cost Investment • the investment cost of delayed cokers as a function of tons per day of product coke as well as barrels per day of feed.
which produces a high-pressure (2500 to 4500 lb/in2gage) and high-volumetric-flow (900 to 1300 gal/min) water stream. . or twomode drill bit. that first drills the pilot hole and then switches modes to cut the remainder of the coke from that drum. and into the coke handling area. • Most cokers today use a combination tool. through the coke shroud. • The cutting water and coke flow from the bottom of the drum.Coke Drum • Coke is hydraulically removed from the drum using a jet water pump.
The Flexicoking Process 37 .
The Flexicoking process • Feed is preheated to about 310-370oC and sprayed into the reactor where it contacts a hot fluidised bed of coke • The coke is recycled at a rate that maintains reactor fluid bed between 510-540oC • The coke produced is deposited as thin films on the surface of the existing coke particles in the reactor fluidised bed • Shorter times than delayed coking • Decrease yields of coke – higher amounts of aromatics produced • This process is very similar to fluid coking 38 .
• Visbreaking is used to reduce the pour point of waxy residues and reduce the viscosity of residues used for blending with lighter fuel oils. . • Residue from the atmospheric distillation tower is heated (425510ºC) at atmospheric pressure and mildly cracked in a heater. • It is then quenched with cool gas oil to control over-cracking. depending on product demand. is vacuum-flashed in a stripper and the distillate recycled. Middle distillates may also be produced. which accumulates in the bottom of the fractionation tower. and flashed in a distillation tower. • The thermally cracked residue tar.Visbreaking • Visbreaking is a mild form of thermal cracking that lowers the viscosity of heavy crude-oil residues without affecting the boiling point range.
Visbreaking • Coke is not produced • Reactions continue in the soaker – 2 phase system .
Visbreaking • Alternatively. The severity of the visbreaking depends upon temperature and reaction time (1-8 min). vacuum residue can be cracked. • Usually < 10 wt% of gasoline and lighter products are produced. .
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