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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
Coke can be formed from the condensation of polynuclear aromatics (such as nbutylnapthalene) .Coking Coking is a severe method of thermal cracking used to upgrade heavy residuals ("bottom-of.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.the-barrel”) into lighter products or distillates. in early refineries extensive thermal cracking would result in deposit of unwanted coke in the heaters. . • It is the process mostly used today – other processes compared with delayed coking • First developed in 1928.
but before subsequent processing.Coking • Solution: raise rapidly the temperature of the residue above the coking point without depositing the coke in the heater itself.In the early 1930s the drums were limited in size to 10 ft in diameter. Coke drums as large as 30 ft in diameter have recently been installed . Provision of an insulated surge drum downstream of the heater so that the coking took place after the heater. 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.
Delayed Coking .
Delayed Coking .
.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. where the charge is rapidly heated to the desired temperature level for coke formation in the coke drums.
• The total vapors rise upward through the drum and leave overhead. where the trapped liquid is converted to coke and light-hydrocarbon vapors. • The vapor-liquid mixture leaving the furnace enters the coke drum. One drum receives the furnace effluent. which it converts to coke and gas while the other drum is being decoked. .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. • A minimum of two drums is required for operation.
These operations clean and cool the effluent-product vapors and condense a recycle stream at the same time.Fractionation Section • The coke-drum overhead vapors flow to the coker fractionator and enter below the shed section. • This recycle stream. • The coke-drum effluent vapors are often "quenched" and "washed" with hot gas oil pumped back to the trayed wash section above the sheds. together with the flesh feed. is pumped from the coker fractionator to the coking furnace .
Delayed coker maximum drum size US Coking plant statistics .
• Feedstock variables are the characterization factor and the Conradson carbon which affect yield production. while existing units work at 2.4 bar gauge (35 psig). These include mode of operation.Effect of process variables • Increasing pressure will increase coke formation and slightly increase gas yield. Units are operating at a recycle ratio as low as 3%. coke removal and handling equipment. Engineering variables also affect the process performance. . capacity. Recycle ratio is used to control the endpoint of the coker gas oil. New units are built to work at 1 bar gauge (15 psig). It has the same effect as pressure. a pressure of 150 psig is required. In a case of production of needle coke. Sulphur and metal content are usually retained in the coke produced. refinery economics require operating at minimum coke formation. • However.
where the hydrocarbons (wax tailings) are recovered.Decoking Scedule • Steaming: The full coke drum is steamed out to remove any residual-oil liquid. . This mixture of steam and hydrocarbon is sent first to the fractionator and later to the coker blowdown system. • Draining: The cooling water is drained from the drum and recovered for reuse. • Unheading: The top and bottom heads are removed in preparation for coke removal. allowing it to cool below 93°C. The steam generated during cooling is condensed in the blowdown system. • Cooling: The coke drum is water-filled.
High-pressure water jets are used to cut the coke from the coke drum. • Heading and testing: After the heads have been replaced. • Heating up: Steam and vapors from the hot coke drum are used to heat up the cold coke drum. . and the cycle is repeated for the other drum. The water is separated from the coke fines and reused. • Coking: The heated coke drum is placed on stream. and pressure-tested. Condensed hydrocarbons are sent to either the coker fractionator or the blowdown drum. the drum is tightened. Condensed water is sent to the blowdown drum. purged.Decoking Schedule • Decoking: Hydraulic decoking is the most common cutting method.
put by filling the coke drums faster (14-16 typically) ." which have cycle times less than the design cycle.Decoking schedule • Cycles are typically 36-hour coking cycles. It allows the refiner to increase the unit through. This has an operating advantage. composed of 18 hours of coking and 18 hours of decoking. they are often referred to as 18-hour cycles. • Refiners sometimes operate on "short cycles.
certain highly aromatic heavy oils or blends of such heavy oils may be used instead . For special applications in which high-quality needle coke is desired.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. in general. considered to be proprietary information to the companies which have developed these correlations. relatively little information is given in the published literature on how to predict coking yields .
New York. (2001).8 + 0. and Handwerk.Prediction yields Gas(C4-) wt% = 7. ‘‘Petroleum Refining. .144*(wt%CCR) Naphtha wt% = 11. G...’’ Marcel Dekker. Gary.6 * (wt% CCR) .. J.H.E.29 + 0343 * (wt% CCR) Coke wt% = 1.
Empirical correlations The two impurities in the products from delayed coking which are of greatest concern are sulfur and metals .
It is produced as green coke which requires calcination to remove the volatiles as fuel product.Types of coke produced Coke amount can be up to 30 wt% in delayed coking.1–0. (2–5 cm) in diameter are produced. . Needle coke: This coke has a needle-like structure and is made from feed having no asphaltene contents such as decant oils from FCC. It is produced from feeds having low to moderate asphaltene content.2 in. Green coke can also be used as fuel. It is used to make expensive graphite electrodes for the steel industry. 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. Discrete mini-balls of 0. 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 .
It owes this application to its excellent electrical conductivity. A heavy feedstock which is highly aromatic and. 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 . in addition. good mechanical strength at high temperatures. low sulfur content. low coefficient of thermal expansion.Needle Coke Production Used in the manufacture of high-quality graphite electrodes for the steel industry. and low metal content.
in a more desirable aluminum-grade coke. if structure and impurity levels are acceptable.Temperature • Temperature is used to control the volatile combustible material (VCM) content of the coke product. • At constant pressure and recycle ratio the coke yield decreases as the drum temperature increases. • This results in a harder coke and. • In general produce coke is produced with a VCM ranging between 6. .0 wt %.OPERATING VARIABLES .0 and 8.
. 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. • Higher temperatures also increase the potential of coking the furnace tubes and/or transfer line. • If the temperature is too low. • Typical Temperatures 460-525oC.
. 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. • The use of a heavier coker feed. • This increases the coke yield and slightly increases the gas yield while decreasing the pentane and heavier liquid-product yield. • As a result. units are currently being designed with coke-drum pressures as low as 150 lb/in2. • Typical values of pressure used is 15-35 lb/in2.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.Pressure • Increasing pressure is to retain more of the heavy hydrocarbons are retained in the coke drum.
• The recycle ratio is used primarily to control the endpoint of the coker gas oil.Recycle Ratio • As the recycle ratio is increased. Units operating at recycle ratios as low as 3 percent have been reported . the coke and gas yields increase while the pentane and heavier liquid yield decreases. The same economics which are forcing the operation of cokers to lower operating pressures are also at work on recycle ratios.
This type of estimate typically has an accuracy of 30%. • For a delayed coker a cost in the range $45. preliminary budget-type estimate.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.000 to $95.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. it is often necessary when carrying out economic evaluations to develop a rough. . This cost excludes the vaporrecovery unit and is based on the following assumptions.
that first drills the pilot hole and then switches modes to cut the remainder of the coke from that drum. • The cutting water and coke flow from the bottom of the drum. which produces a high-pressure (2500 to 4500 lb/in2gage) and high-volumetric-flow (900 to 1300 gal/min) water stream.Coke Drum • Coke is hydraulically removed from the drum using a jet water pump. . and into the coke handling area. or twomode drill bit. • Most cokers today use a combination tool. through the coke shroud.
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 .
. which accumulates in the bottom of the fractionation tower. is vacuum-flashed in a stripper and the distillate recycled. • Visbreaking is used to reduce the pour point of waxy residues and reduce the viscosity of residues used for blending with lighter fuel oils. Middle distillates may also be produced. • It is then quenched with cool gas oil to control over-cracking. • The thermally cracked residue tar. • Residue from the atmospheric distillation tower is heated (425510ºC) at atmospheric pressure and mildly cracked in a heater.Visbreaking • Visbreaking is a mild form of thermal cracking that lowers the viscosity of heavy crude-oil residues without affecting the boiling point range. and flashed in a distillation tower. depending on product demand.
Visbreaking • Coke is not produced • Reactions continue in the soaker – 2 phase system .
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.Visbreaking • Alternatively.
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