Beruflich Dokumente
Kultur Dokumente
CHE 735
Purpose
Process heavy residuum to produce distillates (naphtha & gas oils) that may be catalytically upgraded Hydrotreating, catalytic cracking, and/or hydrocracking Attractive for heavy residuum not suitable for catalytic processes Large concentrations of resins, asphaltenes, & heteroatom compounds (sulfur, nitrogen, oxygen, metals) Metals, sulfur, & other catalyst poisons generally end up in coke Sold for fuel & other purposes Carbon rejection process
Development of Coking
Coking evolved from the Dubbs cracker After World War II railroads shifted from steam todiesel locomotives Demand for heavy fuel oil sharply declined Coking increases distillate production & minimizes heavy fuel oil Between 1950 and 1970 coking capacity increase five fold More than twice the rate of increase in crude distillation capacity
Development of Coking
The increase in heavy high sulfur crude, together with the decrease in fuel oil, accelerated the use of coking Coking capacity is measured in terms of both coke production in tons per day & residual oil feed rate in barrels per day 2002 EIA database: Unit Crude Units Vacuum Units Bbl/day 17.6 MMbpd 8.1 MMbpd Relative Capacity 13% 28%
Coking Units
2.3 MMbpd
Delayed Coking
Predominate coking technology is Delayed Coking Fluid Bed Coking Flexicoking Delayed Coking technology is relatively inexpensive Considered open art Companies do license technology emphasizing coke furnaces, special processing modes, & operations
Coking Chemistry
Carbon rejection process Also removes hydrotreating catalyst poisons May be considered a cycle of cracking & combining Side chains cracked from thermally stable polynuclear aromatic cores
Cleavage of C-C bonds tend to make light hydrocarbons & polynuclear aromatics Liberated side chains can over crack to form light gases
Coking Chemistry
High temperatures & low pressures favor cracking More distillate liquids Lower yields of coke & hydrocarbon gas High residence time favor the combining reactions Over conversion will reduce distillates & produce coke and hydrocarbon gases
Coking Chemistry
Cracking reactions Saturated paraffins crack to form lower molecular weight olefins & paraffins Isomerization is insignificant Side chains cracked off small ring aromatics (SRAs),cycloparaffins (naphthenes), & polynuclear aromatics (PNAs) Naphthenes may dehydrogenate to aromatics SRAs may condense to larger polynuclear aromatics (PNAs) leave thermally stable PNAs
Coking Chemistry
Combining reactions. Low molecular weight olefins form higher molecular weight compounds Two ethylenes to butene SRAs combine (condensation) to form resins Resins after cracking off side chains combine their remaining polynuclear aromatics (PNAs) to form asphaltenes Asphaltenes after cracking off side chains left with large PNAs Partially saturated with short side chains & entangled with heteroatoms The large PNAs precipitate to form crystalline liquids & ultimately solidify to form coke Metals & sulfur embedded
Solid Products
Coke with large amounts of metals & sulfur may pose a disposal problem Refiner may have to pay for disposal Product grades Needle coke Anode grade Fuel grade Shot coke
Solid Products
Hydroprocessing upstream of delayed coker may be used to make high quality coke Needle coke FCC cycle oils, gas oils, & resids with low sulfur & aromatics used as feedstocks Used for electrodes in steel manufacturing Anode grade coke Resids with small ring aromatics Used for electrodes in aluminum production
Solid Products
Fuel grade coke About 85% carbon & only 4% hydrogen 11% heteroatoms sulfur, nitrogen, oxygen, vanadium & nickel Resid high in polynuclear aromatics & sulfur used as feedstock Shot coke From size of small ball bearings to golf ball Nearly always try to avoid! Little market Operational problems
Light Products
Light ends processed in coker gas plant. Liquids Reduced aromatics & heteroatoms concentrated in coke, but still contain large amounts of sulfur & olefins Naphtha fraction may be used as catalytic reformer feed after hydroprocessing Only small fraction of gasoline pool Gas oil fed to catalytic cracker or hydrocracker Hydrocracker preferred does better job of processing aromatic rings
Feedstock Selection
Amount of coke formed related to the carbon residue of the feed Since this parameter correlates well with hydrogen/carbon atomic ratios and indicates coking tendencies, this parameter is especially useful for screening feeds Three main tests Ramsbottom method (ASTM D-524) Conradson Carbon (ASTM D-189) Microcarbon Residue Test
Yields
Low yields of liquids relative to hydrocracking Mass conversion of vacuum resids to liquids about 55% to about 90% for hydrocracking Coke & liquid yields may be estimated by simple equations (misprint pg. 75 see pg. 89) Coke Yield (wt%) = 1.6 (wt% CCR) Gas (C4-) (wt%) = 7.8 + 0.144 (wt% CCR) Gasoline (wt%) = 11.29 + 0.343 (wt% CCR) Gas Oil (wt%) = 100 - (wt% Coke) - (wt% Gas) - (wt% Gasoline) Gasoline (vol%)=186.5/(131.5+API) x (wt% Gasoline) Gas Oil (vol%)=155.5/(131.5 +API )x (wt% Gas Oil)
Operating Modes
Filling of coke drums Feed heated in the furnace to cracking temperature Hot feed routed up from bottom of coke drums coking reaction occur in drums & solid coke deposited Gas from top of coke drum fed to fractionator Continue for full cycle time until coke drum is full Decoking At end of cycle empty drum switched on-line & filling operations continue Off-line drum filled with coke undergoes operation Quench step hot coke quenched with water giving off steam &volatile hydrocarbons Vapors fed to the fractionator Coke drilled out with water drills
Operating Modes
Fractionator Vapors compressed & sent to gas plant Naphtha is condensed from fractionator overhead Gas oils are two sidestream draws from the fractionator
Number of coke drums Even number of coke drums, typically two or four One set on-line in a coking step while the other set is being decoked
Coke Product
Coke cut out of drum called green coke Varies in size from fines, to particulates, to chunks Shot coke Hard spheres resembles shot Sizes from small ball bearings to golf balls High asphaltene content feed requiring very high coking temperatures
Decoking
Each coke drum has a drilling rig that raises & lowers a rotating cutting head Uses high-pressure (4,000 psig) water Steps Drum cooled & displaced with water to remove volatiles Pilot hole is drilled through the coke to bottom head Pilot drill bit replaced with a much larger high-pressure water bit Cut either from top to bottom or bottom to top The coke falls from coke drum into a collection system
Coke Handling
Collection systems Direct discharge to hopper car Coke drums straddle railroad track Water drains from cars, collected in pit beneath track, & sent to reprocessing Pros Lowest cost option Disadvantages Only used for two drum cokers Logistics of moving cars under the drums Slow cutting rate to avoid damage to cars & give even distribution in cars Personnel required to move cars & distribute load during cutting Fines & dirty water control Dusting controlled by water spray in the cars
Coke Handling
Collection systems Pad loading Coke dropped down inclined slide from the coke drum bottom to a pile sitting beside but not under the drum Water drainage from pile on the pad Ports packed with sized coke to retain the fines Coke moved to stockpiling by a front-end loader Pit & Crane loading Provides for both storage & dewatering of coke Coke loading crane system transfers coke to railway cars Pit minimizes elevation of drums Pit makes dust control easier
Coke Handling
Collection systems Slurry loading Most elegant of coke handling options Scheme Coke drops from drum during decoking Passes through crusher Conveyed by a sluiceway to a slurry sump Slurry pump sends coke slurry up into dewatering bins Water from bins drain back to sump Drained coke sent to silos Must handle slurry water & process discarded water before it goes to refinery water disposal system
Coke Handling
Other considerations Method used establishes height coke vessels & drilling derricks above them Method used determines nature of environmental measures Coke is handled wet but it dries, leading to dusting & dirty water management Switching coke drums imposes an incremental cyclic steam & vapor load on the refinery system Steam is consumed in only parts of the decoking cycle Vapor recovery system must handle vapor from flushing a drum before decoking
Fractionator
Fractionator feeds Coke drum overhead Early designs Refluxed by cooled fractionator bottom recycle stream Now sent to bottom of fractionator above liquid level Fresh resid feed Early designs Routed directly to furnace Above hot vapor feed from the coke drum Provided refluxing of hot vapors Now typically sent to bottom of fractionator below the liquid level Strips light ends from the feed Preheats feed Condenses heavy ends from coke drum vapor Suppresses coke formation by cooling and reducing the concentrations of resins in the hot coke drum vapor.
Fractionator
Flash Zone Space above the feed to the bottom of the heavy gas oil draw Height of the flash zone about one column diameter(typically 25 feet) Necessary for liquid disengaging & wash zone equipment Feeds introduced at liquid pool at bottom of flash zone Quench oil from the gas oil stream injected in the line at the top of the coke drum Suppress coking in line to the fractionator
Fractionator
Wash Zone Upper part of the flash zone just below the heavy gas oil draw Washes vapors coming up the column to remove coke fines, resins & asphaltenes Could cause coking in upper sections of fractionator Washing is done by a series of spray nozzles across the column area using cooled gas oil Low cost & low pressure drop Current spray designs minimize amount of spray liquid & hence recycle May use a grid section washed with cooled gas oil Higher pressure drop & prone to clogging Sieve trays, shed trays, and decks used before grids Often washed with fresh feed slipstream Rarely used Coking, mechanical damage, fluid distribution, high recycle ratios
Fractionator
Recycle Ratio of furnace charge (fresh feed plus recycle) to fresh feed Throughput ratio of one indicates no recycle Used to decrease contaminants (metals, sulfur, Conradson carbon residues) in the heavy gas oil Recycle ultimately cracked & contaminants contained with the coke Types Internal condensed liquids to fractionator from coke drum overhead feed External quench flows to the top of coke drum & gas oil flows to the wash section Current designs minimize recycle Increased resins & asphaltenes in coke decreases gas oil yields Equipment is larger Anode & needle grade cokes usually made with higher recycles than fuel grade coke
Fractionator
Avoiding Coking in Fractionator Major design consideration Black oil passing down to the surge section of the fractionator is heavy with resins & solublized asphaltenes Produces more coke than gas oil in the coke drum Also likely to coke in bottom of the fractionator Several methods Surge time limited to several minutes since coking is a function of time Slipstream from the bottoms cooled & recycled back to the surge section Remove some oil from bottom of fractionator & dispose of as No. 6 heavy fuel oil or mix with HGO Historical option Common when the demand for heavy fuel oil was high This reduces the amount of coke made
Fractionator Products
Gas Product During coking cycle vapors from the drum go to the fractionator Fractionator overhead produces liquid naphtha & gas light ends Light ends compressed and sent to gas plant The gas plant is usually built as integral part of the coker unit It has the same configuration as the saturates gas plant or catalytic light ends gas plant Absorber Deethanizer Sponge oil absorber Fractionator
Fractionator Products
Naphtha Product Naphtha fractions high in sulfur & olefins but low in aromatics If naphtha products processed further in a catalytic reformer they are hydrotreated first Sulfur hydrogen sulfide Olefins saturates Aromatics naphthenes
Fractionator Products
Gas Oil Side Draw At least one gas oil sidestream but two are common Steam stripped to narrow end point Part of side draw cooled & pumped back for reflux Cooling also helps to prevent coking Two pump around configurations Cooled liquid is fed back to tray above the draw tray Ensure sufficient liquid from the draw tray Mainly for heat transfer Fed to the tray below the draw tray Fractionation is better & number of trays may be reduced Amount of oil to be recycled back to coker controlled by varying end point of the lower gas oil draw