Delayed Coking Chapter 5 Updated: July 12, 2018 2 Copyright © 2017 John Jechura ([email protected]) U.S. Refinery Implementation Coking capacity reported in terms of both coke production in tons per day & residual oil feed rate in barrels per day EIA, Jan. 1, 2018 database, published June 2018 http://www.eia.gov/petroleum/refinerycapacity/ Updated: July 12, 2018 3 Copyright © 2017 John Jechura ([email protected]) U.S. Refinery Implementation EIA, Jan. 1, 2018 database, published June 2018 http://www.eia.gov/petroleum/refinerycapacity/ Updated: July 12, 2018 4 Copyright © 2017 John Jechura ([email protected]) 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 “Improve coker efficiency with reliable valve automation” B. Deters & R. Wolkart, Hydrocarbon Processing, April 2013 Updated: July 12, 2018 5 Copyright © 2017 John Jechura ([email protected]) Characteristics of Petroleum Products Conversion to light products w/o extra hydrogen requires significant coke formation Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000 Updated: July 12, 2018 6 Copyright © 2017 John Jechura ([email protected]) Coking History After World War II railroads shifted from steam to diesel locomotives . Demand for heavy fuel oil sharply declined . Coking increases distillate production & minimizes heavy fuel oil 1950 to 1970 coking capacity increased five fold . More than twice the rate of increase in crude distillation capacity . Increase in heavy high sulfur crude combined decrease in heavy fuel oil Delayed coking . Predominate coking technology . Delayed Coking technology is relatively inexpensive • Open art available • Companies do license technology emphasizing coke furnaces, special processing modes, & operations Updated: July 12, 2018 7 Copyright © 2017 John Jechura ([email protected]) Coking Chemistry “Carbon rejection” process Conditions . Coke has very little hydrogen – contained . High temperatures & low pressures favor in lighter products cracking . Metals (catalyst poisons) concentrate in • More distillate liquids coke • Lower yields of coke & hydrocarbon gas . High residence time favor the combining Cycle of cracking & combining reactions . Side chains cracked off of PNA . Over conversion will reduce distillates & (Polynuclear Aromatic) cores produce coke and hydrocarbon gases • Heteroatoms in side chains end up in light products . PNAs combine (condense) to form asphaltenes & coke • Metals & heteroatoms in PNA cores end up in coke Figure: “Comparison of thermal cracking and hydrocracking yield distributions,” Sayles & Romero http://www.digitalrefining.com/article_1000070.pdf Updated: July 12, 2018 8 Copyright © 2017 John Jechura ([email protected]) Feed for the Delayed Coker Delayed Coker can process a wide variety of feedstocks . Can have considerable metals (nickel & vanadium), sulfur, resins, & asphaltenes . Most non‐volatile contaminants exit with coke Typical feed is vacuum resid . Atmospheric resid occasionally used . Specialty cokes may also use gas oils, FCC cycle oils, … Feed composition dependent on actual crude & crude blend. Some typical values: . 6% sulfur . 1,000 ppm (wt) metals . Conradson Carbon Residue (CCR) of 20 – 25 wt% Feed ultimately depends on type of coke desired . Specialty cokes require careful choice of crude oil feedstocks • Using feedstocks other than vac resid may lessen this requirement Updated: July 12, 2018 9 Copyright © 2017 John Jechura ([email protected]) Solid Products Coke with large amounts of Fuel grade coke metals & sulfur may pose a . Feedstock – resid high in polynuclear aromatics disposal problem & sulfur . Oil sands pile it up . Value similar to coal Product grades High quality products . Needle coke . Needle coke . Anode grade • Feedstock – FCC cycle oils & gas oils . Fuel grade • Used for electrodes in steel manufacturing • 10X or more value of fuel‐grade coke Product Morphology • Hydroprocessing upstream of delayed coker may . Needle coke be used to make high quality coke . Sponge coke . Anode grade coke . Shot coke • Feedstock – resids with small ring aromatics, low metals, & low sulfur • Used for anodes in aluminum production Updated: July 12, 2018 10 Copyright © 2017 John Jechura ([email protected]) Solid Products Morphology . Needle coke • Very dense & crystalline in structure . Sponge coke • Is sponge‐like in structure . Shot coke • Cannot avoid – based on asphaltene content of feed • From size of small ball bearings to basketball • Operational adjustments required in cutting & handling of coke “Managing Shot Coke: Design & Operation,” John D. Elliott http://www.fwc.com/getmedia/5fec2c99‐879e‐4bbc‐a296‐77971b85df89/ManagingShotCoke‐Design‐OperationA‐4Rev1.pdf.aspx?ext=.pdf Updated: July 12, 2018 11 Copyright © 2017 John Jechura ([email protected]) Light Products Low yields of liquids relative as Liquids compared to other refinery processes . Hydrotreated for sulfur removal . Mass conversion of vac resids to . Naphtha fractions liquids ~55% • Light fraction may to isomerization Composition • Heavy fraction to catalytic reformer • Small fraction of gasoline pool . Some of the lowest quality in the refinery . Light Gas Oil • Used in diesel pool after . Reduced aromatics but high olefin hydrotreating content • Hydrocracker—processes aromatic . Vapors & liquids high in sulfur even rings though heteroatoms are . Heavy Gas Oil fed to catalytic cracker concentrated in coke or hydrocracker (preferred) Vapors processed in refinery’s gas . Flash Zone Gas Oil ‐‐ increases liquid plant yield & reduces coke make Updated: July 12, 2018 12 Copyright © 2017 John Jechura ([email protected]) Feedstock Selection Amount of coke related to carbon residue of feed . Correlates to hydrogen/carbon ratio & indicates coking tendency Three main tests . ASTM D 524 — Ramsbottom (RCR) . ASTM D 189 — Conradson (CCR) . ASTM D 4530 – Microcarbon (MCRT) CCR & MCRT essentially give the same results & can be usually be used interchangeably Approximate correlation between RCR & CCR: 2 RCR exp 0.236 0.883ln CCR 0.0657ln CCR Updated: July 12, 2018 13 Copyright © 2017 John Jechura ([email protected]) Yield Estimation Updated: July 12, 2018 14 Copyright © 2017 John Jechura ([email protected]) Reported Coker Yields Actual yields are dependent on operating conditions, process configuration, … Handbook of Petroleum Refining Processes, 3rd ed., Robert Meyers (ed.) “ConocoPHillips Delayed Coking Process,” Hughes, Wohlgenant, & Doerksen McGraw‐Hill, Inc, 2004 Updated: July 12, 2018 15 Copyright © 2017 John Jechura ([email protected]) Boiling Point Ranges for Products 1,000 42-hcgo 900 53+55 40-lcgo 800 37-unstab 33-wetgas lab-vac-resid 700 600 500 400 Incremental YieldIncremental [bpd] 300 200 100 - 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 BPT [°F] Based on example problem in: Refinery Process Modeling, A Practical Guide to Steady State Modeling of Petroleum Processes, 1st ed. Gerald Kaes, Athens Printing Company, 2004 Updated: July 12, 2018 16 Copyright © 2017 John Jechura ([email protected]) Configuration Typical equipment . Heater (furnace) & Preheat train . Coke drum vessels . Fractionator . Downstream vapor processing vessels Coke drums run in two batch modes . Filling . Decoking Both modes of operation concurrently feed to the fractionator Updated: July 12, 2018 17 Copyright © 2017 John Jechura ([email protected]) Delayed Coker Updated: July 12, 2018 18 Copyright © 2017 John Jechura ([email protected]) Typical Delayed Coking Unit Original Source: “An Oil Refinery Walk‐Through”, by Tim Olsen, Chemical Engineering Progress, May 2014 Updated: July 12, 2018 19 Copyright © 2017 John Jechura ([email protected]) Typical Delayed Coking Unit Petroleum Refining Technology & Economics, 5th ed. Gary, Handwerk, & Kaiser, CRC Press, 2007 Updated: July 12, 2018 20 Copyright © 2017 John Jechura ([email protected]) Typical Delayed Coking Unit Fresh Feed & Furnace Coke Drum Configuration . Fresh feed to bottom of fractionator . Flow up from bottom . Total feed (fresh feed + recycle) heated in . Coking reaction are completed in drum furnace . Vapors out top of drum to fractionator Furnace . Even number of coke drums . Outlet temperature about 925oF • Typically two or four o • Operate as pairs, one filling while the other . Cracking starts about 800 F decoked . Endothermic reactions . Superheat allows cracking reactions to Fractionator continue in coke drums– “Delayed . Vapors compressed & sent to gas plant Coking” . Naphtha condensed from fractionator . Steam injected into furnace overhead • Reduce oil partial pressure & increase . Gas oils are side stream draws from vaporization fractionator • Maintains high fluid velocities . Flash Zone Gas internally recycled to coke drums or recovered as additional liquid Updated: July 12, 2018 21 Copyright © 2017 John Jechura ([email protected]) Typical Delayed Coking Unit Coke Drum Cyclic Operation . Fill Coke Drum . Coke Collection Systems • Coking reaction in drums & solid coke • Direct discharge to hopper car deposited • Pad loading • Gas from top of coke drum to fractionator • Pit