Petroleum coke

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Petroleum coke Petroleum coke (often abbreviated Pet coke or petcoke) is a carbonaceous solid derived from oil refinery coker units or other cracking processes. !" #ther coke has traditionally been derived from coal. $his coke can either be fuel grade (high in sulphur and metals) or anode grade (lo% in sulphur and metals). $he ra% coke directly out of the coker is often referred to as green coke. !" &n this conte't, (green( means unprocessed. $he further processing of green coke by calcining in a rotary kiln removes residual volatile hydrocarbons from the coke. $he calcined petroleum coke can be further processed in an anode baking oven in order to produce anode coke of the desired shape and physical properties. $he anodes are mainly used in the aluminium and steel industry. Petcoke is over )* percent carbon and emits + to !* percent more carbon dio'ide (,#-) than coal on a per.unit.of.energy basis %hen it is burned. /s petcoke has a higher energy content, petcoke emits bet%een 0* and 1* percent more ,#- than coal per unit of %eight. -" $he differences bet%een coal and coke in ,#- production per unit energy produced are small and depend upon the moisture in the coal (increases the ,#- per unit energy .. 2eat of combustion) and volatile hydrocarbon in coal and coke (decrease the ,#- per unit energy).

Contents

! 3arketable coke - 4eedle coke 0 Fuel grade coke 5 ,alcined petroleum coke + 6torage, disposal, and sale 7 6ee also 8 9eferences

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Marketable coke
Marketable coke is coke that is relatively pure carbon and can be sold for use as fuel (i.e. fuel grade coke), or for the manufacture of dry cells, electrodes, etc. (i.e., anode grade coke).

Needle coke
Needle coke, also called acicular coke, is a highly crystalline petroleum coke used in the production of electrodes for the steel and aluminium industries and is particularly valuable because the electrodes must be replaced regularly. 4eedle coke is produced e'clusively from either F,, decant oil or coal tar pitch. Catalyst coke is coke that has deposited on the catalysts used in oil refining, such as those in a fluid catalytic cracker. $his coke is impure and is only used for fuel.

Fuel grade coke

Fuel Grade Coke is classified as either sponge coke or shot coke morphology. While oil refiners have been producing coke for %ell over !** years, the mechanisms that cause sponge coke or shot coke to form are not %ell understood and cannot be accurately predicted. &n general, lo%er temperatures and higher pressures promote sponge coke formation. /dditionally, the amount of heptane insolubles present, and fraction of light components in the coker feed contribute. While its high heat and lo% ash content make it a decent fuel for po%er generation in coal fired boilers, petroleum coke is high in sulfur and lo% in volatile content, and this poses environmental (and technical) problems %ith its combustion. $o meet current 4orth /merican emissions standards, some form of sulfur capture is re;uired, a common choice of sulfur recovering unit for burning petroleum coke is the 64#< Flue gas desulphurisation technology, 0" %hich is based on the %ell.kno%n W6/ Process. Fluidi=ed bed combustion is commonly used to burn petroleum coke. >asification is increasingly used %ith this feedstock (often using gasifiers placed in the refineries themselves).

Calcined petroleum coke

Calcined petroleum coke (,P,) is the product from calcining petroleum coke. $his coke is the product of the coker unit in a crude oil refinery. $he calcined petroleum coke is used to make anodes for the aluminium, steel and titanium smelting industry. $he green coke must have sufficiently lo% metals content in order to be used as anode material. >reen coke %ith this lo% metals content is referred to as anode grade coke. $he

green coke %ith too high metals content %ill not be calcined and is used for burning. $his green coke is called fuel grade coke.

Storage, disposal, and sale

4early pure carbon, petcoke is a potent source of carbon dio'ide if burned. 5" Petroleum coke may be stored in a pile near an oil refinery pending sale. #ne e'ample, as of -*!0, %as the large stockpile o%ned by ?och ,arbon near the @etroit 9iver %hich %as produced by a 3arathon Petroleum refinery in @etroit %hich began refining bitumen from the oil sands of /lberta in 4ovember, -*!-. Aarge stockpiles of petcoke also e'isted in ,anada as of -*!0. ,hina and 3e'ico %ere markets for petcoke e'ported from ,alifornia to be used as fuel. /s of -*!0 the :P/ %as declining permits to use petcoke as fuel in the Bnited 6tates but markets e'isted in &ndia and Aatin /merica %here it %as used to fuel cement manufacture. /s of -*!0 #'bo% ,orporation, o%ned by William &. ?och, %as a maCor dealer in petcoke, selling !! million tons annually. +"

Petroleum Coke
Petroleum coke is a solid material and a byproduct of the coking unit, a residual fuel upgrader. $he ;uality of the coke is dependent upon the crude oil processed in the refinery. ,okes produced from sour crude oil are high in sulfur and trace metals. $hese cokes are used in fuel applications such as utility boilers and cement kilns. ,okes produced from s%eet crude oil can have properties that are suitable for calcining are used in carbon anodes for aluminum smelting and electrodes for electric arc furnaces. Product Information 3arathon Petroleum ,ompany AP has cokers at four of its refineries, @etroit, 3&, >alveston Day, $<, >aryville, A/, and 9obinson, &A. >aryville produces high sulfur, lo% grind shot coke. >alveston Day produces a mid sulfur coke and 9obinson produces anode grade coke. Transportation and Marketing /ll >aryville petroleum coke is transported directly from the refinery via river barge. 9obinson petroleum coke is transported via railcar (directly) and also can be transloaded from railcars onto river barges. @etroit coke is loaded out by truck %hile >alveston Day coke is trucked to a storage terminal and loaded into an ocean going vessel.

Crude Selection & Calcined Coke

uality

,rude oil is a comple' mi'ture of hydrocarbons, sometimes characteri=ed as (a useless mi'ture of useful products.( Petroleum coke is, essentially, the (bottom of the crude barrel( . the carbon in the crude charge that cannot be recovered in normal refining processes . comprising about +.8 %tE of each barrel of crude.

/ refiner must carefully balance crude characteristics against refining unit capacities and product slates. &f the facility produces anode.grade carbon, other impacts must be considered. Consistent !uality coke begins "it# consistent !uality crudesF (trim( crudes introduced at the (front end( of the refining process to control eventual carbon ;uality results in much more consistent finished carbon product to the end userGsmelter as opposed to trying to blend solids (green andGor calcined) to spec. (after the fact(. ,rude @istillation $he first step in any refining process is to fractionate the crude oil charge into intermediate and finished products:

Crude Selection & Calcined Coke

uality

,rude oil is a comple' mi'ture of hydrocarbons, sometimes characteri=ed as (a useless mi'ture of useful products.( Petroleum coke is, essentially, the (bottom of the crude barrel( . the carbon in the crude charge that cannot be recovered in normal refining processes . comprising about +.8 %tE of each barrel of crude. / refiner must carefully balance crude characteristics against refining unit capacities and product slates. &f the facility produces anode.grade carbon, other impacts must be considered. Consistent !uality coke begins "it# consistent !uality crudesF (trim( crudes introduced at the (front end( of the refining process to control eventual carbon ;uality results in much more consistent finished carbon product to the end userGsmelter as opposed to trying to blend solids (green andGor calcined) to spec. (after the fact(. ,rude @istillation $he first step in any refining process is to fractionate the crude oil charge into intermediate and finished products:

$he crude charge is first %ater.%ashed in a (desalter(s)( to remove solids and salts, and then separated into various fractions (by boiling point) in an (atmospheric distillation( unit . here, the ,rude Bnit. $he desalted crude charge is preheated, and is then vapori=ed in a fired heater. $he vapori=ed charge is fed to a distillation to%er, %here it cools and condenses as it flo%s up the to%er. (&ntermediates( (feedstockHs for further processing in do%nstream units) and finished products are %ithdra%n from the to%er at various points. $he (bottoms( from the first distillation of the crude charge ((reduced crude() are routed to another unit, %here the charge is reheated, and subCected to a vacuum in another distillation to%er. $he vacuum causes the charge to boil at a lo%er temperature than %ould be the case at atmospheric or positive pressureF this allo%s distillation of additional intermediates %ithout thermally decomposing the still.valuable reduced crude to carbon (or coke). $he bottoms from the vacuum distillation operation cannot be further distilledF instead, the (vacuum residuum( is routed to the ne't unit in the process, the ,oker. $he operation of the ,rude and Iacuum units can have a tremendous impact on finished calcined coke ;uality: $esalting: While desalting the incoming crude charge is intended primarily to prevent corrosion in do%nstream piping, e;uipment, and process units, finished carbon products benefit from reduced levels of iron (less corrosion products J less iron in the finished calcined coke). $istillation: Proper distillation in the Iacuum Bnit is critical to resid (,oker feed) ;uality control. 6pecifically, the amount of vacuum gas oil sent to the ,oker %ith the vacuum residuum (determined by the efficiency of the fractionation in the Iacuum to%er itself) must be carefully monitored and controlled to insure ade;uate hardness of the green coke produced by the ,oker. /n (optimal( resid yield for a refiner more concerned about do%nstream catalytic units may not necessarily be optimal for eventual calcined coke propertiesK ,oking &n a delayed coker, the incoming resid charge is mi'ed %ith coker gas oils (,>#), and the resultant bottoms stream is fed to a fired heater(s). &n the heater(s), this heavy oil charge is thermally cracked into vapor and li;uid. $he vaporGli;uid effluent from the heater(s) flo%s into a coke drum, %here the li;uid drops out and solidifies (eventually filling the drum), and the vapors are returned to the fractionation process. Dy progressively condensing the vapor coming from the ,oke @rums in a distillation to%er(s) (here, the Fractionators), useful intermediates are collected for further processing. ,oke drums operate in pairs %ith an associated heater. While one coke drum is filling, its t%in is being drilled. When one of the drums is full, the effluent from its associated heater is rerouted into the empty drum of the pair. $he full drum is isolated and cooled, and the collected (green coke( is drilled out of the drum %ith high.pressure %ater. #nce the drum

has been completely drilled out, it is preheated %ith effluent (vapors) from the associated heater, and the heater effluent is s%itched into it so the other drum can be drilled. $he green coke is collected in a containment basin, %here it is allo%ed to drain. $he green coke is then reclaimed from the (coke pit( %ith clamshell bucket ganty cranes, and conveyed to covered storage facilities. $he best last step in calcined product ;uality control is control of the green coke feed ;uality. ,oker operations can impact coke ;uality in a number of %ays:

Product Si%ing ,oking is essentially a time.temperature phenomenaF the longer the coking cycle, and the higher the temperature, the harder the resulting green coke. 2arder green feed translates to larger calcined product. 2o%ever, longer cycle times limit ,oker (and, conse;uently, crude) rates, and higher heater outlet temperatures result in shorter run lengths for the ,oker heaters (%hich must be periodically taken off line for decoking of the heater tubes). / ,oker that is more concerned %ith li;uid yields than %ith green coke ;uality %ill operate at lo%er heater outlet temperatures (to minimi=e %ear and tear on the heaters and ma'imi=e run lengths bet%een decokings) and shorter cycles (to ma'imi=e crude and coker feed rates), both of %hich adversely affect finished coke properties. 2eater outlet temperatures must also be carefully adCusted throughout each fill cycle to ma'imi=e consistency (specifically, hardness) of the green coke in the drum from bottom to top. T#roug#put &or 'ecycle( 'atio $he ratio of heater feed (combined heavy coker gas oil and fresh resid) to fresh resid feed

(only) is referred to as throughput, or recycle, ratio. &f a ,oker is optimi=ed around li;uid yields (gas oils, for do%nstream upgrading in a hydrocracker andGor fluid catalytic cracker), this ratio is minimi=ed (to minimi=e the amount of valuable gas oil coked). 2o%ever, higher recycle ratios may be desirable if coke ;uality control is the end goal. 2igher recycle ratios, %hile (destroying( highly.valued (gas oils) feedstocks, also reduce metals and sulfur levels in the green coke. $rilling ,onsistency of drilling techni;ue is another key to consistent coke ;uality, specifically, si=ing. Aonger drilling times result in smaller, easier.to.handle green product. 6horter drilling times, conversely, result in larger green coke feed, %hich translates into larger calcined product. 6urface contaminants can have a tremendous impact on air reactivity and other coke characteristics. #ften, cokers use drilling as a means to recycle or dispose of %aste %ater. ,areful control of drilling %ater chemistry and scheduled replenishment of the drilling %ater supply %ith clean, fresh %ater is crucial to controlling surface contaminants. )andling &n transferring green coke to handling, and on to calcining, several things can impact the ;uality of the final (calcined) product. &f the green coke is handled repeatedly by mobile e;uipment, si=ing can be negatively impacted by crushing, dropping, and the like. &f the green coke feed is stockpiled in the open, surface contaminants can also become an issue. &n addition to %indborne silica and other pollutants, any material applied to the coke pile(s) for dust control, such as %ater sprays, can introduce sodium and other contaminants. $o protect final product ;uality, green feed is best handled by dedicated e;uipment (e.g. gantry cranes and conveying the feed to storage, as opposed to reclaiming and transporting via front.end loaders), and should be conveyed and stored under cover from the environment (e.g. enclosed conveyors and inside storage). ,alcining &n the calcining process, the green coke feed is heated to a sufficiently high temperature to drive off any residual moisture, and to drive off and combust any residual hydrocarbons (the combustion of the evolved volatile materials provides the necessary heat for the calcination process) in the green coke feed.

/t ,herry Point, this is accomplished in three rotary hearths. $he hearths are comprised of fi'ed roofs over rotating tables. Fi'ed ploughs ((rabbles() in the hearth roofs gently move the material in a spiral fashion from the perimeter of the hearth, %here the green feed is introduced, to the center of the hearth, %here the product is %ithdra%n. Bnlike kilns, rotary hearths rely solely on volatiles in the green feed and preheated combustion air to calcine the green feedF no (e'ternal( fuel (i.e. burners) is used. /fter cooling (and, for customers re;uiring it, oiling for dust control), the calcined product is routed to %eather.tight silos for storage prior to shipment to the end user. ,herry Point produces high 9@ (-.*8* gGcc), high bulk density calcined coke.

/t Wilmington, >elsenkirchen and Aingen, this is accomplished in conventional rotary kilns. For each ,alciner, green coke feed, produced by DPHs nearby 9efineries, is stored under cover in a ,oke 6torage Darn and at Wilmington and >elsenkirchen a feed reclaimer is used to ensure a consistent feed si=e is processed by the calciner. /t Aingen, the green coke is segregated by si=e in various silos and reblended as calciner feed for feed consistency. /s opposed to rotary hearths, %hich rely solely on volatiles in the green feed and preheated combustion air for calcination, rotary kilns commonly employ large fuel gas burners or o'ygen inCection at the (do%nhill( end of the kiln to calcine the green feed. $he finished product is in turn transported by truck, conveyor or rail to the Port for

e'port, or is loaded into railcars for shipments to domestic customers. $he calcining operation is the last, and arguably one of the least, influential tool to control the eventual ;uality of the carbon product. 4o calcining operation can compensate for poor feed resulting from upstream operationsK $here are several considerations involved in any calcining operation: Feed consistency: Dlending solids to meet green feed and product specifications (vs. blending crudes at the (front end( of the refining process), and careful control of upstream (crude distillation and coking) operations to insure consistent, high.;uality green feed. Feed #andling: 9eclaiming feed %ith dedicated e;uipment (e.g. bridge reclaiming from covered storage) vs. front end loaders or other heavy e;uipment, enclosed handling systems, covered feed storage to prevent atmospheric contamination, etc. Calciner operation: ,onsistency and control of operations, application of statistical process controls, ;uality and intrinsic process control capabilities of the e;uipment and units. 6ummary

Consistent !uality carbon begins "it# consistent !uality feedstocks and upstream process unit operations*no calcining operation can turn poor !uality or inconsistent feed into consistent or #ig# !uality calcined product+ T#e most le,eraging controls for e,entual calcined coke !uality are all upstream of the calcining operation* only an integrated refining operation - "#ere coke !uality is considered, day-in and day-out, rig#t along "it# li!uid product yields and !uality - offers t#e most consistent carbon.