I

'se8 'f-rlsnpur lernleu qlr^\ req1e3o1 Ieels eql roJ eloc eprnord pue speo.r 'tuneloJled :no ened selrlenrJep uneloJled larreq-eq]-Jo-tuollog uo4 pe^uaF 'sure4 's1cn:1 ere sdlqs 'solrqotuolne pu 'seueld-rre .rnt-' IIo IenJ fq pe.reznod JoJsluclrqnlpue slenJseprnordlI eSeuuole uo Surddrqs s.plro,^A 3ql ,'srseq ']leq u purr8 o1 plno,l\ srql uo serlrnrtrf 1eue1d Jo %09 roJ slunocceunelorled 'llo 'fruouor;,lrrou,(pee1s uerunr{ e Jsor.u }noq}r^\ }eq} }ueuodur os Jo ",(epo1 unolorled'69gl relJv s6plro./K eq] ol luepodur eJorupue eJou eueceq Jo fler.rer ,_r'sluotuluro opllA e uI pue 'seltlcefordSunueg JoJ 'uor1cru1suoo ur elrseqpu ue se 'sdrqs goord-re1e,^a ol posn se,^A punor8 eql Jo lno dn pedeesfldurs teql Jo peuru.r s,r eroJeg'l9gI eroJeq runelorledgo frolsq eq] s^\oqsI atqDJ ]eql IIo'6S81 ']ol e 'enlezreruosseq punor8 eqt tuor; 'f11en1cy lou ]nq }q8ru.r1s lro epruc ielqenls^ os Iro se{el'uleq^(\ eqclr oq sl ,(qzno5

uollJnpord runoloJlodJo,{ro1sr11 I ' I

'lro >l3ruls f11eugeq 'epuerg old eql pue relru peu oql uoo.^Aleq ,Qunoc,fueneur selorl ftp EurlllrpJo srue,,( roUV irlclr s(eq esnecegi,{ddeq os oreq rno sr {q,,Vt 'llor o] srsnru eql Irlun uels sltpsrceql pu? slle,^As Kselsce qll,K ecuepf,r,11 '1eB seqselds lseq srq pue {oDl-eprsslq 'rulq uo u,,\\op pue rru eq] olul sgnds oo3 >1ce1q qsnSu 'fpeppns 'repnol s,LrorS Surlquru 3o eql se eJeJslq seseeJc elltus 'esJor{ sry lsureEe V Jlesurq eceJqo} }no seqceer - IJ;'Eslq uo elleuruq snoe8roE pue leq slq Jepun,lef arenbse qlrl\ ,(oq,,r,ror -xe ueol e - tulg eqtJo oreq eq1 'e{eqs ueqt 'elqturuo} sur8eqpunor8 eq1

i{OIIJ|I(IOUII\iI

'I

0gtll

'soxal '{1oy 'am"tg ytnd .ra1ou-,rDatJ g l tt')u['san^-tas uotlDzrruUdO Aa

uosurqod'u InEd

1Kf,IAUIAO ONISSIJOUd HINETOUIId I retdeqJ

Robinson

industries' At petroleumprovides precursorsfor the world's petrochemical oil per day.5 of the end of 2003, the world was consuming78 million barrels billion per day' In August 2005, that volume of petroleumwas worth $4'6 or $ 1.7trillion PerYear.
Table 1. Histo Date of PetroleumBefore 1861 Description mosaics. Sumerians use asPhalt as an adhesive for making build and boats, seal canals, water line to bitumen use Mesopotamians asphalt to roads. Egyptians use Pitch to srease chariot wheels, and embalmmummies. The chinese use petroleum for lamps and for heating homes. gas Confucius writes abbut the drilling of 100-foot (30-meter) natural poles. bamboo using for oil pipelines build chinese The wells in china. Greek Arab and Persianchemistsmix petroleum with quicklime to make fire, the napalm of its daY. The Persiansmine seepoil near Baku (now in Azerbaijan)' lamps' Seep oil from the Carpathian Mountains is used in Polish street deep. (600 meters) feet 2000 than Ino.. *.llr oil dig the chinese Oil is extractedfrom oil sandsin Alsace, France' Oil is producedin United Statesfrom brine wells in Pennsylvania' The unit England.6 JamesOakesbuilds a'orock oil" refinery in Jacksdale, James lamps. for "paraffin oil" processes300 gallons per day to make Scotland'' in Whitburn, refinery coal-oil Young builds a F.N.Semyenovdrillsthefirst..modern,'oilwellnearBaku' oil' CanadiangeologistAbraham Gesnerdistills kerosenefrom crude at Ignacy I-u-tasiewicz drills oil wells up to 150 feet (50 meters) deep B6brka, Poland. Michael Dietz invents a flat-wick kerosenelamp (Patentissuedin 1859)' ^ Ignacy Lukasiewiczbuilds a crude oil distillery in Ulaszowice,Poland'8 T;he first oil well in North America is drilled near Petrolia, Ontario, Canada. a colonel Edwin L. Drake triggers the Pennsylvaniaoil boom by drilling 35 produced and deep 69-feet was that Pennsyivania well near Titusville, barrels-per-day. An oil refinery is built in Baku (now in Azerbaijan)' Oil refineries are built near Oil Creek, Pennsylvania; Petrolia, Ontario,

BC 3000

BC 1500 600BC BC 600-500 AD 1 200- 1300 AD 1500- 1600 AD 1735 Early1800s 1847

I 848 I 849 1854 I 857 I858

18 5 9

I 859 I I 860-6

Arlqryes. andUnionCountY. Canada;

of petroleum So what happenedin 1859? What began the transformation often is the As energy? of source primary from a convenienceinto the world's not instigated was oil toward move shifts,the casewith major socioeconomic by just a singleevent,but by the juxtapositionof several: lamps burned whale oil or other animal . In the 1850s,most home-based had always fluctuated wildly, but they prices fats. Historically, whale-oil over-hunting of whales; by some the peaked in the *ia-r850s due to were almostextinct. Whale oil sold for in 1860 severalspecies f stimates, 1855' In an averageprice of US$L77 per gallon between 1845 and more was Lard oil contrast,lard oil sold for aboutUS$0.90per gallon.e'r0 but it burned with a smoky, smelly flame' abundant,

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,{peerle ere esoqr pue sser'o:d u1 ^ou,rntf#"Jo.iJH:11"T#lj Jo002

o]]s eq]

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.Vd .AIIIASNJIJ .UOII3OIIOJ I'UNESNA IIEA\ O{EJC 'UOISSIIUIUOJ luESNI\ PUE UOI]CEIIOJ

IBCIJO]SIH etuunlfsuuod orll ruoJJ uorssruuedqlr.4A .1 pasn o}orld .69gl ul pleg IIo und reeuo14 a,rnilt7

o1 peu8rsep seJrlepIeJeAes Jo lrysseccnslsotu eql .(lqzn8te se,n druel 4e!q. eqJ 'rsg l ul duel euesore{ {cr^\-leg e pelualur z}et6l Ieeqorl4l
C

'ollr^snlrJ ruoJJ solru A\eJ B pleg Iro unu reeuord eql ur 6sg l ur dn Suerdsleql slle,/v\ peceds.,{1eso1c erll Jo eruos 'qsnr s.&\oqs 1 ernSrg eqt pere38rr1 ,{lureuec}i pue .{cor Iro erue^lz(suue4 q8norql pelllrp tsrg er{}ueeq o^eq .,(uru 1r}nq - sree,( 007,2 $oqi'Kqr{irq leq aseulqf, eq] 'ecrnos euo ol Surprocce- lsJU eq] lou se^\ lle,K Iro s6e{erc ,runs red uorllru of rr'srellopz00z ut ree.,{ rptl s$sn }uelelrnbe e se.a{ fep red ggt$Sfl ,l9gl uI .llo elq,lr3ro ecud rql onqj ssel pue %0, Iro prel go ecud aq] ueql ssel el]]ll e .lerreqred gTggn roJ yro e{} ol IIes erq?s3^\ e{erQ red sraxeq gg,(1uopecnpord pue oeap(sreleu lr 17) "'(ep reeJ69 lnoqe - A\olleqsse^\ IIea oqr 'sprepuels s,.,{epo1 ,(g .eruen1,(suue 6ellr^snlrJreeu Suillrrp se^\ oq IIe.,!\oql r{lr^\ Iro Icruls e{eJC ._I ul^\pg '69g 'LT ueq.^\ $nanv uo lsooq ueppnse lo3 euesorarJ0f1l1quF'^e eqr . l 'sleJ Ieturueueql ror{}oBurqleuos tunq

twalLta Ao 3u t s,sa t ot 4 tana p4a d

Robinson

"When oil first startedflowing out of the wells in western Pennsylvaniain barns,cellars,stores,and farmhouses, oil men ransacked the 1860's,desperate beer, whiskey, cider, turpentine, trashyards for any kind of barrel molasses, sale,fish, and whateverelsewas handy.But as coopersbeganto make barrels and that size continues size emerged, especiallyfor the oil trade,one standard gallons. It ts 42 to be the norm to the present. "The number was borrowed from England, where a statutern 1482 under 42 gallonsas the standardsize barrel for herring King Edward IV established "divers deceits" in the packing of fish. At the and skullduggery in order to end time, herring fishing was the biggest businessin the North Sea. By 1866, seven years after Colonel Drake drilled his well, Pennsylvaniaproducers confirmed the 42-gallonbarrel as their standard,as opposedto, say, the 3lt/z gallon wine barrel or the 32 gallon London ale barrel or the 36 gallon London beerbarrel." In sharpcontrastto the situationtoday, in 1870 America was the world's leading oil producer,and oil was America's 2nobiggest export."Agricultural products were first, accounting for 79% of exports that were worth, on of Despitethe ravages uu.rug., US$573million per year from 1870to 1879.14 "King Cotton." the U.S. Civil War, the main agriculturalexportwas still

1.2

What Is Petroleum?

Before we go on to talk about petroleum processing,it is important to know something about petroleum itself. Petroleum is called a fossil fuel becauseit is formed from the bodies of ancient organisms primarily onecelled plants and animals (see Chapter 2). Contrary to modern myth, only a tiny fraction (if any) of the molecules in crude oil are from dinosaurs.When thesecreaturesdied, their remains accumulatedat bottoms of ancient lakes or seas, along with sand and other sediments.Over time, a combination of pressure,heat, and bacterial action transformedthe depositsinto sedimentary rock. The incorporated organic matter was transformed into simpler water, carbon dioxide, hydrogen sulfide, chemicals,such as hydrocarbons, and others. rock was porous, The chemicalsdidn't always stay put. If the surrounding into a reservoir or surface to the up either migrate, liquids and gasescould of salt. Today, dome or a (Figure 2) that was capped by impermeablerock when petroleum geologists look for oil, they actually are looking for structuresthat might be traps for liquid hydrocarbons.

's}socSurssecord 'sro}cJJeq}oq}I \\ s1ceJ;e s1y\or{s }ue}uocJnJInseql a"tnStl 3uo1y 'epruc eql tuo:; pelll}slp eq ueo ''J1e 'euesoJel 'eutlose8qJnru lrtoq qclq^\ 'setgedorduorlellllslpJo uol]eolpurq8nor e st fltner8 Idy eurrrrrelep epruc eql qslq^\ tuoJJpleg Iro og} sr ocrnos eql '}ue}uo.'r eqJ 'pecnpord se,iy\ rnJlns pue '(&lsuep Jo ernseeu e) ,{lrnzr8 Idv 'ecrnos s}I 8ut}tc .(q eprur e e relleJeqcsJOpurI'sepruopelceles IZ JoJseqredordsereduroc e alqoJ 'peuru .(eq1pr1os eJe ag o] e^uq os eruospu 'lole,lt 'peleeq fltsee A\oU A\oU sJeqlo su se etuos 's33a feql ssalun ere l,uop 'ueer3 ecnpo.rd uelloJ e{rl Ileus Jo Jnos e}sel eruos 'sepruc {clq Jo u.A\oJq eruos tuor3tsllo epruJ sllo,/KreWO 'lro elqele8e'r s Jeelc se eJ slle.,tn. 'spuoq Iscrruegcr(q suoqrecorp,,(q ol pe{ull ete ,(eql esnceq o^otueJ o} JepJeq oJ slelelu pue ue8r(xo 'ue8o;lru 'JnJIns- slueultueluoJ rofeur Jel{lo eq} lnq '(7 uorlceg ees) qse^\ 'ueSfxo 'ue?ot1tu pe^olueJeq uec suseqJ 'sllspue 'sle1eru e glr,^A Jelsl!\-loq Jo slunorue Jelletus qlr^\ 3uo1eJnJIns o/olw t ol I uleluoc osl sllo epruJ 'uoqJc 'uoqrec q pue ?ututeluoc pue ueSoJpfq ol uorlrppe ueSoJpr{q lsou 'serldur eluu eql sv ere suoqJcoJpr(q slJrruoqJ lueJeJJrp rr.er'suoqJecorp,,(q SututluoJeJnlxlruxelduoc e sI IIo opruJ 'ut8uo sll ol enCJ Jo spuesnoql 'tunelorledyoSuruger pue 'uorlcnpord 'uorlerurogeq] ]noqe uorlerruoJur IeJeueB leuotllppe seprno-rd pue .re8reg fq >1ooquelllJln-llo1!\V 'selels pallun eq] pue sruosropuv 'runalorled cr1eq1u.,{s epeueJ ur sorJeugeJ Iro luolluenuoc o1 lues sI qclql\ 'epeueJ go ,(ep-red-sleueq 000'001 ue{} eJolu olul pouonuocere spuusIIo 'se8 srseqlufs roTpusleonueqce{eru o} pesn sr qJrq.tA q 'tunelorled cr1eq1u,(s e 6ecl4v rllnog pue euqJ uI olur peueluoc sr luecrJru8rs ]unotu Ieoc Jo 'Jorneoq ,(11ensn selnceloruuoqrecorpfq oq] pue ;eq8rq sr ere lueluoc lreulru 'olBqs '1eoc - IenJIISSOJ pllos uI eq] - spuesJl puBspuEs IIo Io Jo socJnos
JToAJOSaU uneloJlod '7 atn8tg

tial Ar a^o 8ut ssa tot 4 una p$a d

Robinson

that light crudes(thosewith high API gravities)often contain less sulfur and nitrogen than heavy crudes,but not always.
of 21 Selected Crude Oils Table2. Properties Specific Sulfur (wto/o) API GravityT Gravity Crude Oil l.l 0 .8 9 73 2 6 .2 Alaska North Slope 1.8 0 .8 5 60 33.8 Arabian Light 2.6 0.8740 30.4 Arabian Medium 2.8 28.0 0.8871 Arabian Heavy 4.8 1.0143 8 Athabasca(Canada) 3.6 t6.2 0 .9 580 Beta (California) 0.37 0 .8 333 38.3 Brent (North Sea) 0.14 35.4 0 .8 478 Bonny Light (Nigeria) 0 .9 986 5.3 t0.2 Boscan(Venezuela) 0.25 0 .8 363 31.7 Ekofisk (Norway) t6.4 0.9s67 0.32 Henan (China) 4.3 2 0 .8 09291 Hondo Blend (California) 1.1 0 .9 752 13.6 Kern (California) 2.5 0 .8 686 3 1 .4 Kuwait Export 1 7 .9 0 .9 471 0.26 Liaohi (China)\ 2 2 .2 0.9206 3.4 Maya (Mexico) 13.8 0 .9 738 0.82 Shengli(China) 45.9 0.7976 0.03 Tapis Blend (Malaysia) a1 1 J I.J 0.8383 0.32 West Hackberry Sweet* 39.6 0.8270 0.34 West Texas Intermediate 0 .9 309 0.15 20.5 Xiniiang (China) * Producedfrom a storagecavern in the U.S. StrategicPetroleumReserve I ,qpt Gravity is relatedto specific gravity by the formula: oAPI : 141 gravity@ 60'F) - 131 .5 .5 + (specific Nitrogen

(wl%L
0.2 0.07 0.09 0.15 0.4 0.81 0.10 0.10 0.65 0.10 0.14 0.62 0.7 0.21 0.41 0.32 0.72 nil 0.10 0.08 0.35

15

25
API Cravity

35

45

O SulfurContentr Nitrogen Content Figure -1.Sulfur and nitrogen versusAPI gravity for selectedcrude oils

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Mat ^-taAO ?ut ssa to.t4 runa p&a d

Robinson

Tables 3 and 4 show that isomers have different physical properties.rs They also can have significantly different chemical properties.For gasoline, one of the most important chemical propertiesis octanenumber. The research octane number (RON) for n-octane is -27 comparedto a RON of 100 (by For heptaneisomers,RON definition) for isooctane(2,2,3-trrmethylpentane). values range from 45 for 2-methyl-hexaneto >100 for 2,2,3-trtmethylbutane, comparedto zero(by definition) for n-heptane.Octanenumbersare discussed in more detailin Section8.2.
Table -1.Boiling Points of SelectedLight Paraffins Boilins Point Formula -2s9.9 CH+ Methane -127.4 CzHo Ethane -43.7 C 3t.7 C+Hro n-Butane I 1.9 H Isobutane 96.9 CsHrz n-Pentane 82.3 CsHrz Isopentane 49.0 C.H Neopentane 258.0 CsHrs n-Octane 2t0.7 C Isooctane Boilinp Point

-t62.2 -88.6 -42.1 -0.1 -tt.2 36.1 28.0 9.5 t25.6 99.3

The melting points of paraffin isomers also can differ significantly. As shown in Table 5, long-chain n-paraffins melt at relatively high temperatures, This explains while their branched-chainisomersmelt at lower temperatures. their different behaviours as lubricants. Long-chain norrnal paraffins are waxy, so as lubricants they are terrible. Conversely, iso-paraffins with the samenumber of carbonsare excellent lube basestocks.
Table 4. Fusion Points for SelectedC16Paraffins. Melting Point ("F) Formula Name
Hexadecane 5-Methylpentadecane CroH:q CroH:+ CroH:q

Melting Point (oC)

7.8-D imethvltetradecane

64.1 -29.s -t23.r

17.9 -34.2

1.2.1.2

Aromatics and NaPhthenes

are also found in petroleum.Aromatics contain Aromatics and naphthenes carbon rings are one or more unsaturated5 to 6-carbon rings. In naphthenes, hydrogen. with saturated that Figure J shows structuresfor a few of the aromaticsand naphthenes ring, the have been found in crude oils. For aromaticswith one six-carbon ofld for naphtheneswith one ring, the general general formula is CnHzn-6, formula is CnH2n.

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'reqrunuuoqJc 'sJeqrunu eJescrlruoJ ou]coreq8rq eneqpu Jesuep erus eql qll/\\ saueqlqdeupu? sug3eredo1 pereduroJ 'sergedord 1ecrs,{qd feldstp seuaqlqdeupue s3I}ruoJV pu Iscnuegc ]uereJJrp,{11uecgru8rs
Iro epruc ut punoJ seueqtqduupu scrleruorv
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Robinson

.CH, --S-.- -CH, HrC'

-CH,

methy propylsulfide

3-methylthiacyclohexane

dibenzothiophene

nlnr
V\Nl,
quinoline

M l\|tv

t\/\N-^\7 H carbazole

-7\'v^ tl \t l \ )t t\7\*Ao
H

2 ( 1 H )q u i n o l i n - o n e

\-*'u *1\ /
\-.\ loll /\l
Vanadium-containing porphyrin R = -CH., -CrH' etc.

Figure 6. Hetero-atom compounds found in crude oil

H2C-CH2 CrHo ethylene

HrcT

" C H- c H .

-.'' -CH -Ch^ Hrc/ \crf

CoHu trans-2-butene H"C

C.Hu propylene

HrC\

\c' .zCHs
v-vl I

CH. coHu isobutene

H.C-

-c{._ \ C H .cHz- C H ,
crH,o trans-2-pentene

H.C

/\

CHr CuH',0

isopentene

Figure 7. Selectedlight olefins

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t2 Processing, l86l - 2000 Table5. SignificantEventsin Petroleum Description lamps startsto decline. 1878 ThomasEdisoninventsthe light bulb. The use of kerosene Karl Benz build gasoline1889 Gottlieb Daimler, Wilhelm Mayback and (separately) poweredautomobiles. productionof the Curved Dash Oldsmobile. 1901 RansomE. Olds beginsassembly-line 1908 Ford Motor Companyoffers Model T's for US$950 each. l9l2 William Burton and Robert Humphreys develop thermal cracking. Pennsylvania. l9l3 Guif Oil builds the world's first drive-in filling stationin Pittsburgh, the Dubbs thermalcrackingprocess. UOP commercializes l9l9 1929 StandardOil of Indiana (now BP) commercializesthe Burton processfor delayed coking at Whiting, Indiana. 1933 UOP introducesthe catalytic polymerization of olefins to form gasoline. EugeneHoudry, working for Sun Oil, patentsHoudry Catalytic Cracking (HCC). 1934 1938 A consortiumof refinersdevelopssulfuric acid alkylation,which is first commercializedat the Humble (now ExxonMobil) refinery in Baytown, Texas. 1940 Phillips developsHF alkylation. Oil of New Jersey(now ExxonMobil) commercializes the FCC process at 1942 Standard Baton Rouge,Louisiana. 1949 Old Dutch Refining in Muskegon, Michigan startsthe world's first catalytic reformer basedon the UOP Platforming processes. 1950 Catalytic hydrotreatingis patentedby Raymond Fleck and Paul Nahin of Union Oil. processes. Ca and C5lC6 isomerization 1960s UOP introduces StandardOil of California (now Chevron) introducescatalytic hydrocracking. 196l Earth Day. The newly createdU.S. EnvironmentalProtection The world celebrates 1970 the CleanAir Act, which requiresa 90o/o reductionin auto emissions Agency passes by 1975. The EuropeanUnion issuessimilar requirements. this shape-selective catalyst 1972 Mobil inventsZSM-5. During the next threedecades, includingFCC, catalyticdewaxing,and the finds usesin numerousprocesses, of methanolto gasoline. conversion 1975 The catalytic convertergoescommercial. The phase-outof tetraethyl lead begins. issues the CleanAir Act Amendmentsof 1990,which lay the 1990 The U.S. Congress framework for reformulatedgasolineand low-sulfur diesel. are developedto remove sulfur from gasoline.These include 1990s Severalprocesses SCANfining (Exxon), OCTGAIN (Mobil), Prime G (Axens), and S Zorb (Phillips). 1993 Chevron commercializesIsodewaxing for converting waxy paraffins into high-quality lube basestock. The EuropeanCommission issuesthe Auto Oil il report, which includes a timetable 2000 for low-sulfur easolineand ultra-low-sulfur diesel.

In 1914, Jesse A. Dubbs and J. Ogden Armour founded the National Hydrocarbon Company, which later becameUniversal Oil Products(UOP).20 UOP grew to becomethe world's largestlicensor of processtechnologyfor the oil refining industry. In 1919, UOP commercializedthe Dubbs process, which solved some of the problems associatedwith the Burton-Humphreys process.The Dubbs processproducedfewer coke deposits,it could process heavierpetroleum fractions,and it ran longer betweenshutdowns. Standard Oil of Indiana commercrahzedthe delayed coking process at Whiting, Indiana in 1929.In 1933, UOP commercializedthe conversionof olefins to gasolinevia catalytic polymerizatron.Later in the 1930s,refiners beganusing tetraethyllead to boost the octaneof gasoline.A consortiumof

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controls (including catalytic converters)on diesel-powered cars and trucks. Refiners are respondingby installing additional hydrotreatingcapacity.

1.4

Modern Petroleum Processing

All refineriesare different. They have different histories, locations,and market drivers.Therefore,no single illustrationcan captureall of the possible combinations and permutationsof the processes that fit together to comprise an oil refinery.But despitetheir differences, most refineriesperform the seven basicoperations namedin Table 6.
Zable 6. SevenBasic Operationsin PetroleumProcessing Separation Combination o o Distillation Catalytic polymerization . . Solvent refining Alkylation Conversion Treating, finishing, blending o o Carbon removal Gasoline,kerosene and diesel o o Hydrogen addition Lubes and waxes Reforming . Asphalt o Catalytic reforming Protecting the Environment o o Steam/hydrocarbon reforming Waste water treatment Rearrangement o Disposalof solids o Isomerization Sulfurreco

Figure 8 shows a simplified layout for a high-conversionrefinery in the United States. The diagram doesn't show product blending and sulfur recoveryunits, but theseare almost always present.Lube-oil processingand hydrogenproductionunits also may be present. The depicted plant is configured for maximum fuels production. In a typical Europeanrefinery, the coker would be replacedwith a visbreaker.In many Asian refineries,where diesel demandis higher than gasolinedemand, the coker would be replacedby a visbreakerand the FCC by a hydrocacker. The rest of this chapterprovidesa brief overview of the processes shown or mentioned above. The chapters that follow p.rovide detailed process descriptions, with emphasison recentdevelopments. Generalinformation on refining technologycan be found in the excellentbooks by E.I. Shaheen,22 and W.L. Leffler,23and in a manual published by the U.S. Occupational Safety and Health Administration.2aEach year, Hydrocarbon Processing compiles a widely read refining processhandbook,which gives descriptions of about 120 licensed processesoffered by engineering contractors,oil companies, and of courseprocess licensors.25

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are addedto the solids. In chemical desalting,water and surfactants suspended crude, heatedto dissolve salts and other impurities, and then sent to a settling In electrostaticdesalting,chemicalsare tank where the water and oil separate. which drives the separationof charge, electrostatic a strong replaced with water from oil.
LPG, Propane

Light Naphtha

HeavyNaphtha Light GasOil HeavyGasOil VacuumGasOil Atmospheric DistillationUnit VacuumResidue

Desalter Crude Oil

Vacuum DistillationUnit

Figure 9. Crude distillation

Modern crude distillation towers can process200,000 banels of oil per day. They can be up to 150 feet (50 meters) tall and contatn 20 to 40 fractionationtrays spacedat regular intervals. In some towers, the trays in the top sectionare replacedwith structuredpacking. Before reachingthe tower, desaltedoil goesthrough a network of pre-heat to a fired heater,which brings the temperatureup to about 650"F exchangers (343'C). If the oil gets much hotter that this, it startsto crack and deposit carbon inside the pipes and equipmentthrough which it flows. The hot crude entersthe distitlation tower just above the bottom. Steamis addedto enhance vapor pressurein the column. it doesso largely by decreasing separation; When hot oil enters the tower, most of it vaporizes. Unvaportzed heavy fuel oil andlor asphalt residue drops to the bottom of the tower' where it is drawn off. The vapors rise through the distillation trays, which contain perforationsand bubble caps (Figure 10).Each tray permits vapors from liquid on top of the tray. This below to bubble through the cooler, condensed

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Table Z. Destinations for Straisht-Run Distillates

Fraction LPG Light Naphtha Heavy Naphtha Kerosene Gas Oil Vacuum Gas Oil

Approx. Boiling Range oC oF

-40to 0 39-85 8 5- 2 0 0 t7 0 - 2 7 0 - 340 180 340- 566

Next Destination -40to 31 Sweetener 8 0 - 1 8 s Hydrotreater - 3 9 0 Cat. Reformer 185 3 4 0- 5 1 5 Hydrotreater 3 5 0- 6 s 0 Hydrotreater 650- 1050 FCC Hydrotreater Lube Plant Hydrocracker >1000 Coker Visbreaker Asphalt Unit Hydrotreater

Vacuum Residue

>540

Ultimate Product(s) Propanefuel Gasoline Gasoline,aromatics Jet fuel, No. I diesel HeatingOil, No. 2 diesel Gasoline,LCO, gases Fuel oil, FCC feed Lube basestock jet, diesel,FCC Gasoline, feed,lube basestock Coke, coker gas oil Visbreaker gas oil, resid Deasphaltedoil, asphalt FCC feed

Table 8 shows that straight-run yields from various crude oils can differ The naphthacontentof Brent is twice as high as Ratawi, and its substantially. residue content is 60oh lower. Bonny Light yields the most middle vacuum distillateand the leastvacuumresidue.
Iable 8. Typical Straight-runYields from Various Crudes26'27 Brent Bonny Lt. Green Canyon Source field Country API gravity Specific gravity Sulfur, wto% Light ends Light naphtha Medium naphtha Heavy naphtha Kerosene Atmospheric gas oil Light vco Heary VGO Vacuum residue Total naphtha Total middle distillate Norway Nigeria USA

Ratawi Mid East

38.3 0.8333 0.37

z.)

35.4 0 .8 4 7 8 0.14 1.5 3.9 14.4 9 .4 t2.s 2r.6 20.7 10.5 5.5 2 7 .7 34.1

30l . 0.8752 2.00 1.5 2.8 8.5 5.6 8.5 t4.l 18.3 14.6 26.1 16.9 22.6

24.6 0.9065 3.90 l .l 2.8 8.0 5.0 7.4 10.6 t7.2 15.0 32.9

Yields. wtTo feed

6 .3 t4.4 9 .4 9 .9 1 5I. t7.6 t2.7 t2.3 l 30. 25.0

r5 . 8 18.0

Atmosphericdistillation of the best crudesyields about 60% naphthaplus and gas oil), but the averageis closerto 40Yo.In middle distillates(kerosene contrast,Table 9 shows that during 199l-2003, the United Statesconsumed, on average,70yo of its petroleum as gasoline and middle distillates. This

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In traditional solvent deasphalting, residual oil and propaneare pumped to tower at 150 to 250'F (65 to 120'C) and 350 to 600 psig (2514 an extraction occurs in a tower, which may have a rotating disc to 4240 kPa). Separation (Figure products are evaporatedand steam stripped to 11). Liquid contactor recoverthe propanesolvent,which is recycled. version of solventdeasphalting An advanced is "residuumoil supercritical extraction," or ROSE. The ROSETMProcesswas developedby the KerrMcGee Corporationand now is offered for licenseby KBR Engineeringand a subsidiaryof Halliburton. In this process, Construction,, the oil and solvent are mixed and heatedto above the critical temperatureof the solvent, where the oil is almost totally insoluble. Advantagesinclude higher recovery of liquids, lower operatingcostsdue to improved solventrecovery, deasphalted and improved energy efficiency. The ROSE process can employ three the choiceof which depends differentsolvents, upon process objectives: Propane: Preparation lube of basestocks Asphalt production Butane: Pentane: Maximum recoveryof liquid 2.2.2 SolventExtraction

Solvent extractionis used to remove aromaticsand other impurities from lube and grease stocks.The feedstock is dried,then contacted with the solvent in a counter-current or rotating disk extractionunit (F;gure I 1). The solvent is separatedfrom the product stream by heating, evaporation,, or fractionation. traces of Remaining solvent are removed from the raffinate by steamstripping precipitatorsmay be used to enhanceseparation or flashing. Electrostatic of inorganiccompounds. The solventis then regenerated and recycled.

Solvent Evaporator Extracted aromatics Extract and Solvent

Raffinate (lube oil)

Figure 11. Rotating-disk solvent extraction

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22

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heavy carbon is removed from every molecule. Rather, it means that and moleculesare split ("cracked") into a smaller molecule with a higher H/C H/C low with Molecules HlC. lower a with another smaller molecule hydrocarbons(PAH) - can condenseto form coke (Figure l2). polyaromatic ^Cond.ntation hydrogen,lowering H/C evenmore' release reactions

3.1

Visbreaking

Visbreaking is a mild form of thermal cracking that achievesabout 15% a conversionof atmosphericresidueto gas oils and naphtha.At the sametime' low-viscosityresidualfuel is produced. "soaker." In Visbreaking comes in two basic flavors "short-contact" and and sent (480'C) visbreaking,the feed is heatedto about 900'F short-contact The to a "soaking zone" (reactor) at 140 to 300 psig (1067 to 2110 kPa). formation. coke restricting while to occur cracking elevatedpressureallows To avoid over-cracking,the residencetime in the soaking zone is short hot oil severalminutes comparedto severalhours in a delayedcoker and the vacuum to a sent is quenchedwith cold gas oil to inhibit further cracking and at tower for product separation. "Soaker" visbreaking keeps the hot oil elevated temperature for a longer time to increase the yield of middle distillates.The low-viscosityvisbreakergas oil can be sentto an FCC unit or hydrocrackerfor further processing,of usedas heavy fuel oil'

3.2

Coking

come in two basic forms - delayedcoking, which is a Coking processes and fluid-bed coking, which is continuous' process, semi-batch 3.2.1 DelaYedCoking

In a delayedcoker, vacuum residuefeed is heatedto about 900 to 970"F (4gj to 520"C) and sent to a large coke drum. Cracking begins immediately' generating coke and cracked, vap orized products. Coke stays behind in the d-* while the vaporsrise to the top and flow to the product fractionator. Liquid productsinclude coker naphtha,light coker gas oil (LCGO), and heavy-cokergas oil (HCGO). A11of theserequire further processingdue to their high olefins content, which makesthem unstable and poorly suited for direct blending into finished products. The coker naphtha and LCGO are hydrotreated.The HCGO can go either to an FCC unit or a hydrocracker.

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coke rapidly grow due to the heat produced by asphaltenepolymerization, producingdiscretemini-balls 0.1 to 0.2 inches(2 to 5 mm) in diameter.In the center of the drum, the mini-balls can stick together to form clustersas large as 10 inches (25 cm). On occasion,a cluster breaks apartwhen the coke drum is opened, spraying a volley of hot mini-balls in every direction. Adding aromatic feeds, such as FCC decant oil, can eliminate shot coke formation. Other methods of eliminating shot coke - decreasingtemperature,increasing drum pressure,increasing the amount of product recycle - decreaseliquid yields,which is not desired. A quantitativemeasureof the quality of coke is the coefficient of thermal expansion(CTE). A low CTE meansthat the product has a low tendency to expand when heated.Rangesof CTE for the three major types of petroleum coke are shown in Table I I .
Table 11. Coefficients of Thermal Ex Needle coke Spongecoke Shot coke nsion for PetroleumCoke Products CTE (cm/cm/oC x 10-')

0to4 8 to 18 >20

Shot coke cannot be used in making anodes for aluminum production, becausethe outer layer of a shot spherehas a very low CTE while the inside has a very high CTE. When rapidly heated,the interior expands,cracking the outer layer like an egg shell. Consequently,in aluminum smelters,shot-coke anodesquickly turn to dust. Other specialtycarbonproductsmade from petroleum include recarburizer coke,which is usedto make specialtysteel,and titanium dioxide coke, which is used as a reducing agent in the titanium dioxide pigment industry.2e 3.2.2 Fluid Coking

Fluid coking, also called continuouscoking, is a moving-bedprocessfor which the operating temperature is higher than the temperaturesused for delayed coking. In continuous coking, hot recycled coke particles are combined with liquid feed in a radtal mixer (reactor) at about 50 psig (446 kPa). Vapors are taken from the reactor, quenched to stop any further reaction, and fractionated.The coke goesto a surge drum, then to a classifier, where the larger particles are removed as product. The smaller coke particles are recycled to a preheater,where they mix with fresh feed. Coking occurs both in the reactorand in the surgedrum. Installation costs for fluid coking are somewhat higher than for delayed coking, but feedscan be heavier and heat lossesare lower.

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specific information on the manufacture and use of catalysts used for FCC and otherrefining processes. The cracking reaction is very fast. It produces light gases,high-octane gasoline,and heavier products called light cycle oil (LCO), heavy cycle oil (HCO), slurry oil, and decantoil. It also leavesa layer of coke on the catalyst particles,making them inactive. can reach 900 to 1020"F (482 to At the top of the riser, the temperature 549'C). The temperatureat the riser outlet is a key factor in determining conversion and product selectivity, So FCC operatorscontrol it as tightly as favor productionof olefin-rich light gas at the possible.Higher temperatures favor gasolineproduction, and at expenseof gasoline,moderatetemperatures in favor of middle distillates. gasolineyields decrease lower temperatures In the disengagingsection, steam is used to help separatethe nowdeactivatedcatalyst from the reaction products. The catalyst goes to the regenerator,where the coke is burned away by fluidized combustion in the up to 1350'F (132"C) returns of air. The hot catalystat temperatures presence where the cycle beginsagain. to the riser/reactor, In a 60,000 banels-per-dayunit processinga typical mixture of vacuum gas oils, the total catalystin the unit (the "inventory") is 400 to 500 tons. To maintain activity, about 0.5 to I wtoAof the inventory is replacedeach day. If the feed to the unit contains significant amounts of residue, the replacement catalystis cooled and shippedeither to a land rate is higher. The discharged filI for disposal or to another refiner, which may have a particular use for "conditioned"FCC catalvst. 3.3.2 Heat Balance

or they won't run. Understandingheat FCC units must be heat-balanced, FCC variables interact. The burning how balanceis the key to understanding of coke in the regeneratorprovides all of the heat required by the process. breakdownof FCC heatrequirements. Table /3 gives a representative
Table 13. Breakdown of FCC Heat Re Heat-Consuming Event Heat up and vaporize fresh feed Heat recycledoil Heat of reaction (endothermic) Heat steam Heat losses Heat air to regeneratortemperature Heat coke from the reactor to regeneratortemperature Total Heat Duty

Percent of Total

40-50% 0-r0% t5-30% 2-8% 2-5% 15-25% r-2% Btr/lb 500-1000 kJ/ke l160-2325

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3.3.4

ResidueFCC

Many modern FCC units are designedto processsignificant amountsof vacuum residue. These units use catalyst coolers (e.g., steam coils) in the zone to remove excessheat from the or a secondregeneration regenerator more coke than substantially vacuum residuegenerates unit. This is because when the extra coke is conventionalFCC feeds,and excessheat is generated burned away from catalYst. more In vacuumresidue,the metalscontentcan be very high - sometimes are bad metals these unit, an FCC In nickel-plus-vanadium. than 200 wppm yields. Vanadium liquid decreases coke formation and news.Nickel increases liquid yields, and destroysthe catalyst. For reducesconversion,decreases these reasons,refiners pretreatthe residue in a hydrotreaterbefore sending it on to the FCC. the decreases In addition to removing most of the Ni and V, the pretreater part the feed of the FCC, concentrationof sulfur, nitrogen, and aromatics.In sulfur ends up in liquid productsand part ends up as sulfur oxides (SOx) in the flue g&S, so removing sulfur from the feed is beneficial. Removing FCC catalystactivity. feed nitrogen suppresses nitrogen is beneficialbecause FCC conversionby as much as l0 volo/o. feed aromaticsincreases Saturating This alonecanjustify the cost of building the pretreater.

3.4

Hydrotreating and Hydrocracking

A modern petroleum refinery may have four or more hydrotreating units. Strictly speaking,hydrotreatersare not conversionunits becausethe breaking bonds is minimal. However, it is convenientto discuss of carbon-to-carbon hydrotreating together with hydrocracking and mild hydrocracking because flow schemes. and process they employ similar catalysts Table 14. Hydrocrackerstend to presented in The key differencesare operateat higher pressure,using different catalysts,and with lower linear hourly spacevelocity (LHSV). LHSV is equalto the volume of feed per hour divided by the catalystvolume. A lower required LHSV meansthat a given volume of feed requires more catalyst.In terms of processconditions and conversion,mild hydrocrackinglies somewherebetween hydrotreatingand hydrocracking. full-conversion

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so many commercial units Hydrotreating is exothermic (heat-releasing),, quench zones.In a quenchzone, by separated beds catalyst compriseseveral with relatively cold, are mixed preceding bed hot processfluids from the quenchgasbeforepassingto the next bed. hydrogen-rich
RecycleGas Compressor

Make-up Compressor

High-Pressure Amine Absorber

High-Pressure Separator To Gas Plant

Low-Pressure Separator Air Cooler Wash Water

NH*SH(aq)

To Stripper, Fractionator

Figure 14. Gas-oil hydrotreatingand once-throughhydrocracking

Wash water produceHzS and NH:, respectively. HDS and HDN reactions which remove ammonia, reactor to last from the the effluent into injected is The NH+HS(aq). bisulfide, phase as ammonium aqueous goes into the flash drums. in water downstream NH+HS(aq)is rejectedfrom the unit as sour In the high-pressureflash drum, liquid products are separatedfrom the hydrogen-richgas, which is recycled to the reactors.In most hydrotreaters designedfor deep desulfurization,H2S is removed from the recycle gas with a high-pressureamine absorber.The liquids go to a stripping column, which removes entrainedHzS and other light gases.These go to a low-pressure amine absorberand then to either a gasplant or the refinery fuel-gassystem.

'peleerlorpfq eq spo se8 tsnru,(11ensn lqE[ req]o puE 'suor8eJ euesoJo{ uru-1q8rer1s esoq}u1 '8ur1eeq euJorl JoJpesnsr ouesoJe{ JrUIns 'lenJ -A\ol'pForvr q oquo sued r{ueur o}ur euesoJe{ uec 8ur1ee4o-rp.iu }ef UoAuoJ fluenes-,lo1 'saueqlqduu Sununq-reueelJ o]ut spunoduroc cr]eruoJ eruosgeAuo.r ol (VCH) uoqezrleruoreoporp,(q plFu Sursn fg '1ery-1ef rog suorlecgrceds leerlr 1ou ,(eru sl'ueeJlseuesoJe{ uru-1q8rer1g'3u1waqo.tp[H auasony 'euelco eurlose8 Jo ssol 'speq 's1sr(1e1ec eznurunuol uor]uorlce4-eJd roTpue e1dr11nul e1dr11nu 1sr(1e1ec Surpeeleq] lnq 'plpr ,(1errr1e1er esn sessecord eJeseJnssard pue sernleredruoJ_ '3ur1ee4oJp,(r{ eurlosu8sossncsrp uor}ces 'suorlecgrceds JrUIns}ueoar S'7,'g '&u4na4o,tptg auryosng leerrr ol aurlose8Eurleerl-1sod Jo lxeluoc eq] u1 'lueurdrnbe rueeJlsuly\op ut uorsoxoc e]JelooJe pue 'slcnpord peqsrurJeleurrusluoc 's1s.,(1eluc eleArlJeepuec feq] 'penorua: 'serlundrureuosolqnoJ] ]ou lsotu eql eJe sleletu pue 'ue8fxo 'ue8o;1tu JI 'JrUInS'spunodruocclleruore'(ueur pue sugalo osle ]I 'suorlc{ lsoru seleJnles runelorled plnbll tuor3t s}ueurtu}uocseloruoJ SurleerloJpr(q cqf,1e1e3

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)L

Diesel Hydrotreating. From l99I in Sweden,1995 in California, and 1998 in the rest of the U.S., hydrotreatingwas used to make diesel containing <500 than wppm sulfur. Generally, diesel hydrotreatersoperateat higher pressures days, These catalysts. different use often they and units, nup6tfiuand kerosene .rnd.r pressureto make ULSD by the end of 2006, most U.S. refiners either have oi will be (a) building new diesel hydrotreaters,(b) revamping existing units by changing catalysts, modifying reactor internals, adding a highpressureHzS absorber,and/or adding a new reactor, or (c) converting other units to diesel service. FCC Feed Pretreating: VGO, CGO, and VBGO. For hydrotreaters that preparefeed for conventionalFCC units, removing nitrogen (HDN) from the f..O it beneficial, becauseorganic nitrogen (especiallybasic nitrogen) inhibits cracking by binding to the highly acidic active sites in FCC catalysts.The ,.-orrul of sulfur (HDS) can reduce the size of, or eliminate the need for, FCC gasoline post-treating units. By converting aromatics to naphthenes In FCC and other @DAj, FCC feed pretreatersincreasefeed "crackability." But except for products. convert to lighter thermal cracking units, naphthenes losing side chains, aromatics are rather inert. If anything, they tend to form polyaromatic hydrocarbons (PAH) and coke. Pretreatersalso benefit FCC uniis by removing metals (primarily nickel and vanadium) and Conradson carbon (CCR). CCR correlatesstrongly with the tendency of a feed to form coke in a delayed coking unit. It also correlateswith coke-formation in an FCC unit. By reducing feed CCR, a pretreaterallows an FCC to operate at higher feed rates and/or higher conversion.If the feed rate stays constant,the The extent of the increasedepends conversioncan increaseby 10 to 20 volo/o. conditions under which the feed is the and feed raw the of upon the properties hydrotreated. FCC Feed Pretreating: Residue. Originally, residue hydrotreaters were built to reduce the sulfur content of heavy fuel oil. These days, a large percentageof residue hydrotreatersare used to pretreat FCC feeds. Residue hydrotreatingrequireshigher pressure,lower LHSV, and at least one hot flash drum after the reactors. Another main difference is the need to use one or more HDM catalyststo protect the HDS catalyst from metals such as nickel and vanadium. If not removed, Ni and V acceleratedeactivation and the In the Resid Unionfining processoffered by UOP, buildup of pressure-drop. a guard reactorupstreamfrom the main reactors. into is loaded catalyst HDM Chevron Lummus Global, an OCR ("onstream by process offered In the RDS catalyst replacement")or UFR ("up-flow reactor") unit removesmetals from the RDS feed. With OCR, a refiner can process residues containing 400 metals (Ni + V). wppm - -Lube Hydrotreating. The mild hydrotreating ("hydrofinishing") of lube oils improves color, odor, and stability by removing olefins, sulfides and mercaptans. Severe hydrotreating also removes aromatics, nitrogen, and refractory sulfur comPounds.

'8 pue sreldsrlJul peqlrsss: , ele sauoqcs ,Kou ssecoJd SurlcercoJpr(g Jeqlo '1sf1e1ecSurlcerco:pi:. 'lery uleluoc speq 1s,(1e1ec II" leselp Jo uorlcnpord unrurxeru rog peu8rsal sre>lcercoJpfq etuosu1 '1sf1e1ec r.. Sut4cercorpfq ur]uoc speq elrQ luenbesqns SurleerloJpr(q ureluoc o1 f1eT1 eJBspeq A\eJlsJU eql .Je{cercorp 1sr(1e1ec i; 3 uI 're{cerco;pfq uorsJe^uoc-q8rq q8norqt-ecuoe ro 'Eunlcercorp,(q pllu I 'leleerlorpr{q lo-se8 e aqucsopuc 21 a"tnStgur arusrlcs \ou ssecordeq1 ,rold ssaJordSuplcurcorp{g 1.f.r

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'se8,(d;o,{r1lqe1s .su$elo-ouoru eqt selordrul s1qJ, o}ur sugalorF suo^uoc Eu4eerlorp,(qp[[h[ 'sun8 urroJ o] rre q]l^\ ]cer qclq^\ ,sugaloip surluocseEf4 'eurlose8 olul pepuolqse,,K seEfd eruos'euelcoqSU slr ol anp '1sedeql uI 's1ue1d sugelo ruo{ lcnpord-,,(q e '(seEfd) eurloseE srs,(1o;fd1.. ftr1enb eql se^ordrul Surleerlorp{H 'Eu1ruauorytg aunosog slstlo"tt4
g
A aMJaAO 8utssacot4 wnoIot!.-

34

Robinson

3.4.8

Hydrocracker Products

Middle distillates fiet and diesel) from high-conversion hydrocrackers The heavy naphtha,however, meet or exceedfinishedproduct specifications. usually goes to a catalytic reformer for octaneimprovement.The fractionator bottoms from partial conversionunits can be sent to an FCC unit, an olefins plant, or a lube Plant. Due to the fact that products from a hydrocrackerare less densethan the feeds, the total volume of liquid products is greaterthan the feed volume by is calledvolume swell. 10 to 30 vol%. This phenomenon
Table 17. Hydrocracking in a Nutshel! Convert heaw hydrocarbons into lighter hydtqgqllgrtg Usesfor Unconverted Oil Lube basestock FCC feed Recvcle to extinction Olefin plant feed

Pu

Other Reactions

Licensors

Catalysts

Feeds

Nitrogen removal (HDN) Sulfur removal (HDS) Aromatic saturation Olefin saturation Lummus Chevron Axens (IFP) (IFP) KBR ExxonMobil UOP Shell Global Solutions NiMo on y-alumina (HDS, HDN, aromatic saturation) NiMo or NiW on zeolite (hydrocracking) NiMo or NiW on amorphoussilica-alumina (hydrocracking) Pd on zeolite (hvdrocracki Vacuum gas oil Heavy gas oil Residualoils Coker easoil

Typical ProcessConditions Reactortemperature Reactororessure Range of Product Yields Conversion(once-through) Conversion(with recYcle) Ca-PlusnaPhtha Middle distillates Hydrogen consumPtion

- 425"C) 600- 800'F(315 - 17,338 - 2500 psi g(8375 kP a 1 200

20 - 90 volo/o 90 -99 vol% freshfeed Up to 120 volo/ofresh feed Up to 90 volo/ofresh feed 1000to 3000 scf/bbl 175 to 525 Nm3/m3

3.5

Ebullated Bed Units

to processVGO, residualoils in the designed In fixed-bedhydrocrackers contain even trace amountsof salts, if they life cycle catalyst feed can reduce (Fe, Ni, V), or particulate matter. metals trace refractory carbon, asphaltenes, designedto processresidue units Ai mentionedin Section 3.4.2, fixed-bed remove metals and other contaminantswith upstreamguard beds or onstream can technology.In contrast,ebullatedbed hydrocrackers catalystreplacement fresh is because This oils. residual of amounts significant process and do

snutur-tJ rruoJ ol 3ur1ce;corp,{g sug;u;ed Joqlo uuoJ ol uorluzrJotuosl seueqlqduu truoJ ol uorlezrretuosl luereJJrp scrlsruoJer.ruoJ o] uorlezrlcr{corpr{qaq scrle[uoJer.ruoJol uo4eueSo:pfqeC suopJuell uuJErBd suoqcuag auaqlqtlugsuorlcueg Euruuogegcrflele3go lsl-I g/ anDl

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Suguro;og rl1ztlvlvJ

I.V

's>lcols puelq eurlose8 e1e;eue8 ro eper8dn Jeqlre eql Jo ,^AeIAJoAo uu senr8uorlJossrql 'sJeqlopue 'se1eue8r(xo ]eql sessecord 'eurlose8 'eleroruosr 'e1u1,,(11u 'eleuuo3ter 'eur1ose8 'seuelnq uru-1q8rer1s JJc - srueJlsf-reuger ]uaJeJJrp lere^es Surpuelq fq pecnpord sr eurlosec

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'V

'slurup qsu ruseJlsu^\op 'splnB q peleredes ere r{crq.^A ssecord lsol^tr egl ruo{ 'rolceereql dol er{l 'zfirzrrlceles pe8e8uesrp eJeseycrgud 1s,,(1e1uc }S lcnpord Jo senorduttqclql\ 'leuueqlost ,(peeu eq uec lueruuoJrlue uorlceeJeql 'Surxrur epr^ord o1selcrged1s,(1elec pue IIo Jo ornlxnu e qSnorq] luolnqrn] eseqd-eerql dn selqqnq se8 alcr(cer qcu-ue3oJp,(q'srolceer peq petllnqe uI 'snturun-I ggv (agD suoxv ,{q esuecll roJ pereJJoere sessecord peq pe}ellnqE 'uolsJeluoc Jo uollceles peeJ uo suorlelnurl esodun]ou seopegrllsf1e1ec 'flsnonurtuoc penorueJsr 1s,,(1e1ec lueds pue peppe sr 1sf1e1ec "(lluenbesuoJ

MarA,taAO 3u t ssato.t4 wna pqa d

36

Robinson

T"
nr6lc\ "6"

'-"6""-".

&
CHq

cH s

H2

2-methylheptane

1,2-dimethylcyclohexane

1,2-dimethylcyclohexane

&
I

cHs

6a v
o-xylene

t"

cH e

3Hz

Figure 15. Dehydrocyclizationand dehydrogenation

Hydrocracking and isomervation reactions are shown in Figure 16 and in this process, Hydrocracking,which is undesirable Figure 17, respectively. high temperatures. occursto a greaterextent at
CH. l" H2 ----+

Hrc/

..CH --cH, -c4 -CHz

2 C aH s propane

2-methylpentane
Figure 16. Hydrocracking in catalytic reformers.

CHe

Hrg/cH'-"6""'"6"*'

-cn -cHz --cH, Hrct -c4

2-methylpentane

t"

tl \-/
1,2-dimethylcyclopentane cyclohexane in catalytic reformers. Figure 12. Isomerizationof paraffins and naphthenes

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96 01S8 (ru7rru51 961 - SI I) lqqiJcs00I I 099 %lo^ 98 ol t8

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dg s1ue1d lcltueqcorledro3 ftfO

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38

Robinson

unit, desulfurizednaphthais mixed with hydrogen, In a semi-regenerative through a seriesof fixed-bedreactors. heatedto >900oF(>480"C) and passed and dehydrocyclization- are reactions dehydrogenation chemical The major themselves are essentially the reactors endothermic (heat absorbing), and adiabatic.This means that heat can't enter or leave except by the cooling or heating of reaction fluids Consequently,the temperaturedrops as reactants flow through a reactor.Betweenreactors,fired heatersbring the processfluids back to desiredreactor inlet temperatures.
Heaters, Reactors

Naphtha Feed

Recycle Gas

H2- Rich Make Gas

Recycle Gas Compressor

High-Pressure Separator

Reformate Product F igure / 8. Semi-regenerativecatalytic reforming

Some catalytic reformers operateat low pressure(100 psig, 791 kPa), while others operate at >500 psig (3549 kPa). Low operating pressure improves yields of aromatics and hydrogen, but it accelerates catalyst deactivationby increasingthe rate at which coke forms on the catalyst. In a so increasedcoking is CCR reformer, the catalystalways is being regenerated, In low pressures. at operate very units can Therefore, CCR problematic. less to which converts organic chloride, most reformers,the feed is spiked with an hydrogen chloride (HCl) in the reactors.The HCI increasescatalyst acidify and helps to minimrze catalystcoking. The effluent from the last reactor is cooled and sent to a separator,from which hydrogen-rich gas is removed and recycled to the reactors.The liquid product flows to a stabtlizer column, where entrained gases are removed, before going to the gasolineblender or aromaticsplant.

Jo ued

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Euru;oger cr1,.(lelec UIJ '6l a.rnBtg

,&a,rroceX lcnpord

slcnpord

ptnbtt rolurudag

I I I I I

JalEaH

sJopBaU

roleraue8ag

'Iuels sr sroleqporg er{}uro{ suEenlg 'emleredrue}uol}oer 01pesnf11ecrd,Q elereueE pesn eJ sJeleeqos 'cruueglopueoJE o1 e8reqc eql teogal ol sJolceJuee.&qoq 'speq Jlnuue eql ssoJJe.(11erpe: Stmruoger suorlceeJ 1s,(1e1ec luuruoperd eql '{cls rKou splnu uorlceeJeql elq.,\l,'4ce1seql ui!\op s^\ou 1s.{1e1e3 lclue.\ 'ctleqetpe .,\\og-letpeJ e ur pe8ueu sJolcoJ Jo selJoso1 seoEpue ueSoJpfq e uI e1c.{cerqlp\ soxrru peeJ peler1orp,(qaqt '(6t am8tg) }lun gp
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40

4.2
4.2.1

Isomerization
Isomerization Objectives

in all conversion As we have seen,isomerizationoccurs aSa side-reaction we are process," "isomerization But in refining, when we say processes. n-pentane, n-butane, of iefening specifically to the on-purposeisomerization isoThe main purposeof n-pu.uffin isomerizattonis to produce and n_hexane. reaction itigtter octanenumbers.An isomerization faraffins with substantiuity io. no*al hexanewas shownrn Figure 17' are glverr in Tabte 20. Some details about paraffin isomerizationprocesses
Table 20. Isomerizationin a Nutshell Convert n-butane to isobutane Convert n-pentaneand n-hexaneto branchedisomers Licensor (Ca) Licensors(CsCo) ABB Lummus Global UOP Axens (IFP) UOP Catalysts(Ca) Catalysts(CsCo) Feeds(Ca) Feeds(C5) Pt on y-alumina, HCI Promoter Pt on y-alumina, HCI Promoter Pt on zeolite Pt on zeolite

BP BP

dry n-butane (71"C) endpoint<160"F Light straight-run,

Light reformate Natural gasoline Light hydrocrackate Lisht aromaticsraffinate

Fffi,

conoitions (Pt on alumina,chlorided)

Reactor temPerature ReactorPressure

- 300"F (l2l - 149'C) 250 (2859- 3204kPa) psig 400 450 - 545"F(230- 285'C) 445 - 440psi g(141 kP a) I - 3135 190
up to 97o/o 85 to 90

Proc.st Conditions (Pt on zeolite) Reactor temperature Reactorpressure Cor*-ertion and Product Properties (CsCo) Conversion(with recYcle) RON

and somenormal and section 8.2.1lists octanenumbersfor heavy naphtha so refiners blend as (92), number iso-paraffins.N-butane has a high octane evaporateseasily' also much of it as possible into gasoline. But n-butane (volatility) of gasolinelimit which meansthat tighter restrictionson the RVp of nan excess In many locales,this creates its C+content(seeSectton8.2.2). alkylation in is consumed butane. By converting it into isobutane, which of n-butane' units, refiners can reduceor eliminate this excess

'aJruIeJodtuel uorl3?eJ01 peleq uegl 'ue8orp,(q pelcfceJ pue eprrolgc crue8roJo lunoruE 'pepp '1run 'eurlose8 Ilerus r{lrllr poxru sl peeJ pe}eor}orp,(q lecrd.Q uI sessecord uorlezrretuosr (eCsC)euexeq/euelued ]qAI Jo euelco eql eseeJcur uolluzlJaruosleJsJ :.,!rolf, sseJoJd V'Z'f 'e1e1&11e ro ouelnqosr olul euelnq-u Jo uoISJOAuoc Ielol .,{peeu elerr{ce o} }fun uor}ezrJeruosr ou1nq e ol pelcfcar oq uc lrun uor1e1,{11e u ruo{ ou}nq-N '}run u ol ro eurlose8olur .{11ceJrp uor1e1.(>11e pepuolqeq uo e}eJeruosr egl ]ues 'oAtl 'suoqJcoJpr(q JorleqJo }unotu 1 ue{} ssel eJeEunlcerco} enp sosso'I 'seuelnqoslpue eulnq-u eJnlxnutunrJqrlnbe-reeu u sesuduroc Ileurse snld Jo 'sese8 lcnpord ppbll pez\rqets eqJ ]qEII peleredaseql ruor; IJH so^oruar 'Jezrlrqlse o] s,,\\og (elereurosr) Jeqqrucs ortsnc JolceeJoqI tueng;e V 'eleredo sanulluoJ ol Jeqlo eq] elrr{A\ pecelder eq uec Jo}ceJ euo ur 1sf1e1ec 'ueUO rueoJ}s-uo eq1 'r{cuolclJJe oseoJcur pesn o} oJ serJes ur sJo}ceeJ o./Kl 'sJolceJ 'f1rril1ce eql uI sue^uoc urelureu 1sf1e1eJ IJH ol ,(1e1e1druoc 'uorlceal eq} ol peppe sr qcrql\ 'reloruord eprJol{c crueEro Jo }unotueIIus V Surrnp peuuoJ eJleqt selelperruelur ugelo ar{}Jo uor}zueurflod sesserddns ,{q peunsuor tou sr zH '(ed{ 01rc o1ggyl) Srsd tl lnq'suotlceer uol4ezrreruosr ot ytz uortces peEreqc rolceer eql o] ] 008 ol 002 pu (J"gll o] 0l I) C "yVE pue 'ueSoJpr(q dne4eur,{rp qtr,r.pourqtuoc'peup sl peeJeql 'lerJoltu Jerleoq pue 'seuelued 'euelnqosrJo slunotue llerus .(1uo pue euelnq-u Jo slunorue turuurxru ureluoc plnoqs lrun uorlezrreuosl (tC) euelnq e o] paoJ oqJ 13 :mo1gssaJoJd uolluzlJoruosJ E'Z'V

's1s,{1e1ec surrunl poprJolqc q}lllr sernleredruel Je.,!tol elrlooz l epetu slcnpord ol ellllor lcnpord eql Jo oulco oql ecnper slsr(1e1ec ,(q perrnber sernleredruelq8rq eql 'sJoruosrpeqcueJq JoAeJsernleredtual uollceJJe^/\olos 'tunrrqrlnbe fq pellorluoc eJ suo4ceoJeq] 'uorlezrJeruosr ouelnq ql1ll\ sv 'JelA\ ol elrlrsues ssel ere f.,{l }nq 'sernleredurel reqSrq errnber s1s.{1e1ec e}rloez eql 'o}lloez uo }d ro eurunl/}d ,{q reqlra pez(leryc eJesuollceeJeql 'euexeq-upue ouelued-uezrJeruosl lql slrun uI slusunuluoc Jeqlo pue Jel.,\^. flq8q ere ,(eql pue 'pelereue8er ol oAIlISues eq s1sf1e1ec eurunle/ld l.uc 'ouelnqoslsJoAeJ 'arnleredruel untrqrpnbe A\ol lunuqrpnbe ,{q polloJtuoosr le 'eJnleredruel uollceoJoql esneceq mo1,(lenlleloJ1euorleredo IelcgeueqsI srql slt{} s,rolle 1s.(1e1ec f]1nr1cu qSlq eqt 'eprrolgc ,(q pelouord euurnle Jo uo (u) urnurleld sr ouslnq-u Sursr-reruosr rog lsfleJec uoturuoo lsoru eqr s1s^,t1e1u3 uorluzrJoruosJ Z'Z'?
A^a rAJaAO 3 u t ssatot 4 wna I oJp d

Robinson 42

are used' In twoProcessobjectivesdeterminewhether one or two reactors reactor' which reactor units (Figure 20), the feed flows first to a saturation saturation' the feed removes olefins *a (to a large extent) benzene' After are converted to paraffins normal go.r to an isomerization reactor, where isoparaffins.
Desulfurized

Hydrogenation Resctor

Gas to Scrubber

i'r""ff:?"
Figure 20. csc6isomerization: two reactors,once-throughhydrogen

is The reactor effluent flows to a product separator, where hydrogen go to a can hydrogen separatedfrom the other reaction products. Recovered and treated be recycle compressor,which returns it to the reactors,or it can which column, go a stabilizer to liquids Separator sent to the fuel gas system. liquid stabilized The hydrogen. removes light gur., and remaining dissolved nand n-pentane goesto storageor gasolineblending. If sentto a fractionator, conversion' hexanecan be ,..ytl.d to the isomerizationunit for increased

'8urpue1q eurloseF ere sese8aq1 'lcnpord ol seo8 lcnpord plnbll eql pue 'rolceel oql ol pe1c,{cer pue pelernles- sese8eleredas ppbll eql tuor; - spunoduroctJ-iJ potrnlsun ol suralsfs Joleuollcer; rolpve uol}zlllqe}s o} oB slcnpord uol}ceg '(ilt 9tt8 pue (C.0tZ ot o1ggtl) Ersd002'I ol 002 luor; e8uersernsserd Co0g?ol 0gI) 'rotceer eq} ur spoqueo^ueq(qcuenb) {rolspaal 008 uro{ e8uer sernterodurol Surlcefur.(q pue lcnpord qlp,\ peeJ oql Eu4nyp ,(q pe11o4uot ploc .(1e'rltler 'JolceJ eql ol luas sI poeJqJIJ eJuseJnlereduelos 'crrrueqloxesr uorlceeJeqJ -urJeloeql 'spunodruocelqJrsepun Jeqlo pu JnJInsoAoIueJol luotule4-ard regy 's1sf1e1ec lrun roJ qcle{s sluesofi eZ a"m8rg VdS esn ot peuErsep ,rolf, ssoJoJd 'gf 'sJo]ooJ ut pesneq uJ elrsuedxe-sse1 loels-uoqJec 's1sflewcse pesn ere (y4g) s1e11ad 'elrsouoc-uou sr 1sf1e1ec l[ os VdS eq1 'ptce cuoqdsoqd 'ptce cIrlUInS rqnEleser{ uo plc clroqdsoqd pllos pue

sls^IBIBJ z'E r
'1 aue1,lnqosr Jo uoquztJatulq 7 a"tn&g

eua;r{lnqosr-tp srH83 eHc zHO

aua;r{lnqosr tHoc zHc

rtl

#ll

,r"/'>*".23\re,-.,

tHcl"\ctH

'eue1,qnqosr oql JoJuorlceJ Jo uorlezrJewrp 'suoqeclldde lecrueqco4ed JoJ oluoluno I?cruer{o urru eql s^\oqs 17 a"tnBtg s qcns sc4eruoJ?pu sugelo req8rq o>lelu ssecord eqt uo suollelJe4 ' ueqt releer8 oJesouoluedl.(qleulut-F L6 Z(Z pue souelued-3-lfqteu se qcns sugelo 8J pue eJ roJ sJequnu ouelco qcJeosoJ 'sugalo 6J eqt 'ZZ anDJ Jed '$lcols puelq eurlose8 luellocxo oJ rlcn{11| cr1f1e1ec pue ol eJ olw sugelo tJ pu" iJ speluoc ssecordeql 'uorlsuopuoc 'f1od1uc 'uorlezrteurflod clq(letroc pollec sI osle uorlezrrcuroEtlo cr1f1e1e3 serr;1ce[qO uollBzrraruo8qg crlt{1u1u3 I''t

uollBzlrotuoSllo c1ry(1u1u3 E'i

tn
&Larttalo 3m ssato"t4 unap4ad

Recycle

Recycle

Quench

Flash Drum Stabilizer

Propylene, Butylene Feed

Figure 22. Catalytic oligomerization of olefins

4.4
4.4.1

Atkylation
Alkylation Objectives

Alkylation processes combine light olefins (primarily propylene and butylene) with isobutane in the presenceof a highly acidic catalyst, either sulfuric acid or hydrofluoric acid. The product (alkylate) containsa mixture of paraffinic hydrocarbons. Figure 23 illustratesthe high-octane,branched-chain Alkylate is a highly desirable reaction between isobutaneand trans-2-butene. in addition to its high octane,it has a low vapor gasolineblend stock because, pressure.The octane of the product dependson the operating condition and the kinds of olefins used.
HsC..- ..CHs -c H
cHa

-cH -cH. Hrc/ \cri

coHu trans-2-butene

Hscr HsC

,.c\ -cH, lc-.-ct-i,

crH ,, isooctane

cH e 9H a |

coH',0 isobutane Figure 23. Alkylation of trans-2-butene

4.4.2

ProcessFlow: Sulfuric Acid Alkylation

In sulfuric acid (H2SO4)alkylation units, the feeds - propylene, butylene, amvlene" and fresh isobutane - enter the reactor and contact sulfuric acid

uolllf)le lH're
JOlBurJOnUaO

arn8ry

elet,qlv

JolBrauaSeu dH Jezruulnqosle(J

JszruElnqa(J

euelng-N

eudord eulnqos I alJ,{3eu euelnqosl

'suueto

'8utpue1q lcnpord o1seo8rezruelnqep eql ruo{ tueerJsruonoq eqJ 'peycfcar sr Joleuol}ceg uretu gIC eq} ruo{ 'reddrrls euelnqosl 'e8erols ol pue ollsnec qlr1!\ peleoJl ueql sr uE luos 11 CH o] seo8per{reloEJo(I oqJ '(tJeq) rezruedordep e o1seoS'CH Ienprser pue 'euelnqosr'euedordSurureluoc'rueJlspeeqJolo eqJ, '(gtc) Jozruelnqosrap e ol seo8 asuqd uoqrucorp,(q eqJ 'pelcfcer puu JJo u^\erp sr plre eqJ 'esqduoqreco;pfq eq] ruor; seleredes eseqdproe oq} ereq./('re1}}es e o1 rolceoJeql '1sf1ele3 eql relo sllrou eceld se{} uor}ceruorlelr(11e luenuJe cH 'rolceer e o} peJ pue perJp ere eulnqosrpue er{l eJeq,ry\ sugelo 'uor1e1,(11u (gD plJe cuongorp,(q roJ orlutueqcs ssecord e s^\oqs rc a"tnBtg uo11u1,{41v.fH :arolCssaJord E V.f

pu prce crrrg:lnspu 'ovoz qoee o] srolnqlJlslp qEnorql poJ ere seu]nqosr suualo'souoz olur pepr^lp sl rolceer eqJ-'%96 ot sg Jo uor]srluocuoc e qlr^\
9V
Mat ^J a^O 8ut ssat o"t4 wnap.u ad

'pe1cr(cer sr euelnqosl'ewlose8eperS-uorlerle ecnpordot pessecordeJ eq uec lI ro 'SutpuelqIery-Jolou o1fllcerrp oA uel Jezruelnqosrep 'Jozruelnqop e pue 'tezruelnqosrep eq] ruo4 e1e1,&11y e 'tezruedo.ldep e sosudruocuorlcasuorleuollJe4 oqJ 'uorluorlcJJ 01 pue q}r^\ cr}snec }ues 'prce oql poqsea ere suoqrecorp,(qaqJ, 'rolseer potunleJ oql ol prce sr eqJ ruoJJolerudessuoqJcoJpr(q qclr{A\ur 're1}}es e o1seoS}uenuJeJolc?eJ er{J 'lxeu eql ol euoz euo tuoJJseuJsqJeAorvroll

40

Robinson

5.

LUBES,WAXESAND GREASES

"Bottom of the barrel" fractions - atmosphericand vacuum residues can describedin Sections2 and 3, or they can be be convertedby the processes greases. and usedto make lubes,waxes

5.1

Lube BaseStocks

Refiners prepare lube base stocks from residual oils by removing aromatics, and waxes. Lube base stocks are hydrofinished, asphaltenes, btended with other distillate streams for viscosity adjustment, and with additivesto producefinishedlubricants. compounded aromaticsand waxes for removing asphaltenes, processes Solvent-based give a quick overview in Section2.2.The next few paragraphs were discussed of catalyticdewaxing. 5.1.1 CatalYticdewaxing

The by Exxon Mobil in the 1980s. Catalyticdewaxing(CDW) was developed zeolite called ZSM-5, which selectively processLmploys a shape-selective hydrocarbons. lighter into n-paraffins convertswaxy in 1993 by ChevronTexaco, commercialized The Isodewaxing Process,, the wax This decreases iso-paraffins. catalyticallyisomerizesn-paraffins into both of low-viscosity hydrocarbons, the concentration content and increases which are desirable.Isodewaxingalso removes sulfur and nitrogen,,and it have a high viscosityindex (VI), low pour point, Products aromatics. saturates to additives. and excellentresponse in more detail in the Catalytic dewaxing and Isodewaxingare discussed secondvolume of this book.

5.2

Waxes

The raffinate from the solvent extraction unit in a traditional lube plant contains a considerableamount of wax. To recover the wax, the raffinate is mixed with a solvent, usually propane, and cooled in a series of heat Further cooling is provided by the evaporationof propane in the exchangers. chiller and filter feed tanks. The wax forms crystals,which are continuously by removed,filtered, and washedwith cold solvent.The solventis recovered solvent, hot with heating purified by is wax The flashing and steamstripping. after which it is re-chilled,re-filteredand given a final wash. paraffin waxes are used to make candles and coated papers for use as bread wrappers,cold-drink cups, and beveruge cartons.They are also used in

sel8urqs Suuoorpeseq Jo slsrsuos -lleJJo uortcnpordt,{J 'sselSreqg pue (11e3 reded) cruuSro- tleqdseSugoo: roJ solerlsqns,tteurud o^U or ereql 'fep rnoq-p7 rcd tleqdseJo seqclEq 'oleJ xrs o] JnoJ s,^AolQ uolleJleued pue ernleredruel Suruegos lueld 1ecrd,,Q V perrsepuo spuedep^\olq eq] se qcns 'seruedord tllSual eq1 lcnpord Jo 'lesse^ Oql fq osye'(eru Jele.,l\ 3ur1oo3 'ureaJJsu,^Aop peJoloJaj Jo eprslno oq] uo pe.,(e;ds 'seseF snoese8 Joqlo pu 'suoqrecoJpr(q ete eseqJ 'sJueurtueJuoJ lgSll sernldec tuuels Surureluoc-Jrglns e Surleerc'lessen8ur.ano1q ler{} }eluelq Jo sr Je}e./v\'8ur1ooc er{}Jodo1eql olur per(e:ds eprnordoI 'cruuoq}oxe eJqorq.\\ 'suorlcee;Surmolq er{} seleJ eql eseJcur pue sergedo;d lcnpord lsnfpr Jo ol posn eq feu (ttcag) oprrolqcclxeJ se qrns s11es cr1,(vleJ'zg5 pue 5.9 ol pope^uoosr rnJlns crueSro'sseco;dsrq] Suunc 'sJnor{ 0l ol I roJ (C"00S, J.1gZ 1elleqdseplnbll q8norqt rre Surlqqnqfq xng lleqdseJo uorlprxoaql pecnpo"rd sr tleqdseSugoog qnqdsV &ugfooy sellonur rlclq^\ '8urmo1q,,(q 'uorleJJSruFup\ ,(e,tq8rg IerepeC eql ,(q perosuods lceford qcreser uorlpur 0S$S-l ur pedole^epservr ened;edng'lleqdsexru-lor{ e ?uunp E6-L861 ,renedtedns sr setls petluf] eq] uI sr(eAqSrqSurnedJoJ Ierre]IUpepueuruoser er{J 'A.lrlrqErnf pue qfuerls elordruy o1ropulq eql o] peppere s;eu,(lod 'ernlxru Iug or{lJt' e1e8er88e eql '1ene.r8 lo 'pues'euo1s epnlcutuec qcrq\.. %96lnoqe sesudruoc 'e1e8er88e 'Surned-peoJ JoJ Jopurq e s selJes onprseJ uneloJled eql ul 'petldde sr tunncA e eJeql\ uruflloJ E tr. pue (J.00t) C.gS, lnoqe ol peleqsr 1r'spue]q8ll SurureruerJJo peS;eqc o,\rri

rer-peor ere." ol posn srenprse, o1 '11eqdse T;.?fr :i::{:Kiy;"#;{r"r,

NOIIJIIOOUd IfYHdSY

lue^los ,{q ro enprseJrunnce^ tuou ,(1}cerrppacnpord eq uec lleqdsy

'9

't1es Prce-flr-: eqt ut ('c1e'unl{lll 'unurunle 'runrpos'unrclec) uor-Je}unoc eql uo Juot\; eq; ',(lsnonurluoo epetu a-ri leet3 e o] puedep eseer8 e go scrlsrJeloererlJ 'pecnpord-qc}eq ore seseer8 sreqlo elll{,,rn. euog 'firpqe1s eprnordo} peppe ari stueprxorluv'(f.glE o] V1d C.009 ot 00tJo sornlereduel te slro Surlecr:qr' olul sptoe ,fueJ peureqc-8uolJo slls Surpuelq fq epIu ere seseer0

sosBOJS

t's

'esu aql uc ur ,(llercedse rr'uorlJrulsuos eJBsesnJeqlo 1nq'Sutullcopsr Sur8zlcedrog lo{Jetu eql 'slerJe}etu Eurppnc
LV Mat^-ta^O Surssato.t4 tattolot.: -

48

Robinson

Saturatingthe paper felt with asphalt felt with filled asphalt Coating the saturated granules Pressing of sand,talc or mica into the coating Cooling with water, drying, cutting and trimming, and packaging If fiberglassis used as the baseinsteadof paper felt, the saturationstep is eliminated.

. . . .

7.

DRYING, SWEETENING,AND TREATING

Drying, sweeteningand treating are not as glamorous as extraction and or even distillation,but they are essential conversion, to the performance and safety of finished products. In lubricating oils, traces of olefins and sulfur compounds can form gums and accelerate degradation. At high altitude, excesswater in jet fuel can freeze and plug fuel lines. Traces of mercaptans and disulfides in "sour" gasoline can react with water in storage tanks to producetoxic levelsof hydrogensulfide.

7.1

Drying and Sweetening

Light gas streams produced by various refinery units are collected and piped to treatingplants,where: o Propane is recovered for LPG o Propyleneis removedfor use in petrochemical plants o Butanesand butenesare removed for use as alkylation feeds . Heaviercomponents are recovered and sentto gasolineblending Knock-out drums collect easy-to-condense liquids, but if necessary drying agents- alumina, silica, or molecular sieves- are used to remove the final traces of water. Some processes use beds of molecular sieves to dry and at the sametime. sweeten Gasescontaining hydrogen sulfide are scrubbedin trayed contactorswith aqueousamines such as diethanolamine(DEA). Hydrogen sulfide is stripped from the "rich" amine with steamand recycled to the contactor.In a properly gas contains<10 wppm H2S. operatingunit, the sweetened

7.2

Treating

Treating improves the odor, color,,and stability of straight-runliquids and conversion-unit products. Sulfuric acid treating removes olefins, sulfur, nitrogen, oxygen compounds,and other contaminants.Clayllime treating of oil removesany residual tracesof asphaltenes. acid-treated Caustic treating

6lenJ oJe sJano.rdtur-euelec luenerd leql sellllppe pue leselp of pepp,(1eur1nor 'ocuuru;o3red 'eldruzxe Joc ecuque pue seruedord A\og enordur 'rQrpqels {eqJ 'slery peqsrug eseaJcur uE ere so^r}lppv lueuoduroc Jo Ierluesse 'seesuecrl ssecord ol spoqleu lsol elnqrrlsrposl sJosuecrl Jeqlopu Irqo6uoxxg 'ocexeluor^or{J ,(agt) suexv 'slenJ pu slecruaqJ 's1s,{1u1ec ?urz(leue JoJ soJnpecordperpunq IJeAos seugep 'I trJSV fq pelnqlrlslp 'spoqtaygtsal t-to1otoqoTs,do11 .elduexa Joc 'srosueJrl'(q peugep eru suorlecurceds pue slsel pesn flepr1l Jeqlo ',(lenrlcedser 'u[0-tl gtCI pue o]ul t0-S16CI 's'II pelerofuosureJe ,,{cue8yuor}seloJd eq} ruoJJ se^rlcaJrp I}uoluuoJr^ug 'eyduexe JoC 'sJolelnSer lueceJ lueuuterro8 Iosalp pue eullose8rry1ns-A\ol 'reqlo qcse qll,^(l. qll^\ ,,(1eso1c eleredoocsursnocIeuor]uelur lJo.^A,(eql pue slr puu I IJSV 'slerJelelu o] pesn spoqleu ]sol ;o flsrre^ epr^\ e ezfi1euu qsrlqndpue do1e.r.ep suorlnlllsureseql'suorlecgrceds 3ur11es ol uorlrppeuI ' sessecoJd SuunlceJnuzru 8ur?eueu JoJ spJepuzls 'suorlcunJrelrurs elros (fSg) Jo serros 000605I eq] pedole,repISg uortntrlsul sprepuls qsrlrrg eql pue (f,Slf) eeilrturuo3 spreputs lrrlsnpul eseuedel 3q] 'eldurexe JoJ - serJlunooJeqto ut suorlnlrlsur snoSoleuy
IIO IENJ Iesarc euesoJ0) t0f eurlosec lrnpord ',lZ anDJ slrO IonCroJ uortucgrcedg prepuets 866 I 96tA slro IonCloserq roJ uortecglcedg prupuels v00z 9L6A ouosore) JoJuortecUrcedg pJ?puetS t00z 669tA slenCeurqrnl uoqer^V roJ uortecgprjs prupuuts t00z S99I CI Ienc eurduguorlrudl ->1redg e^rlotuolnv roJ uortecgrcedgprepuuls EOOZ 'I8'C uorldrJJse(I palupdl uorlucgrcadg ISE'I ruISV slonc uoqrecoJp^HroJ srequnN uorl?cgr I IJSV

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Robinson

8.2

GasolineBlending

Forty yearsago, making gasolinewas a relatively simple task.If a mixture for volatility and octane,it could be shipped met specifications of components to retail outletsand sold as-was.If the octanewas low,,the problem could be fixed by adding a little tetraethyllead. Butanescould be addedas neededto adjustvolatility. In fact, volatility and octaneare still the two most important propertiesof The volatility must be high enoughto vaporizeduring cold weather; gasoline. otherwise,engineswon't start.And octaneis still one of the bestpredictorsof gasolineengine. in a spark-ignition performance 8.2.1 Octane Numbers for Hydrocarbons startto burn beforethey reach engine,somecompounds In a spark-ignition the spark plug. This prematureignition causesknocking, which reducesthe serious enginewear, and'in somecasescauses power of the engine,increases damage. of the propensityof fuels to knock in gasoline Octanenumber is a measure scale in which the octanenumber of narbitrary an on based is It engines. is (2,2,4-trimethylpentane) of isooctane number is zero and the octane heptane of mixtures 100. When a fuel is testedin a standardsingle-cylinderengine, ASTM D2699 and ASTM isooctaneand n-heptaneare used as standards. octanenumber (RON) and research measuring for methods D2100 describe speedfor the RON The engine motor octanenumber (MON), respectively. test is 600 rpm, while 900 rpm is used for the MON test. RONC and MONC are sometimesused instead to RON and MON. The "C" standsfor clear, additives. which meansthat the fuel doesnot containlead or manganese pure compounds. Table 22 presentsRON and MON values for several Aromatics, olefins, and branchedisomershave higher octanenumbersthan straight-chainisomers with similar carbon numbers. Octane numbers for lower than thosefor aromatics. are substantially naphthenes Octane numbersdo not blend linearly. For example,while the RON for is 99, its blendedRON is 130. pure 4-methyl-2-pentene of RON and pump octaneof gasolineis the average the America, In North filling stations. pumps at on MON: (R+M)/2. This is the numberdisplayed Typical gradesare "regular" with a pump octaneof 87, "mid-grade"with a pump octaneof 89, and "premium" with a pump octaneof 91 to 93. In some can dial in any octanethey want between87 and 93. locales,customers

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52

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to impose emissions limits on automobiles and to require reformulated gasoline(RFG). Phase I RFG regulations (Table 24) required a minimum amount of chemicallybound oxygen, imposedupper limits on benzeneand Reid Vapor Pressure(RVP), and ordered a l5o/oreduction in volatile organic compounds (VOC) and air toxics. VOC react with atmospheric NOx to producegroundlevel ozone. Air toxics include 1,3-butadiene, acetaldehyde, benzene,and formaldehyde. Oxygen can be suppliedas ethanolor C5 to C7 ethers.The ethers(Table 25) have excellent blending octanesand low vapor pressures. This makes gasolineblend stocks.Due to the Cetection them highly desirable of MTBE in groundwater, the future for MTBE is questionable, especiallysince 1999,when the Governor of California issuedan executiveorder requiring the phase-out of MTBE as a component of gasoline. But in Finland and many other European countries, MTBE is still considereda premium, relatively safe blend stock."
Table 24. Simple Model RFG Specifications

Property Specification Oxygen, wto% 2.0 max Benzene, volo/o 1 . 0m a x RVP, Summer ClassB (psi) 7.2 max ClassB (kPa) 50 max ClassC (psi) 8 . 1m a x ClassC (kPa) 56 max VOC (summer) 15% reduction Air toxics l5o% reduction Sulfur Sameas 1990 T90*, olefins,aromatics Sameas 1990 *T90 is the temperatureat which 90o/o of a gasolineblend evaporates.

RFG was implemented in two phases. The PhaseI program startedin 1995 and mandatedRFG for 10 large metropolttan areas.Several other cities and joined the program voluntarily. In the year 2000, about 35% four entire states of the gasolinein the United States was refonnulated. The regulationsfor PhaseII, which took force in January2000, are based on the EPA Complex Model, which estimates exhaustemissionsfor a region
Tqble 25. Blending octaneand RVP of ethersand alcohols Blending Octane Blending RVP (RON) Ether or Alcohol (nsi) Methanol 133 58-62 Ethanol 130 t8-22 Methyl-t-butyl ether (MTBE) 118 8 -l 0 Ethyl-t-butyl ether (ETBE) 118 J-) t-Amyl methyl ether (TAME) lll t-2 Blending RVP (kPa)

400-427 124-152 55-69 2r-34 7-14

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8.2.4 Low-Sulfur Gasoline and Ultra-Low-Sulfur Diesel In recentyears,the U.S. EnvironmentalProtectionAgency (EPA) and the promulgatedclean-fuelregulations that are lowering the Parliament European for gasoline fuel. New sulfur-content standards and diesel of sulfur content several developedcountriesare shown in Table 28, which also shows the targetdatesfor implementation.
Table 28. CleanFuels:Limits on Sulfur Fuel Sulfur Content,wppm

Gasoline Diesel,on-road Diesel,off-road Canada Gasoline Diesel Germany Gasoline Diesel Sweden Diesel Other EU Gasoline Diesel Australia Gasoline Diesel Korea (South) Gasoline Diesel Japan Gasoline Diesel

>300 500 - 3500 2000

30 15 500 15 30 15 l0 10 l0 50 10 50 l0
150 30

2004- 2008 July 1,2006 July1,2010 2007 20r0 2005 2006 2003 2003 r 995 2005 2008 2005 2008 2005 2008 2006 2006 2008 2004 2008

150 500 t0 l0 10 150 350

500 500 100 300 100 500

30 50 l0 50 10

Table 29 shows that, prior to 2004, FCC gasolinewas by far the major typically accountingfor 85 - 95% of the total sourceof sulfur in gasoline,a3 pool.aa Obviously, to reduce the sulfur content of blending in the sulfur gasoline,sulfur either must be kept out of FCC feed or removed from FCC product(s). Both approachesare being used. FCC feed desulfurizationis post-treating is discussed below. in Section 3.4.2.FCC gasoline discussed

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gives off The flash point is the lowest temperaturc at which a liquid freezingpoint enoughvapor to ignite when an ignition sourceis present.The the is esfecialiy important for jet aircraft, which fly at high altitudes where corrosiveness. of measure is very low. Sulfur contentis a outsidetemperature of smoke point goesback to the days when the primary The measurement lamp, use for kerosenewas to fuel lamps. To get more light from a kerosene it high, got too flame the if But wick. could turn a little knob to adjust the you 'gave maximum the is point off smoke.Even today, per ASTM D1322, smoke using a teight of flame that can be achievedwith calibrated wick-fed lamp, wick "of woven solid circular cotton of ordinaryquality." The smokepoint of a test fuel is comparedto referenceblends.A standard 40%160%(volume/volume) mixture of toluene with 2,2,4-trimethylpentane has a smoke has a smoke point of 14.J, while pure 2,2,4-trimethylpentane aromatics. than points smoke better have point of 42.8.Clearly, isoparaffins known jet otherwise fuel' Toble j0 shows specificationsfor five gradesof as aviation turbine fuel. The JP fuels are for military aircraft'
Table 30. Specificationsfot euiution f"tUln Jet A ecification 38 Flashpoint, "C (min) -40 (Jet A) point,'C (max) Freeze -47 (JetA-l) API Gravity Distillation,'C 107omax 20ohmax max 50olo 90ohmax EP Sulfur, wtolomax Aromatics, voloZmax max Olefins, volo% Jet B JP-4

-5 0 45-57

-58 45-57

JP.5 60 -46 36-48 205

JP.8

38 -47

3 1- 5 r 205

3 7- s l 205

t45 190 245

:oo
0.3 22 0.3 22

t45 190 245 270 0.4 25 5

290 0.4 25 5

300 0.3 25 5

8.4

DieselBlending

the limitations Diesel blending is simpler than gasolineblending because aromaticsand countries) (in some and number, are fewer. Only sulfur, cetane heavily to contributes Sulfur density are regulatedfor environmentalreasons. of a measure is number particulateemissionsfrom diesel engines,and cetane number trrrning quality in a diesel engine. As with octane number, cetane It is measuresthe tendency of fuels to auto-ignite in a standardtest engine. high. is fuel the of number cetane the when easierto start a diesel engine the test method for fuels for ASTM D613, which describes The reference heptamethylnonane' and cetane number, are n-cetane,0,-methylnaphthalene, for which cetanenumbersare defined to be 100,0, and 15, respectively. pure compounds'4s showscetanenumbersfor selected Table-31

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TableJJ. EU S ecification Cetanenumber Cetaneindex Density C@ 15"C

ificationsfor Automotive Diesel Units Year 2000 Limits 5l (min) No spec glcm3 0.845(max)
OF OF OF OC

PossibleFuture Limits 55 (min) 52 (min) 0.84 608 (max) 644 (max) 662 (max) 320 (max) 340 (max) 350 (max) 2 (max) l5 (max) l0 (max)

Distillation 90% boiling point 95% boiling point Final boiling point 90% boilingpoint 95% boiling point Final boiling point Polyaromatichydrocarbons(PAH) Total aromatics Sulfur o

"C
oC

no spec 680 (max) no spec no spec 360 (max)

no spec

wto/o
wto/o

wppm

I I (max) no spec 350 (max)*

As discussed elsewhere, dieselsulfur will be limited to 50 wppm in 2005.

Catalytic converters led to the elimination of lead from gasoline,because lead poisons the converter catalyst. Similarly, sulfur poisons catalyststhat may be usedon future vehicles.Hence,the reductionof sulfur in gasolineand dieselfuel to ultra-low levelsis a key requirement of Auto oil II. Around the world, the transportation and fungibility of ultra-cleanfuels is a major concern. For common-carrierpipelines, which transport various productsmade by different refiners,cross-contamination is a major concern. The interfacelayer betweenshipments is called "trans mix." If a shipmentof gasolinecontaining 30 wppm of sulfur follows a batch of diesel containing 500 wppm of sulfur, the sulfur-contaminated trans mix could comprisemore than 20o/oof the gasoline. Consequently,severalpipeline companieshave announced that in the future they will not transportany high-sulfurmaterial. Other important diesel-fuel properties include flash point, cloud point, pour point, kinematic viscosity, and lubricity. Cloud point and pour point indicatethe temperature at which the fuel tendsto thicken and then gel in cold weather.In additionto providing energy,dieselfuel also servesas a lubricant for fuel pumps and injectors,which prolongsthe life of the engine.Viscosity measuresthe tendency of a fluid to flow. In a diesel engine, viscosity indicateshow well a fuel atomizesin spray injectors. It also measuresits quality as a lubricantfor the fuel system.Lubricity measures the fuel's ability to reducefriction betweensolid surfacesin relative motion. It indicateshow the enginewill perform when loaded. 8.4.1 DieselAdditives Chemical additives improve the performanceand extend the tank-life of dieselfuels.Typical typesof additivesare shown in Table 34.

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Robinson

due to the relativelyhigh cost of buying low-sulfur fuel oil the most expensive or hydrotreatinghigh-sulfur fuel oil. A large fraction of the sulfur in the feed to an FCC unit endsup in coke on the catalyst. SOx is formed in the regeneratorwhen the coke is burned away. SOx emissions. removingsulfur from the feed decreases Therefore, As statedin Section 3.4.2, using a hydrotreateror hydrocrackerfor feed equipment. HDS eliminatesor minimizesthe cost of post-FCCdesulfurization deactivationof acid sites on the FCC Removing basic nitrogen decreases catalyst, which allows the FCC to reach a given conversion at lower The saturationof aromatics in the feed pretreaterprovides the temperatures. biggest benefit, becauseit converts hard-to-crackaromatics into easier-toThis alone can justify the installation of an FCC feed crack naphthenes. pretreater.Therefore,in addition to abating SOx, hydrotreatingthe feed to an return.a3 FCC can generatea substantial (Oxidizing Environment) FCGRegenerator + Oz+H2O - CO,+ SO2, (gas) (solid) HrSO" SO3, on catalyst Coke + Oz-- M'SOa + M (solid) (gas) (solid) HySO, SO3, SO2, (Reducing Environment) FCCRiser/Reactor
M.SO4 (solid) + 5 Hz --+ M (solid) + H2S (gas) + 4 HzO Figure 2-J.Mechanism of SOx transfer in FCC units.

SOx Transfer Additives. Arguably, SOx transfer additives are the most way to lower SOx emissionsin an FCC unit. Thesematerials, cost-effective by Davison Chemical,reactwith SOx in the FCC regenerator first developed to form sulfates (Figure 25). When the sulfated additive circulates to the riser/reactorsection, the sulfate is reduced to HzS, which is recoveredby amine absorption and sent to the sulfur plant. In some units, these additives if a pre-treater by more than l0o/o.Consequently, reduceFCC SOx emissions still must be installed,its sizecan be reduced. or post-treater Flue-Gss (Stack-Gul Scrubbing. Flue-gas scrubbing is a refiner's last chanceto keep NOx and SOx out of the air. In wet flue-gas desulfurization, gas streamscontaining SOx react with an aqueousslurry containing calcium CaCO3.Reactionproductsinclude hydroxide Ca(OH)2and calcium carbonate which precipitatefrom calcium sulfite (CaSO:) and calcium sulfate(CaSOa), the solution. NOx removal is more difficult. Wet flue-gas scrubbing removes about 20% of the NOx from a typical FCC flue gas. To remove the rest, chemical reducingagentsare used.In the SelectiveCatalyticReduction(SCR) process, anhydrousammonia is injected into the flue gas as it passesthrough a bed of

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Robinson

As shown,elementalsulfur is producedby the reversiblereactionbetween SOzand HzS.COS and CSzappearin small amounts, but even tracesof these compoundsare hard to remove in tail-gastreating units. Ammonia comesin with the sour-waterstripper off-gas. In the Claus process,it is thermally into nitrogenand water. decomposed In the Claus burner, combustion temperatures reach 2200"F (1200'C). Needless to say,this generates a tremendous amountof heat.Much of the heat is recoveredin a waste-heatboiler, which generates steam as it drops the temperature to 700"F (370'C). Next, the processgas goes to a condenser, where it is cooled to about 450"F (232"C). At this temperature, sulfur vaporscondense, and the resulting molten sulfur flows through a drain to a heatedsulfur-collectionpit. At the bottom of the drain, a seal leg maintains system pressure and keeps gases unconverted out of the pit. Uncondensedsulfur and other gases flow to a series of catalyst beds, which recover additional sulfur by promoting the reactionbetweenleft-over HzS and SO2.With fresh catalystand a stoichiometricgas composition,the cumulativerecovery of sulfur after the four condensers is about 50oh,80o/o, respectively. 95o , and96-980%, Tail-gas treating units (TGTU) bring the total sulfur recovery up to >99.9o4.Most tail-gas treating processes send the tail gas to a hydrotreater, which convertsall sulfur-containing compounds (Sor, So:, CoS, CS2and S.) into H2S.In the SCOT process, offered by Shell Global Solutions,the H2S is aborbedby an amine and returnedto the front of the Claus furnace.In the LOCAT@ process,offered by Merichem, HzS is air-oxidized to sulfur in an aqueous solutioncontaininga chelated iron catalyst. For all tail-gastreatment processes, the last tracesof unrecovered sulfur go to an incinerator,where they are convertedinto SOz and dispersedinto the atmosphere.

9.2

Waste Water Treatment

Wastewater treatmentis usedto purify process water, runoff, and sewage. As much as possible,purified waste-water steamsare re-usedin the refinery. Wastewaterstreamsmay contain suspended solids, dissolvedsalts,phenols, ammonia,sulfides,and other compounds. The streamscome from just about every process unit, especiallythosethat usewash water, condensate, stripping water. caustic.or neutralization acids. 9.2.1 PrimaryTreatment

Primary treatmentuses a settling pond to allow most hydrocarbons and suspended solids to separatefrom the wastewater.The solids drift to the

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Due to clean-fuel regulations,many refineries are implementing hydrogen refoffners recovery/purification projects and/or installing steam/hydrocarbon to generateon-purposehydrogen.

10.1 Power
Refineriespurchaseelectricity from outside sources,but they also produce much of their own power with steam turbines or gas engines. Electrical substationsdistribute power throughout the facility. For safety reasons, are locatedfar away from sourcesof combustiblevapors. substations

10.2 Steam
Steamproduction and distribution systemsare quite complex, involving 3 to 4 different steam qualities and hundreds of pipes and valves. Cooling are usedto dispose of unusedsteam. towersand evaporators process by boilersand heat-producing units. FCC units, Steamis generated reformers (hydrogen plants) are major Claus units, and steam/hydrocarbon sourcesof refinery steam. Steamboilers are fired with refinery fuel gas, natural gas, and/or fuel oil. Fuel oil is a blend of residualoils with flow-improving cutter stocks.Usually' it is pumpedthrough a seriesof strainersbefore being burned. Refinery fuel gas is collected from processunits, sweetenedin amine absorbers,and sent to a balance drum. Natural gas and LPG may be used to augmentthe fuel gas supply, and to replaceit when needed.The balancedrum stabilizessystempressureand calorific content.It also provides a place for liquids to separate from the gas. suspended Boiler feedwater(BFW) is used for steamgeneration. BFW must be free becausesalts and dissolvedgases, particularly CO2 and 02, of contaminants, corrosion. can causeextensive

10.3 Hydrogen and COz

Due to the extra hydrotreatingrequired by clean-fuel regulations,refiners are looking for additional sourcesof hydrogen,which can be recoveredfrom off-gas streamsor generatedby new hydrogen plants. Chapter 26 by Nick Hallale, Ian Moore and Dennis Vauk describesa methodology for optimtzing hydrogen recovery from existing refinery hydrogen networks. For new reforming is used. This process is hydrogen plants, steam-hydrocarbon described in detail in Chapter 25 by Andrew Crews and Gregory Shumake and in the Chapter24 by Milo Meixell. A brief overview is given in this section. reformer can be natural gas,refinery The feed gas for a steam-hydrocarbon off-gas, or a mixfure of the two. The feed gas is desulfurized, mixed with

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consumptionwithin OPEC is about 15% of the world's proven oil reserves; produced is exported. the oil all of very low, so almost
and Productionae Table36. OPEC Oil Reserves Daily Production,2002 (million barrels) Countrv 1.58 Algeria 1.35 Indonesia 3.53 Iran 2 .0 4 Iraq 2 .0 2 Kuwait 1.38 Libya 2.r2 Nigeria Qatar Saudi Arabia United Arab Emirates Venezuela

2003 Proven Reserves, (billion barrels)

0 .8 4 8.71 2.38 2.91

9.2 5.0 89.7 tt2.s 96.s 29.s 24.0 15.2 26t.8 91.8 ll.8

The Figure 28 illustrates how oil prices have changed since 1861.50 bottom trend shows the actual historical prices. The top trend convertsthe historical prices into 2002 dollars. The big spikes in 1973 and 1978-81 coffespondto actionstaken by the OPEC cartel. In 1973,the first Arab Oil price of oil to rise from aboutUS$4 per barrel to the average Embargocaused more than US$10 perbarrel. In 1978,the revolution in Iran triggeredanother in prices,, which peakedin 1981at aboutUS$38 per barrel. steepincrease
100 90 80 70 60 50 40 30 20 l0 0 I 860's I U70's I 8ll0's I tt90's 1900's l9 I 0's I 9 2 0 ' s s I $ 2000 ofthe day $ money
1930's I 940's 1950's I 960's I 970's I 980's 1990's

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Figtre 28. Oil PricesSince 1861(SUS)

major oil-consumingcountries to thesesevereprice increases, In response The measures. and implementedenergy conservation developedalternatives member countries of OEDC (Organization for Economic Co-operation and Development) decreasedoil demand from 44 million b/d in l9l9 to 37

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68 ConversionUnits. Table 32. Economicsfor Selected Process FCC Cat. Reforming Alkylation Hydrotreating Hydrocracking Operating Costs (US$ per bbl) 2 . 0* 2 . 2 3.0 4.8 - 5.5 1.7 4.0 to 4.5 Major Cost Factor Fuel utilities Utilities Hydrogen Hydrogen Percent of Total Cost 70 90 65to75 60 to 70 75 to 80

Robinson

Net margin ($USper bbl) 4.0to 5.0 2.0to 2.5 3 . 5t o 4 . 5 0.5 1.5 to3.0

11.3 Margins
on location,size,automation, complexity,andcrude Refinerymarginsdepend and product prices. A good indicator of margins is the "crack spread"- the difference in price betweencrude oil and refined products. 11.3.1 Location. Location. Location operating A well-locatedrefinery has lower operatingcostsand increased petrochemical plants near refineries in a located other and When flexibility. the Houston Ship Channel,etc., it coastalindustrialbasin such as Rotterdam, options, has accessto a wide variety of crudes,blend stocks,transportation and services. This enhances its ability to copewith upsets additives,supplies, to suddenchanges in price differentials. and to reactaggressively In a basin, the infrastructure- seaports,pipelines, laboratories,wastehandling facilities - is extensive. Often, a single large supplier provides utilities and commodities such as hydrogen to several different customers, This is because, due to economies of scale, reducing costsfor all concerned. production and distribution costs for a large plant are lower than those for total capacity. multiple smallerplantswith equivalent industrial as space is available, basinstend to grow. They also long As attract and support large pools of operatorsand engineers.Contractors,who perform as-neededengineering,,maintenance, and other important service by "basin gravitation." work, also are attracted Lest we leave you with the idea that non-basinfacilities are inherently handicapped,we should emphasize that other locations also can have For example,the ConocoPhillipsrefinery in Borger, Texas was advantages. built in 1932 in an area that still produces large quantities of natural-gas liquids. Except for a few nearby chemicalplants, the Borger refinery seems by pipelinesto the U.S. Gulf Coast and to isolated.However, it is connected the mammoth hub of pipelines in Cushing, Oklahoma. Through thesevarious pipelines,the Borger complex receivescrude oil from the Texas Gulf Coast and suppliesproductsto Houston,Denver,KansasCity, and beyond.Also, in

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llun sserord

'plro,t\eglJo sued ur ,firxaldruocsareduoc elqeJ pue'sessecord ]ueroJJrp 6t slueserdgt alqoJ uo peseq Inpr^rpulJoJ secrpur,Qrxeldruo3 ,r',firxeldruoo serreurJerJo slsoce^rteloreqt Surlelnsl"c roJ xepu ue pedole^epuosleN'-I'A\ 's096I eql u1 'xeldtuoJ erotu eQ ol pue] serrauuer elqelgord lsoru eql .{lgalduroJ puu f1;gqudeJ uolsreauoJ g..I I 'seuurcolqelle^qllr\\ IUeq] IJII ol pu peor relo ueql eloru ol elqrssod Surlsrxe eq lsnur ll lnq '(sreleurS) leeJ SI poeJxa .,{eusreletuelp rreq}pu suo}00ZZuq}eJoru q8re,l uec,(eq1 'uedel pue r(1e11 ur 'slrun sseco:d salJolceJ sJolceoJ eJnsserd-q8rg letcedslKeJe ul llnq eq '(po uEO eqt JoJJo ozIStunurrxerueql eunrueleplqErel\ pue ezrs e3m1uI slesson 'luepuadepur-ezrs 'roqe1 ,s1soc ,{peeu ere ,(llurcedse pexlI ,{ueuresnecoq s}sooSu4eredo Je,/Kol al?r1s1ue1d re88rq',(pelnurg larreq-red 'slsoc lcefordIlotJo 'sluerulsenur se8eluecred se slueufed lseJelur pecnpeJrolpue'slceqr(ed JelseJ uo srunlerreqSrqolut selelsuJ] eless3o fiuouoce srqJ 'luepuedepur-,,$rcedzr fllerluesse ere slsoo Suueeur8uE'slrun ssecord e8rel pllnq pue u8rsep ol ssolslsoc1l 'srsequo1-red e uo 'sd1aq fpregec ll ]nq 'surqlrire^el6usrezrs azls z'E tl 'se]lspelrun eql 'slecruaqr ,ftluenb ur peJqceJnueu lou eJeqcrq.,!\ uI aSIeereqznr(ue Jo oruos 6slery ernd-er11n roglo pu eurlose8o1 uoqrppc Jo JeqrunueErel e secnpordll
69
A\al AJaAO dUrS Sa J O"td Utna I O.tt,1c

70 TableJ9. Nelson Com Resion C.I.S. Latin America Asia Europe Canada United States Indicesfor Selected Resions

Rohin,son

Throughput
Refineries million b

58 80 135 116
z-)
a a

153

10.0 6.3 t4.7 14.5 1.8 15.3

3.8 4.1 4.9 6.5 7.1 9.5

In short: The petroleum refining businessis highly capital-intensive and competition is fierce. The predominant cost - purchaseof crude oil - is beyonda refiner's control,due to the fact that crude-oilcostsare,for the most part, determinedby OPEC. Even So, large, well-located, high-conversion refineriescan be very profitable,, especiallyduring spikesin productprices.In 2005,crack spreads reached all-time highs,exceeding $ l5 per barrelin most of the United States and >$20 per barrel in California. 11.3.4 Automation As discussed in Chapter22, model-predictive control (MPC) and real-time opttmrzation(RTO) can improve the profitability of a major conversion unit by 5 to l0%. Refinery-wide, benefits from MpC and RTo can exceed US$0.40per barrel,or $US30million per year for a high-conversion 200,000 b/d refinery.

12.

SAFETY,RELIABILITY, AND MAINTENANCE

This sectioncould have been a part of Section 1l: Refining Economics, becausethe most profitable refineriesare also the safestand most reliable. Just considerthis: For a 200,000 barrels-per-day refinery, a minor accident that shutsdown the plant for just one week can cost US$3 to 6 million in lost revenue.An accidentthat damages a major conversionunit can cost between US$80 and US$120million in lost revenue during the l2-18 monthsrequired for reconstruction,plus US$20 to 50 million (or more) in reconstruction expenses. Theseestimates don't include the cost of repairing damageto the surroundingcommunity. To settle lawsuits and pay penaltiesfor a "minor" incident that occurred in 1994, a California refiner paid more than US$S3 million.52

l2.l

Refinery Staffing

Irigure 30 showsa typical refinery organizationchart.

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,{1a;ug Z'(,1
sreeur8ue em o/ogz of pue sJoleredo eJueseqlJoJleq lnoqy 07, 'eldoad 'S'n '1ue1d f;eugor uerpeuJ ro e ur 0S, ol 699 s,(o1due lecld,fi V 'es1a Surqlfue ueql erol^I Iroa oqin eldoaduo puedepfllllqeller pue ,fieJes
f"reugeA 'gg atn8tg ueqJ uorlezruuS.rg

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'72

Robinson

Protectiveclothing is required.Anyone in an operationsarea must wear fire-proof coveralls,a helmet, and safetygoggles.Hearing protectionand steel-toed shoesmay alsobe required. . Safety equipment is well-maintained and readily available. Safety equipmentincludes alarms, intercoms,sprinkler systems,self-contained breathingunits' and first-aidkits. . Safetytraining is rigorousand continuous. Training topics include: o Sa.fetyregulutions. In the United States,safety regulationsare issued and enforced by the Occupational Safety and Health Administration (OSHA). Per OSHA requirements, for every chemicalin the plant, a Material Safety Data Sheet (MSDS) must be available.An MSDS describesthe substance, classifiesits danger,if any, and describes proper storage and handling. o Emergency procedures, including where to go and what to do when they hear different alarms. Usually' there are at least two kinds of alarm sounds- a fire alarm and a toxic-release alarm. Possibletoxic releases includeHzS,which is actuallymore poisonous than hydrogen cyanide,, and carbonmonoxide. o Muintenunce safety.Historically, most refinery accidentsoccurred during maintenance. Now, all proposed maintenance work is reviewed and pre-approved by operations,engineering,craftspeople and management. Lock-out, tag-outprocedures preventunsuspecting employees from trying to startequipmentthatshouldn'tbe started. . Contractorsmust be trained, too. Before they can enter the plant, all contractors are requiredto completesafetytraining. Safety programswork! For example,a report by ChevronTexaco claims that, between1990-91and 2000-01,safetyprogramsreducedinjuriesby 90% at its large refinery in Pascagoula,, Mississippi.53 ln 2003, Valero'sPaulsboro refinery had no lost-timeinjuries and a total recordedinjury rate of 0.7, which is three times better than the industry average. For this and other achievements, the refinery was one of only 13 in the United Statesto be honored as "Star Site" within OSHA's Voluntary Protection Program (VPP). In addition, the plant earned four national safety awards from the National Petroleum Refiners Association (NPRA). "Our successfulVPP efforts have taken the commitment of every person in this refinery, and I'm proud of how everybody has worked together as a team to make it a safety leader,"said Mike Pesch, vice president and manager of the refinery.5a

12.3 Reliabilitv and Maintenance

Most refinery -uin,.nun., takes place during scheduled shut-downs, when refinery personnel,often with help from contractors,clean, inspect. maintainand (if necessary) repair equipment.

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74

Robinson

plants without affecting capacity,because equipmentfrom both predecessors continuesto run at full rate. For example,the 300,000b/d Flint Hills refinery in Corpus Christi, Texas used to be three separate plants owned by Koch Refining, Gulf States and Kerr-McGee. Trends are similar in Western Europe. Total capacityhas levelled off, but the number of refinerieshas decreased, in part due to mergers.Plantsowned by BP and Texacowere mergedto form the 380,000b/d Netherlands Refining Company (NeRefco). MiRo, a 283,000b/d refinery in Karlsruhe,Germany, was createdby a mergerbetweenrefineriesowned by E,sso and by the by the - DEA, Conoco,veba, and Petroleos four oMW partners de Venezuela. In recent years, consolidationhas evolved from relatively small mergers between neighboring refineries into mega-mergers between fully integrated oil corporations. Many of theseare listed inTable 40.
Table 40. Lars.eMe ers and Acquisitionsin the Oil Indus Present Name Component Parts BP BP, Amoco, Arco, Castrol,Veba ChevronTexaco Chevron,Texaco.Gulf ConocoPhillips Conoco,Phillips, Tosco,Unocal ExxonMobil Exxon. Mobil Total Total. Fina. Elf Valero Valero, Phibro, Diamond Shamrock,Premcor"Ultramar* *Valero acquiredits Paulsbororefinery from Mobil and its Benicia refinery from Exxon

13.2 EnvironmentalRegulations
- tightening environmental A secondmain trend in petroleumprocessing regulations- startedin 1970 and accelerated in recentyears.Major areasof improvementinclude: Reducedfugitive emissions. This requiresmodificationor replacement of valvesand compressor seals,along with more-vigilantmaintenance. Reducedparticulateemissions. To reduceemissionof particulates, better cyclonesand high-efficiencyelectrostatic precipitators are being addedto FCC units. At delayedcoking units, enclosed coke conveyorsand storage systems havebeeninstalled. ReducedCO, SOx, and NOx emissions. Reductionof carbon monoxide emissionsrequiresimproved efficiency in the CO boilers of FCC units. SOx emissions from FCC units are being reducedby the hydrotreating of feedstocks, the use of SOx-transfer additives,and the addition of flue-gas scrubbing.At some plants, limitations on NOx may require the addition of post-combustion NOx-removalon boilers and heaters. Heat-efficiency, COr. Energyis the largestcontrollablecost for a refinery. Therefore,, the drive to increase heat efficiency is ever-present, especially in crude distillationunits and other major energyconsumers. In countries honoring the Kyoto protocol, decreased energy consumption also

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76

for 664,000bld with 451'000 b/d of growth in 2003. Overall, Asia accounted demandgrowth in 2003. of the 1.6 million b/d of global incremental China will continue to drive consumption growth and affect regional product trade, prices, and refining margins. India is also likely to return to higher growth, and the region's midsized markets, such as Thailand and Indonesia,will post strong growth. In 2004, FACTS Inc. expectsdemand growth of 386,000b/d in China, 22,000b/d in SouthKorea, and 31,000b/d in worldwide petroleumdemandwill increase India. After 2004, average by 2.5 per year,with Asia accounting for abouthalf of the growth. to 3.0o/o

13.5 Automation
Advancedprocesscontrol (APC) and model-predictive control (MPC) are widely used in the industry.Real-timeoptimization(RTO) is rather new, but is growing Chapter22. its acceptance APC, MPC and RTO require modern instrumentation, which includes actuatorvalves, distributedcontrol systems(DCS), high-flux data highways, analyzers,and dedicatedcomputers.They also require trained support staff, which at this writing is in shortsupply.

L4.

SUMMARY

Modern petroleumprocessing startedin 1860.During the past 14 decades, it has grown in response to market drivers, particularly the demand for transportationfuels. In recent years, in responseto economic drivers and pressurefrom environmentalregulations,the industry has been changing. We sincerelyhope this book is a help to peoplewho wish to gain a better of the industry today. understanding

15.
l. 2.
J.

REFERENCES

4. 5. 6. 7. 8.

Energy in the United States, 1635-2000, Energy Infonnation Administration, U.S. Department of Energy:Washington, D.C., 2003 Moldauer,B. (ed.)All About Petroleum,American PetroleumInstitute:Washington, D.C.. I 998 Weinkauf, K. "The Many Uses of Petroleum from Discovery to Present," Desk and Derrick Club of Tulsa: Tulsa,Oklahoma,2003 Significant Events in the History oJ'Energy, Energy Information Administration, U.S. of Energy:Washington, D.C., 2003 Department "World Oil Balance Data" International Petroleum Monthly,2004 (2) Table 2.1 Scotese,D. "Jacksdaleand the SurroundingNeighborhood" A Village Remembered,from the Ironville Post Office, Number I Market Street:Ironville, Nottingham, UK "Oil Shale" Il'ikipedia, TheFree Encyclopedia,2004 (http://en.wikipedia.org) "Major Developments in the History of the Polish Oil Industry" Polish Oil and Gas Company: Warsaw, 2003 (http://www.pgnig.pUen/pgnig/firma/histria/przemysl)

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