No. 1 202 Composition and Properties of Heavy Crudes M.M, Boduszynski, C.E. Rechsteiner, A.S.G. Shafizadeh, and R.M.K. Carlson, Chevron Research and Technology Company, USA Abstract ‘This per piesa re oversiew fou andertandig of he anpotion and propeter of pelea. The emphasis & on Ia and errheoy cra ls ond how hey compere with ‘comentonalcrder Data ae presented fo strate no ‘Spproah crude of choractersation hich war deep {Cheon Tis approach is bared onthe view tht rade of! 15 a conimuous mice of ergontc compound. I wiles a concp ofthe anospheieequioten Boling pint (AEBP) {ale which encampases the etre ede ol including nom ‘dlite reside, he AEBD sale makes posbe compet ‘inal emporio oferudes ona commen and rational bass Data ae presened 10 strate the continuous changes of ‘rae cil composition and properties a a fiction of inerea Ing AEEP The real provide new ight ino the chemical rar of ey eres Introduction A reseuch eff was underaten to deliente the compleisy ‘fpeoleum and develop beter meas ore o dierent on. Hany ones and beng ens of cometone eres swere of parulr merest_Canent practice of evaluating ay sds is based on comparing» few balk prope (6 vin, vibes) and des no revel important compo- sidool iflerenes, which determine cae ol itis ve Crude Oil Gravity and Viscosity The tem “heavy” refers to crade oil ensiy, Heavy craes Inve hip densities A are of Reavy ede has higher mss (Gsbeave) tan bare of ight erode. The APL ravi sale ‘is commonly used for ranking ees, The API wavy i eine the following formule: (ravi = 1 Sidensty 13.5 PAPA] Arabian cries, light with gravity of 32.5°APL and "esny” ‘vith rity of 27.AP, are classe examples of the gr ised ene il asking Word reserves of bey crue, bv Their canposton and properties are poorly understood igure ils the reationsip beeen cde il gas- ian aco The data demons tht roel viscosity increases pal with decreasing gait. Hea, low-gavy res, re ery ico, ‘The term “hes” als euently refers wo “high bling” petroleum actions. Disa the primary eefnry ope ton tat separates crue olin actions, which then ae feedstock to various conversion and upgrading process tillaion under atmosphere pressure produces high abe islates and lou-value residue (650% of 34°C atmo ‘phere residue) which comprises high molecular weigh ‘on sumber (-300 MW, °€20) pevoleum molecules Tie ‘orton of era ol nally refered to a8 “heny en Figure iarates dramatic eect of "henry cs” og inyand wiscos, The da represent groves and viscosities cof “heny end” facons (C20), whch Were derived fe raed in gure 1. The eaval of “ght en (w-Seiling facions) fom these cds readin «mar Shit ioward lower geviy and edamate increase of weer ly. Figure 3 shows he lationship between cade il avy tnd yield of "envy ens" (60°F or >C20) Cade os wih igh yield of ean ends” (amospheri reside) have kw ety and very hgh viscosity Characteristics of Petroleum “Heavy Ends” ‘The effectiveness ofthe conversion of petroleum feds ‘nto more valle product i adver alee by eae i ‘eden to frm coke ab messed by carbon reside contet (Otero Carbon Resdoe Test MCRT). Figure 4 shows he ‘eltinship between ene oll gravity and MCR. comet envy craes have high MCR coeteat and dus se expense to reine. Mets, parclaly vata and ihe, abo versely affet crude ol convertn proces by paso {atl High metal rues are expensive process Figures, ‘and 6 show the relatonship between crude oil avy ad Vanadium and ihe content respectively The data show ‘ese tend of increasing metal content wi deste rae ol grav Both vamaium (Figure 8) and sckel (Fe {re 6 content boweve, spa avery Wide concen rnge or crules wth th same evi. Thus, rec ravi it «good pedir of he met cote Sulfar and nitrogen ae also uadesinble and must te removed fom enfe l omeet he ng eiement fr Highevalue fel, Both deulfzaton nd deitopcstonpoceses are expenive at they requie lame amounts of Expensive hydrogen. Figures 7 an @illstate the rlaton- ship between erode oll gravity and sir and nogen con- tent respectively, The data show a general wend of nreasing rulfr and nitogen content with derasng gai. The wide Tange of sulfur and nitogencoacntstons ata giten pray, hovtever, demonsoate ht creo yin» good pre itor fsa and nieogen content. Crude Oil — What is It? Cade oi isan immensely complex, continuous miatwe of ‘vere ompnie compounds, epaning a sige molecular ‘weiphveaton munber range Bach ede oil component ct be descied bythe general formule: CaHlaeez.X where C-eatbon 1-mumber of crbon stems in molecule H-hydrogen 2-bydrogen decency vale 2X heteroatoms (uf, topes, oxygen, vanadium, ant ck) The hydrogen decency valu, Z, is perhaps the most important parameter inthe above formula ast ect fess ‘deol gravity This sisted in Figure 9. Te API grave Sy decrees femalably (deny sacs) a molecular soucue becomes more ycropen defer. The Pyrogen: ‘ch para gctre(heradctoe 2-12) hs hgh Baviy of SLS'APL The more hydrogen decent naphene race, involving foo stated rings (peryopytene, =~ 6), hs lew gravy of 124°API, Fall the hydroger-poor aromatic strstr, volving four unsaturated ings (pene, 2-22) Ins avery low gaviy of 202°APL all te compounds Shown i Figure 9, however, have the sme carbon miner (C16) and tei molecular weight decreas only sigh with Increasing hydrogen defi. Thus, ow hyoges ects (igh hydrogen din) of eae components tbe Key rameter affecting cre i gravy Hey eres are hyo en deficient Molecule weigh andr cabon number dsrbution of rate i components parca important or diferett ingheny erases bees of he wide range ty cover. This is ihsoated in Figure 10 Toe plosio Figure 1 give a canal tive yield fom srde ol ar ition of apa equislent ‘bon number The carbon number sel uses pea 4 ‘Sencha The daa show a phe 4GS°AP che than lost 80 percent of componeats with erbonmamber lest than 20 (620°C),Ineresingy, all cade (ght and eae) conan signicant amounts of high boing fsctons (6S0-11S0°F or 343-420°C), which are @ major pat ofthe "heavy end kis wel known tht "euting deeper into te bare” pro- duces heer facts. The elect of et pit on yield td avy ofthe “ear end ils p Tables 1-3, which fe dats forfour pas of cre, spanning the pity range {fom abou 30°AP es ths 10°APL. Daa in Table 1 hom the ye and gravity ofthe 6S0"F* (343°C+) “hey ene also known as stmospheric reside. The resus ustte Bat the ere oil git is ota good predictor ofthe "best ds il. For example, crades A, D, and Ebave vs i= Fea graves bet simi yield of 30°F “hes end” “Table 2 gives yi and gravis of high bing (80- 50°F, 343-€20°C) "heavy en” factions. All rides in “Table 2 ot ight and env) have high yield ofthis fraction, Spaming gravity range. of appoximately10-20°APL Finally data ia Table 3 how that hae eas all have consi rable el of oon-datilae” resus (ISOs, 620°C). ‘This Baton ofthe “hsvy ends har vey lowe API grave nd cn be very diferent ever fr crags with mia gavin Heavy Crude Property and Composition Distribution Curves ‘We have demonstrated that cre il and particu the beaey ones span a wide molecular Weighleabon number range. We wil lusate now bow ede oll prope and entpositon change wih te iacening cron maber Fi tre shows gviydtbuton curves fro cades toe light 42°APD andthe heavy (13 6"AP In both cases, he uty decreases with the increasing catbon umber, Figure Willers the eet of increasing carbon number oa vi cost forthe sume two cules. The vist of low etbon ‘umber factions ow-bolng mateal were calcd fom‘measrements lower temperature. The plots demonstrate x tamatic increase in wscosiy, partly for the hexyy (36aPD creo As metioned ete, the enol tendency o frm cakes an important parameter in te evelsion of refinery feed. Sook Figure 1s sss chinges ithe MCR content Wh {he ines etbon number Da show 2 rp increas ‘be MCR content shove about CAO, Figure 16 shows bys ‘ean al certon caves nth example, be byso- {7 ave decresses fram abot TS wee down to about 9 ‘wes one aC3-C120 range. The sli content creas With ‘be inceasng carton number upto about6 wes a C120. This is verysgniiant because suggests presence of compounds Inveg more tat one sll tom per molecule. For exams, 32 wee Sat ames weight of 1000 (65) means at oF vera every molecule ar afr som, Nrogen conten ‘rade 8 tsaly mock ower thn sth. An example in Figure 1 illastotes changes im nivogen content wih the increning carbon number Major of nivogn is pres in the “hey ends” C20). Vanadium aod nickel ae ypclly presen in reo at pn levels Both met are present the "hey ends An ckample is Figure 18 isaes vans: ‘ium ad cel ditions 21°APL erate ‘Asi anal of Seay eas ivolvet the deter in of our operansly defied actions Sates, Aro ‘mace, Reiss and.Asphaenes (SARA). The. anys Involve preipittion of nolbles with an exces of ane selvestsich a scheptne(a-epane asphaltenes) The ‘bles Calne) are then rer separated sing aorpog ‘romtography it the following wee facons: "sat romatis, and “resins. The “atures cosist of Aiphat hykoearbons, which ae sedi desorbed fom the hromiographic columa, The “womates” const of both tomate hyvctboos and "nual aromatic Btrocon- und (contin SN, and O), which re adsrbed on the Sheomatgrapi came svonge thn sate Fly, ‘te “vexing and “plone” toh consist of poi, redo ‘tl heteroatom contig compounds, O, nS). The “resins at soluble in heptane whe “aphatnes” re at and precipi ou. Figure 19 thstrates how crate oil composton” changes sro the carbon mmber range. A 21°API gravity nue wat frst ile in a series of progressively tgher boing fa ‘ns (ap toa et pint of 1150 AERP. CSS) and a non- ‘ible reside (ahd-AEBP of 1269", C113. All racbons eee spate nto “ature, arms” and "pola “sing gud ehrorstography. The “pol acton consis of oth soluble “esos and insoluble “sepblens” AppoN ately bal ofthe "polars wee isle eepeane (C7 "ephaenes"), The data show aap decease “ures” conte wth the increasing carbon mumbe. The aromas” Increase in concent ofeach a maximum at stout C30- (60 and then thei content pil decrees. The “pos” fist appear in the “heavy emis” (C2) Ther content increases rapily wth the ierening can rmber The tesuls iste thatthe heme era conposton changes Aramatially withthe incresing enbon meer. The blk of the heavy cos above about C65 consis of yérogen de ‘ent, aromatic and Reterestonsish compos, some of ‘which have ited sly aed precipita out when ested with an exces of prin sleet Conclusions Heavy crude ae continuo tues of rinlyhyérogs- oor and heterotomich compounds, sparing wide carbon Funteinoleculr weight ange Aster! of te atanble roel yield and usta function of then Pain Ato Sphenc Equivalent Boing Point (AEBP) provides rato ‘bass for beary ue evaluation and ileetation‘eroupheric Reaiaue TAR] Gue point: -es0°r (-343"¢| wnole Crude Gravity, "API yield, vol.¥ravity, °A 2 3016 ael0 iit e r0.8 20.4 7.6 “al ey End — 650 whole Crude cravity, "API Yield, vol.¥ Gravity, "AH, rm 8 38.9 ile ue Point: s:150°F (26207 Whole c>ude Gravity, "API'¥ield, vol-sGraviey, “A Toles: Heay Ende 1807+OUMIAR can for Hoy Cade ae Tar Sande 868 Figure Gravity Vicon Raltonthip Cree Viscosity # 50%, est Fre 2:Grvy rcontyRalatonshi— Haney Enderavity, Pure Yao aay nce on Heavy Ende (2c Micro Carbon zesidue, wetUMAR arr fr ery Grd an ar Band 806 i | Heavy Ends C20), 3 { ‘Venadion, ppm wt ge Vaan Cot presee, el gue &. rope Cmtont cwaphthents gue: Makes Hen? o.773 may 0.903 ms 3.273 a7{EUNTAR Cano for Hear Cade nd Ter Sands 1008 “oy ya pure 1 aoc ig Dito mative Yield, veh "Sue poime, ce Ge? aoeGravity, “ne Paratesn bqutvalsne’ Carbon’ gue 1: tc of Catan Mameron my oe ae Per] Boop ees TTT L eae | oof seat rt {evi 7 1 [ ior Cason Reade, web ‘gue 1 ect of Con Nombar n VosLSUNTAR Contr for Heat Grade nd Tar Sand 1808 “ ® fabiinicacaa Aaa Sacamsiha theatres gage | | Aiuewecuwcraeo > FI) soncesiccmron | fl T «LE. | | . © 0 0 0 0% @ mm 9 1m 10 1 nn gia Ct ber Fae hyp nd utr itn epraretessbenessostenssoctineriscluseraresastantaateny| jet ee am Seu - ona |_| Figure: hoan Diaton Sa i =e ee] Be | | a ee ! | pibarattin equivalent carbon igure 1: vanaiom and Nl DationSe rrolsre” raronatice Figur 1: Composition —"SARA" ‘n-Paraffin Equivalent’ Carbon