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Handbook of Petroleum Refining

James G. Speight

Feedstock Composition

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The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The publisher shall not be liable for an loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 and physics decomposition.and of thermal provide chemistry of also to the descriptions brief and bitumen heavy and oil, found petroleum, in conventional re ning derived from of is not justapplying amatter know-how materials these Re ning feedstock. the in constituents character chemical to the equated be can feedstocks heavier the processing problemsin encountered The of issome also feedstocks importance. boiling knowledge that heavier recognition well higher- of constituents as of the feedstocks these the as the have approachesre ning to liquid fuels, there different other been and more gasoline obtain to conventional oil. Thus, than constituents less crude hydrocarbon and species more heteroatomic (Speight,bitumen 2014). 97% as high as w/w,be and oil 50% w/w for or less oil heavy crude than example, in alightcrude in content copper. hydrocarbon nickel, may and The iron, vanadium, well constituents containing as oxygen, sulfur, nitrogen, contain as and that constituents of hydrocarbonaceous amounts varying (depending feedstock) upon the with hydrocarbons containing complex are feedstocks mixtures three basis, orthe deposit. amolecular reservoir On the well individual of within the depth the or deposit age location reservoir of not with and but the only with the also vary can feedstocks physical and chemical (fractional) the and composition of re nery of each form materials, these bitumen. sand golden alight, color from ranges the yellow that in gradation (conventional oil) black to crude tar volatile extremely (Speight,and semisolid an uidityto thick, 2014). atremendous is also There lightweight, consistency density thin, very and in range from bitumen sand tar heavy and oil, extra heavy oil, crude state, unre ned its natural, have In properties. unique naturally will locations geographical different from feedstocks any of fact is duethese that the to This produced. was material on where the depending differ physical the and characteristics geneous materials, weight. molecular as conventional aquestion in well as becomes It of then degree occurs petroleum. as bitumen and oil heavy in occur types molecular similar that anticipated it be might mind, in With product. this oil troleum protope formthe that precursors of the by proportions the of is dictated continuum nature the and cursors) processes. (conversion maturation the physical prevalent the and are during conditions that pre oftures, the - struc chemical their of petroleum, precursors of the by nature the limited are fraction speci ed (Speight, generalization acceptable 2014). is an leum porridge”) any in types molecular the And soup” or “petro precursor “protopetroleum” (also as to “primordial referred as to often referred is that formamix precursors petroleum the that theory the addition, geologic In through strata. rocks source the from it migrated has after occurs wheredown, accumulation butreservoirs in were laid found notprecursors usually where the are bitumen sand tar Petroleum, heavyand oil, 3.1 chemical behavior chemical The purpose of this chapter is to present a brief overview of the types of constituents that are chapteris present to are overview abrief of that of constituents this types of the purpose The residuaHeavy and (as bitumen, oil, a result effect concentration of of the distillation) contain categories) not (withinindividual the are bitumen sand uni tar heavyand oil, petroleum, Thus, not homo are bitumen sand tar heavyoil, extra heavyoil, and oil, crude state, natural the In consideration oftypes, acontinuum the molecular ofas in petroleum resulted concept has This

3 INTRODUCTION after which the prevalent conditions become operational in the formation of the nal crude crude nal formation of the the prevalent in which the operational conditions become after Feedstock Composition Feedstock of these more complex of these constituents. crude oils but requires knowledge structure but oils chemical of requires the crude and the amount the and of complex, higher-boiling and and 101 - - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 a role in determining the processability of afeedstock. processability the a role determining in plays also other each with constituents of reactions well these as constituents of the reactions as the ratios.chemical Additional knowledge various these accurately, from the such de ning atall, as if predicted be slates cannot Product data. these from behave feedstock predicted will as a particular that is now on acomparative there may basisfeedstocks, used analyses, no between be guarantee by elemental determined ratios, as atomic although Thus, operations. new dimension re ning to of use composition) of more complex The chemical re ning. a (in terms feedstocks added has before feedstock character for predicting only requirement not the are ratios these that operations, 3.1). (Figure upgrading hydrogen molar weight, for molecular the the with indicates requirements feedstockof and, the quality of indication the elemental of composition the inspection initial Thus, of is an feedstocks Similarly, lower the lower heteroatom content, the the hydrogen the for upgrading. requirements lower of the feedstock because is its valuehigher re nery hydrogen as for upgrading. requirements D4294 ASTM (2015).and ratio, the hydrogen–carbon atomic the higher the feedstocks, For all (2015), D1757 ASTM (2015), D2622 ASTM (2015), D3177 ASTM (2015), (2015), D4045 ASTM oxygen content tent (2015), D3343 ASTM (2015), D3701 ASTM (2015), E777 ASTM (2015); and (2) nitrogen con- for designated (1) methods also are There hydrogen content (ASTM D3178, 2015) for solid designated waste or bymunicipal method (ASTM the E777, 2015). processes. by catalytic re ning during catalyst performance have can deleterious serious effects on materials nickel, these afeedstock and since in vanadium elements, of such trace amounts as the of It feedstock. of isvalue also the determine to character (i.e., for used overall of frequently ments carbon indications to the N/C, S/C) O/C, and are H/C, ele evaluation, various of ratios an atomic the of The afeedstock. perform and nature, general the (elemental composition)sulfur examine to composition, used method ultimate rst the is perhaps analysis of by for percentages feedstocks The weight the hydrogen, of carbon, nitrogen, oxygen, and 3.2 102 FIGURE However, heavier of re nery into introduction the feedstocks the with apparent, it become has For example, carbon content , ASTM D3179, ASTM (2015), D3228 ASTM (2015), E258 ASTM (2015), E778 ASTM and (2015); (3)

ELEMENTAL COMPOSITION 3.1 Atomic hydrogen/carbon ratio and molecular weight of feedstocks. molecular and ratio hydrogen/carbon Atomic , ASTM E385, ASTM (2015); (4) and sulfur content

Viscosity

Nitrogen H/C atomic can be determined by the method designated for coal and coke for and designated by coal method the determined be can ratio 0.5 1.3 1.4 1.6 2.0 Vacuum residuum Crude oil Heavy oil Gasoline , ASTM D1266, ASTM (2015), D1552 ASTM , ASTM D1018, ASTM (2015), D3178 ASTM Handbook of Petroleum Refining of Petroleum Handbook Molecular weight 1,000 10,000 500 300 100 - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock over limits: fairly narrow elements oflarly nickel awholevary these vanadium),oils amounts in and of the crude series and bitumen is generally constant and, like the data for petroleum, falls into a narrow range: anarrow into for falls petroleum, data the like and, constant is generally bitumen et al., (Wallace identi ed 1988).is carefully samples forhave reproducible from sound, origin which produce to the data focused on aprogram However, sand. may on bitumen the thereforeand representative not be total of the efforts recent whichby bitumen, may any one haveofsis for several is quoted obtained procedures separated been covers that bitumen Athabasca several deposits) analy not is site often the addition, and speci c. In (i.e., general is too identi cation source of that disadvantage the the suffer from 2009), data but the composition. amuch to of range narrower elemental is but restricted petroleum coals, of ranges the carbon (Speight,w/w 2013). anthracite in various subdivisions possible the other course, are Of within low as from 75% as vary contents can of is classi ed; coal coal carbon 95% to w/w lignite in hydrogenand content, it is not possible content basis ofas on the carbon petroleum to classify of 1977). range carbon 1969; narrow of et al., the because et al., And Draper Charbonnier also extreme (see other at the oils heavier at oneoils extreme to the crude more mobile asphaltic crude lighter, the from physical in wide variation properties the to is contradictory range narrow This and bitumen viscosity. bitumen and gravity, bitumen curve, point, distillation pour are ratio hydrogen–carbon Elements to the related lower of the feedstock because is its value higher re nery hydrogen as the bitumen, requirements. of ratio hydrogen–carbon the of ratio higher hydrogen-to-carbon 1.5atomic The is more typical. low as ratios hydrogen-to-carbon 1.3 as an although bitumen, have sand for observed been tar its gravity, Atomic point. characteristics, itsmen’s pour and or thermodynamic curve distillation bitu the affects It extraction processes. also for energy heat thermal supplementary required the processing. behave might of during indications how material the history. oxygention, is susceptible bitumen oxygen aerial to the and content dependent is very on sample addi In elemental data. other the in errors of the ofanalysis is subject accumulation all the to 0.2% when since 4.5%. oxygen as high as to is the not by surprising, difference This is estimated as little oxygen as is the from major vary limits exceptionThe can content that narrow these to Hydrogen: Carbon: hydrogen, carbon, nitrogen, oxygen, (particu contains petroleum metals and summary, sulfur, In Sulfur: Oxygen: Nitrogen: Hydrogen: Carbon: available, elemental are composition the conventional that Like of data sand of oil petroleum the (Speight, widely been 1990, also reported elemental analysishas bitumen of The sand oil Metals: Sulfur: Oxygen: Nitrogen: The viscosity of tar sand bitumen is related to its hydrogen-to-carbon atomic ratio and hence and ratio atomic its to is related bitumen hydrogen-to-carbon sand viscosity of tar The only give composition, can these ultimate the from noted be several can Although generalities Metals:

(Ni and V) <1000 V) ppm and (Ni (Ni and V) >1000 V) and (Ni ppm

83.0%–87.0% 0.05%–1.5% 0.1%–2.0% 10.0%–14.0% 83.4%–0.5% 0.05%–6.0% 1.0%–0.2% 0.4%–0.2% 10.4%–0.2% 5.0%–0.5% 103 - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 in feedstocks as organic or elemental sulfur or in produced gas as compounds of compounds oxygen as gas produced or in (SO or elemental sulfur organic as feedstocks in ratio, viscosity, bitumen viscosity. pro le, and distillation content, hydrogen cess. sulfur Elements content, to nitrogen hydrogen–carbon contentrelated are employed catalysts by pro the process poisoning re ning re ning the constituents complicate in the viscosity. and curve, nitrogen content, distillation exceed 10% w/w. hydrogen content ratio, are content, hydrogen–carbon Elements sulfur to related can bitumen sand contents of some tar Sulfur process. re ning and upgrading the some point in of oxygenpounds hydrogen and expensive is an It nuisance. must removed be at bitumen the from 104 and residua are acomplex residuaand are composition of (1) (2) hydrocarbons, (3) nitrogen compounds, oxygen characteristics. different very with petroleum well. individual of Two the depth the with occur that likely produce to adjacent more than wells are age location eld of and the with the addition any to variations in position vary ofcan petroleum for description compound even com would oil the asingle possible. not noted, be crude already As acomplete that itcompound-by- that is unlikely is so great variety fact, the size. In molecular and extreme of functionality range organic an contain bitumen sand tar heavyand oil, Crude 3.3 spectrometry. or by spectroscopy inductively by species absorption for atomic ined metal coupled plasma argon solution the acid and an exam digestedwith be then can ash The remains. ash only inorganic by whole accomplished combustion be in of can sample of so feeds that metals the Determination (ASTMucts D1318, 2015; D3340, ASTM 2015; D3341, ASTM 2015; D3605, ASTM 2015). without loss serious of catalyst or activity catalyst life. develop to made of being concentration tolerate metals ahigh are can that catalysts attempts serious Thus, cracking. such catalytic as processes other nitrogen removal in used catalysts well as the as exceptions the here. are distillates boiling higher- the in appear conditions and distillation the under volatilize may actually constituents that residuum the (Speight, in metallic concentrated The 2000). are oil crude original the in metals the all that dictates virtually by produced process which of residua the are nature the Indeed, feedstock. (such constituents lic extremely whichremove to are metalloporphyrins), dif cult the as the from organometal formof or as relatively salts the eitherresidua in of contain metals proportions high real. becomes hydrogen (H hydrogen routinely remove 90% of the sulfur from afeedstock (Speight,routinely from remove 2000). sulfur of 90% the available easiest are that catalysts remove to the is usually commercial elements, many and sulfur exceed 5% can bitumen sand or contenteven of tar 10% sulfur the by hetero weight.of the all Of of order 1% on the are oil contents of crude many by weight, Sulfur process. whereas re ning and not removed, the potential fornot production removed, of the potential nitrogen oxides the (NO fornitrogen is fewer speci c the nitrogen. If are are there that catalysts and remove sulfur, than employed catalysts by Nitrogening the processes. poisoning to various is more dif cult the in 1.5% as high as be can bitumen by sand weight. ofof presence nitrogen tar complicates re n The Furthermore, heteroatoms in feedstocks affect every aspect of re ning. The occurrence of sulfur occurrence of The every re ning. aspect affect feedstocks in heteroatoms Furthermore, 1.3% as high as be can bitumen sand nitrogen by content ofThe weight tar nitrogen-containing and com as gas produced or in or elemental sulfur organic as bitumen in of sulfur occurrence The In very general terms (and elemental analyses), from observed as terms general very heavybitumen, oil, In petroleum, - prod petroleum in of metals of have tests for determination designated A variety the been and for of constituents causeproblems used feedstocks catalysts sulfur Metal by the poisoning Metals The The CHEMICAL COMPOSITION nitrogen (particularly 2 S) expensive is an of It re ning. must removed aspect be upgrading the atsome in point content of petroleum is usually less than 1% content less of than is usually petroleum by weight, nitrogen but content the vanadium and and nickel ) are found oils. every Heavy in and oils most) are crude Handbook of Petroleum Refining of Petroleum Handbook x ) during processing and use and processing ) during x ) and ) and ------

Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 tic crude oils. Nevertheless, crude oils with as little as 50% hydrocarbon components are still still components 50% are as hydrocarbon little oils. as Nevertheless, with oils crude tic crude oils) crude low or as 50% as by weight by heavy asphal paraf nic the or less illustrated as functions. heteroatomic of the nature the and skeletal structures hydrocarbon the to related inferences designedto draw well as methods as dures must constituents employed. be chemical include of proce Such fractionation a myriad techniques rely that upon volatility). the techniques (using offeedstocks identifying methods analytical Other It is by not possibleheavier of constituents distillation. the the identify obtained isolate to be and can constituents. behavior chemical and knowledge structure chemical ofrequires the ofis not just applying a matter know-how conventional re ning derived from the character chemical the to equated be heavier can the feedstocks processing in encountered problems the Indeed, of issome also higher-boiling feedstocks importance. stituents of these knowledge that recognition con of the the been has liquidfuels, there other and more gasoline feedstock. of the processability the understand to is necessary but much more information true, more hydrogen is indeed require fuels. liquid to for This upgrading character) would in alower (having oil more aromatic being and ratio aheavy crude atomic that H/C indicates property alone. ratio atomic This H/C is the amore conventional and oil material crude aheavy between major the difference that composition surmised it alone. be From might such data, priori a to understand, is dif cult or physical chemical For relate they the example, to composition as it material. ofproperties the bulk the elemental compositionof the knowing of of understanding afeedstock; it amatter is also is not only amatter Processability feedstock. of the processing aspects chemical of the standing operations. re ning during feedstock behavior the determining in important items of are these stituents of a All feedstock. 3.4), (Figure types play which con can functional the between a major interactions role the in of speci c phenomenon well occurrence as the or the as of size molecular addressed, is rarely nature) (i.e., species ior). of acid/base amphoteric havingcompounds amixed occurrence The by feedstock of(perhaps, behav the analogy, makeup human ular just geneticdictates as makeup oils. crude of for variety rich account species the molecular of these characteristics and distribution The phenols, etc.) pyrroles, (such carboxylic forms nonpolar dines, acids, amides, in than ethers). as (pyri forms found more likely polar be to in are oxygen-containing constituents nitrogen- and derivatives thiophenederivatives, (5) doand thioether and as constituents) sulfur tan contain etc.), (naphthalene, analogs multiple ring phenanthrene, fused (4) (mercap constituents thiol extentthe oddity, of considered an being (3) to benzene from range constituents monoaromatic iso cycloalkanes (paraf ns, and alkanes, branched alkanes, include constituents normal urated of compounds:gen, related (1) or nitrogen). several families are class, each there Within sat (sulfur, heteroatoms oxy bearing compounds and aromatics, classes of compounds: saturates, behavior. re ning ity is no of longer for determining task the adequate grav API content, and consideration ratio, the of atomic sulfur hydrogen-to-carbon stocks. Indeed, composition the it behavior ofas relates describe petroleum the to - feed of these is not adequate (4)compounds, (5) constituents. and However, compounds, metallic sulfur de nition general this Feedstock Composition Feedstock The hydrocarbon content of petroleum may be as high as 97% as content high hydrocarbon ofmay as by petroleum be The weight (e.g., lighter the in However, extremely information are bitumen complex, and oil direct little very heavy crude and obtain to bitumen, sand tar residua, oil heavy and oil, of necessity crude With processing the (or types composition) chemical of the under understanding an to lead ofAn any feedstock can consideration the molec of- the through addressed is better re ning behaviorFeedstock during of three terms in composition described molecular be the ofcan petroleum Furthermore, -paraf ns, and naphthenes, in petroleum terms), petroleum in naphthenes, (2) and (ole ns) constituents -paraf ns, alkene to rare are amount of complex, higher-boiling constituents in the feedstock. Re ning these materials materials of complex,these Re ning feedstock. the higher-boilingin constituents , the process chemistry of various feedstocks from the elemental the from feedstocks of various chemistry process , the of these more complex of these crude oils but oils crude and and 105 ------Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 to nished products, leading to discoloration and/or lack of stability during storage. On the other storage.other the On during discoloration to lack of and/or leading stability products, nished to 3.2). (Figure increases also constituents the complexity molecular but the of increase constituents of number the notbitumen, the only does higher-molecular-weightsand to progresses tar to oil heavy to crude oil crude from feedstocks of(Speight, feedstock series petroleum higher-boilingthe fractions as addition, the 2000).In oxygen, one or more sulfur, or nitrogen containing atoms)compounds in concentrate to tend constituents (i.e., nonhydrocarbon The re ning. oil organic those crude in somecauses concern compounds nonhydrocarbon of of these appreciable amounts appearance the and plex mixture, oxygen nitrogen, and ofcompounds even sulfur, as oil only serves present to crude more com 1989; (Green size et al., molecular 2014,their Speight, 2000, 2015). of organic occurrence The of irrespective is important petroleum of the processability on the inuence their and oil crude of the processability the determining in play that constituents metal) part nitrogen,a large and which occur. they in It (sulfur, is, fraction nevertheless, nonhydrocarbon the oxygen, the and size molecular of their irrespective is important petroleum of the processability on the inuence their Indeed, of petroleum. higher-boiling fractions the in concentrate to theytend may quite small, be oxygen, one or more sulfur, fractions containing or nitrogen compounds atoms)organic certain in oils. Even (i.e., constituents of of crude concentration nonhydrocarbon re ning the though those the in causessome concern compounds nonhydrocarbon of of these appreciableance amounts oxygengen, and appear even the as oils and only serves present to crude more complex mixtures, inclusion content. hydrocarbon The the nitro of of compounds sulfur, organic of than petroleum (Speight, future 2011). the in bitumen sand tar heavy and oil, composition But is more the to there oil, of crude processability the determine will and oil crude of the processability the determining (sulfur, nonhydrocarbon oxygen, the in play that constituents metal) part alarge nitrogen, and It hydrocarbons. of is, nevertheless, the characteristics most essential of the retain to assumed 106 FIGURE bitumen the line from 0% to 70% to 0% steeper. is from line the bitumen The presence of traces of nonhydrocarbon compounds can impart objectionable characteristics objectionable characteristics impart can compounds of nonhydrocarbon of presence traces The 3.2

Variation of compound types in petroleum with the boiling point—for heavy oil and tar sand sand tar and oil heavy point—for boiling the with petroleum in types Variation of compound

Increasing aromaticity, decreasing hydrogen content

Increasing nitrogen sulfur and metal content 02

0 Volatile saturates and aromatics Feedstock (wt%) 060 40 Boiling point

350/660 Nonvolatile saturates and aromatics Handbook of Petroleum Refining of Petroleum Handbook 0100 80 Resins

Asphaltenes °C/°F - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5

petroleum into the following three classes: following the into petroleum three It is therefore convenient indeed. components of rare hydrocarbon very divide to the are carbons (Tablegroups 3.1). hydro acetylene-type and oils, found crude not usually in Ole n are groups aromatic naphthenic,and of composed paraf nic, components ofare hydrocarbon petroleum the Nevertheless, of petroleum. well higher-boiling fractions of that many it the been established has constitute that those to hydrocarbons synthetic of the identity or even the similarity the determine to hydrocarbons synthesized from obtained basis data of on It the the is dif cult encountered. ties for causes dif cul oxygen, the of of presence main compounds sulfur, the the nitrogen are and complexity higher-molecular-weight ofwhelming constituents hydrocarbon the of the and fractions over the and task, exceedingly dif cult is an petroleum isolation from The compounds of pure 3.3.1 materials. nonhydrocarbon these of proportions substantial well as oil contain residua as that more heavy crude process to been has industry, of re ning late, the in trend the ofas constituents given petroleum nonhydrocarbon the to considerable that must attention present.Itbe is therefore not are surprising compounds when these sequences re ning most noticeable the effects during are corrosion and catalyst poisoning hand, Feedstock Composition Feedstock 2. 1.

H hydrocarbons”) “alicyclic as (more known sidewhich may chains have correctly one or more paraf nic Naphthenes structure any ring Paraf ns rmtchtraoi ytm Furans(single-ringandmulti-ringsystems) Aromatic heteroatomicsystems Sul des Alkyl sul des Saturated heteroatomicsystems Benzenesystems Ole ns, nonindigenous;presentinproductsofthermalreactions Aromatic hydrocarbons Unsaturated hydrocarbons Saturated hydrocarbons Class Sand Bitumen HeteroatomHydrocarbon and Types inOil, Crude Oil, Tar Heavy and TABLE ydro , which are saturated hydrocarbons with straight or branched chains, but without chains, or branched straight with hydrocarbons saturated , which are C 3.1 ar , which are saturated hydrocarbons containing one or more rings, each of each one or more rings, containing hydrocarbons saturated , which are B on C on S tituent Alkyl sidechainsonringsystems Amphoteric (acid–basesystems) Mixed heteroatomicsystems Pyridines (single-ringandmulti-ring systems) Pyrroles (single-ringandmulti-ringsystems) Thiophenes (single-ringandmulti-ring systems) Alkyl sidechainsonringsystems Cycloalkyl sul des Alkyl sidechainsonringsystems Condensed naphthene–aromaticsystems Condensed aromaticsystems Alkyl sidechainsonringsystems Condensed cycloparaf ns (includingsteranes, hopanes) Cycloparaf ns (naphthenes) Iso-Paraf ns andotherbranchedparaf ns n-Paraf ns S Compound Types 107 - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 108 FIGURE paraf ns. of normal amounts only small very n by up 20%–50% to weight may petroleum contain fact, paraf nic oils. In most in crude portions 2014). (Speight, conditions maturation during prevailing materials relativesource the individual ofas the amounts well as material source of the nature dependent is very apply upon the and constituents other to constituents” (Bestougeff, 1961). “predominant the as to referred been may also generality This have these and fraction, of the part greater the of number forming constituents may asmall be absolutein relative there and fraction, oil values. However,or crude oil crude any particular in systems. invoke that existencepolynuclear proposals of condensed the highly aromatic than ents rather lower-boiling the to related - constitu constituents) asphaltene and constituents structurally are high-molecular-weight contentionsthe that current supports (resin constituents also alone and series hydrocarbon lends even the complexity the to type ofwithin more credence petroleum ascheme of this Indeed, of alteration petroleum. in situ and maturation, formation, the during interconversion of these schemes deny to occurrence is nocomposition, reason the there and gen addition or hydrogen of petroleum 3.3). aspect loss (Figure extremely is an important This (nitrogen,atoms oxygen, 3.2). (Figure sulfur) and relative the of and hetero proportion aromaticity in increase weight is aconcomitant there and molecular increasing with decreases usually hydrocarbons of paraf nic proportion the oil, any one crude but of within crude, type the with varies oil crude in of paraf ns proportion The 3.3.1.1 -paraf ns in the gas oil fraction. However, fraction. oil gas the in contain sometimes oils crude -paraf ns or asphaltic naphthenic Normal paraf n hydrocarbons paraf n Normal homologous same of members considerably the different of varies the series abundance The is one oils of hydro of constituents hydrocarbon crude various relationship the between The 3.

tuted) naphthene rings and/or paraf nic side chains paraf nic and/or rings naphthene tuted) up (substi with systems, which ring may linked be phenanthrene and zene, naphthalene, Aromatics

3.3 Paraffin Paraffin Hydrocarbons Interrelationship of the hydrocarbon types in petroleum. in types hydrocarbon of the Interrelationship , which are hydrocarbons containing one or more aromatic nuclei, one or more aromatic such- ben as containing hydrocarbons , which are P +H CH olynaphthenes Naphthenes Pa 2 3 (C ra ns H 2 ) 4 CH –H 2 3 (n -paraf ns, straight-chain-paraf ns, paraf ns +H +H –H –H 2 2 2 2 Handbook of Petroleum Refining of Petroleum Handbook Polynuclear Aromatics aromatics ) occur in varying pro varying in ) occur - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock troscopic studies that the short chains (methyl and ethyl) appear to be characteristic substituents (methyl chains short characteristic ethyl) be the to and that studies troscopic appear - spec from indications systems.are by There aromatic substituents carried alkyl the than shorter increases. systems ring naphthene systems alkyl-substituted and of ring naphthene condensed occurrence the However, asphaltenes. the in types molecular weight molecular increases, the as fraction of the even systems increase considerationconsiderable more in that of of ring naphthenic the amounts (naphthenic) contain asphaltic can the fraction In oil gas fraction. the oils, the in species crude of cycloparaf n(naphthene) amount the in increase is aconcomitant there increases, fraction weight molecule. per molecular two the rings As six to (or point)tain boiling petroleum of the oils,may lubricating con such the as higher-boiling fractions, The chains. of presence alkyl the lower-boiling by weight or point molecular the in boiling with increased of petroleum, fractions of bicyclic cycloparaf nderivatives major and mono- the types generally The are naphthenes another. to oil crude well one as from as weight fractions molecular of individual of range the function the or boiling a as oil crude same the may constituents of change these within Nevertheless, structure the close rather limits. within considerably may oil remains notgenerally tions vary of and acrude However, hydrocarbons. total of the - frac range cycloparaf ncontent of the boiling different polycyclic content of up The 60% to cycloparaf nderivatives varies petroleum in structures. ve- as combinations, occur or derivatives,six-membered n or their containing rings usually atoms. Several of ve-carbon cycloparaf series more than constituent moleculesthe contain chiey cyclecontain well as cyclohexane as pentane rings. most acids stable. the naphthenic ve- The with are show atoms six-carbon rings naphthene and that studies six-membered have lower-boiling the rings isolated from been Thermodynamic fractions. chiey ve- with naphthenes Only ve- and rings. contain six-carbon and fractions oil crude that four-, three-, of the rings ve-,with six-, seven-, atoms. eight-carbon It is and now believed generally constituents individual are there hydrocarbons synthesized the among and atoms, ofnumber carbon 300°F–390°F). mayup 150°C–200°C, point built of Naphthene be avarying rings tions (boiling such molecules (often- hydrocarbons) even frac bridge-ring heavy gasoline designated occur the in polycyclic contains Petroleum also and fractions. oil in represented such naphthenes, terpenes, as cyclopentane derivatives, (decalin) decahydronaphthalene and derivatives (naphthenes) largely are of number representatives have only asmall Although isolated so far, been cyclohexane derivatives, 3.3.1.2 (Speight, atoms or more carbon 20 1994, contain 2014). can chains alkyl systems. these naphthenic and And, on aromatic side chains alkyl as occur fractions asphaltenes the in vestiges The fractions. asphaltene of paraf ns and oil gas the in not expected are paraf ns free oils, crude naphthenic butthe in fraction asphaltene of the apart as separate will paraf ns free oils, crude vacuum (VGO) gas oil the in For at all example, fraction. paraf nic the in may no paraf ns be there oil, of crude types certain In fraction. the in paraf ns of free amount the in decrease comitant oils. lubricating the have to of physical on the small inuence is too any signi cant properties amount their oils ing iso the if that point;it appears boiling increasing with decrease iso the that It seems materials. over branched highly the predominate paraf ns slightly branched the that it accepted and is generally atall, if 4-methyl derivativethe amounts, small is present in and 3-methyl and most 2- derivatives abundant, the The of petroleum. fraction are gasoline There is also the premise that the naphthene ring systems carry alkyl chains that are generally generally are that chains alkyl systems carry ring naphthene the that premise the is also There molecule. the present in of number of rings is the naphthenes variation structural principal The Cycloparaf n weight molecular the As is a con (or there point) increases, boiling fraction petroleum of the Considerable of quantities iso-paraf ns -paraf ns occur throughout the boiling range of petroleum fractions. The proportion tends to tends proportion The offractions. range petroleum boiling the throughout occur -paraf ns

Cycloparaffin Hydrocarbons derivatives (naphthene which in derivatives) fractions all in represented are have been noted to be present in the straight-run straight-run the have present in be to noted been -paraf ns are present in lubricat present in are -paraf ns 109 - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 particularly in the heavier, naphthenic, crude oils and there are valid reasons to believe that this believe to reasons valid this that are heavier, there the and oils in naphthenic,crude particularly methyl-,and dimethyl-, have methyl oils, found several ethyl-, been in crude tetramethyltetralin and 1-methyl-,such the as 2-methyl- and 7-methyltetralin. 2-methyl, and Tetralin 4-methylindanes and of aromatic and naphthenic rings. The rst members of the bicyclic of members the rst The C rings. series naphthenic and of aromatic number equal an with series is the distinguished be to molecules. rst The their in rings of aromatic number the to classi ed according components are tions. Usually, naphthene–aromatic different the major- formthe content series, offrac hydrocarbon higher-boiling petroleum naphthenic the with together hydrocarbons, systems. naphthene–aromatic The naphthene–aromatic in occur structures atoms. atoms) nonaromatic six-carbon carbon is by substituted more than that many isolation aromatic the result an of in as acompound have (Speight, that petroleum to applied been 2014, procedures Many separation compounds. 2015) classi ed molecule, aromatic as same are the within rings naphthenic and chains ence of alkyl favoredare derivatives. over anthracene derivatives phenanthrene of petroleum, productorigins consideration of the natural ofbecause the derivatives. may phenanthrene Currently, be rings and aromatic derivatives three with those and naphthalene be to presumed are together.condensed rings components two with Thus, aromatic of (e.g., petroleum oils). lubricating higher-molecular-weight the In usually are rings the fractions, relatively be to heavier the fractions in appear without rings naphthene rare oil. Aromatics crude derivatives simple have 2-methylnaphthalenes, isolated from other alkylnaphthalene and been also homologues, benzene the to such toluene xylene as the compared and isomer. 1- addition the to In aromatics. low-boiling these with identi cation concerned of been such has compounds spectrographic that it is not surprising notwithstanding, of instrumentation limitation the Thus, fractions. petroleum lower the derivatives only in appreciableor alkyl-substituted present amounts in be to seem weight.molecular However, rings naphthene accompanying without the hydrocarbons aromatic side. by side rings aromatic and rings, naphthene chains, paraf nic contain By aromatics far,of majority these the evident of of extent petroleum. becomes aseries in upon that examination it difference and is the product chemist. natural of the domain well as chemist the as petroleum of the repertoire of the nonvolatile part integral ofshould constituents an be petroleum Welte,and 1978; Welte, Brooksand 1984). such systems identify to the Therefore, in attempts Murphy, and (Eglinton 1969; is petroleum ignored systemsis often of that aromatic source Tissot Ludwig, and 1971; (Sakarnen umented 1980; Weiss Durand, 1980). Edwards, and However, one ofrence monocyclic is well polycyclic- productchemicals and doc systems natural in aromatic occur the and is a reality of identi ablesystems nature in aromatic concept occurrence of the The 3.3.1.3 (pseudo-aromatic)aromatic systems (Speight, 1994, 2014). the favored on or within are heteroatoms occur to constituents. The asphaltene of the for polarity the responsible systems are aromatic evidence the general systems. isthat also by There stituted alkyl variously sub systemsare that of aromatic–naphthenic observations favor combined occurrence the compounds. weight molecular the to naphthene–aromatic of the according increases length, well as six, their as four to general which is in of number chains, total The cycloparaf nrings. the to may attached be (one number molecule, of or the two) alimited whereas portion aromatic of the of longer chains 110 It should also be emphasized that in the higher-boiling petroleum fractions, many polycyclic many fractions, higher-boiling petroleum the in that It emphasized be should also - pres addition the to in have that rings, compounds hydrocarbon aromatic all summation, In low content is usually benzene but the fractions, gasoline present in are aromatics known All increasing with hydrocarbons of aromatic proportion the in increase is a general There petroleum, all to common are compounds aromatic of and compounds is amixture oil Crude systems may ring occur, but naphthenic condensed general free constituent, asphaltene the In Aromatic Hydrocarbons even (i.e., is only one such there ring if six- Handbook of Petroleum Refining of Petroleum Handbook 9 –C 11 are the simplest, the are - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 the fraction produce a multicomponent chromatogram, but aless subfractions produce complex amulticomponent produce chromatogram, fraction and the of constituents of constituents The asphaltenes. functional individual of the made be to ti cations iden- detailed allows but also fraction further complex asphaltene of the the nature only con rms 1985; Readman, not and technique the Killops Speight, 1986). approach is taken, when this Indeed, et al., 1981; (Lee (HPLC) chromatography Bjorseth, 1983; Pelet, and 1983; Monin et al., Felix 1985; liquid condensation of polycyclic auspices of the high-performance systems through ring aromatic However, of terms. degree general about valuable in the add made can information technique the only be can of such a spectrum Interpretation two major structure. ne regions little very with 1981; et al., copy (Lee Bjorseth, 1983). Typically, shows asphaltene of an ultraviolet the spectrum oneconsiderable with butasphaltenes, given is potential, ultraviolet least- attention, the spectros nonvolatile residue. a as remains that of material amount is the systems asphaltenes in aromatic study of the the to (Speightasphaltenes Pancirov, and 1984). major py/gc/ms drawbackof use The the the to technique (coke)rial the present in by overall but originally low also the heteroatoms of these proportions not of only oxygen by concentration nitrogen and the resolved, nonvolatile part, the in in mate is matter systems. oxygengen and This aromatic with associated or not whether be they species convertedcoke. to fact, are in and, material more complex basis that nonvolatile on the as volatile anticipated systems is be to products remain emphasis on low-molecular-weight The over material. aromatic material the in saturated material (cycloparaf n of of single-ring well domination preponderance alkylbenzene) as species the and as which possible anoteworthywas from also is here point distribution hydrocarbon compute to the (Speight was not distribution constant but volatile the the Pancirov, matter in and tems 1984). It of polycyclic type same the produce sys fraction asphaltene constituents of- aromatic different the over material. aromatic material of saturated domination wellas the as Speight, 1987). (cycloparaf n of single-ring was apreponderance alkylbenzene) species and There strong evidence (1–4 for of presence rings) small systems the (Speight aromatic Pancirov, and 1984; 1979a,b; Schucker Keweshan, and 1980; Gallegos,1981). have techniques produced thermal These (Speight, bitumen heavyand oil, 1971; crude in side chins alkyl systems the and et al., Ritchie aromatic of the nature the to relating data some interesting produced has asphaltenes petroleum apply nonvolatile also the to fractions. productcounterparts, natural any volatile or in the fractions, in identi ed nucleus are aromatic of that the substitution patterns that productsystems. argued be It also might on natural based but fact, are which, in fractions tile volatile from nonvola to differ might that petroleum systems of throughout is- acontinuum aromatic 1979, (Long, uct origins 1981; Speight, 1981, 1994, 2014). there that such, As anticipated it be might or by heteroatoms. chains by alkyl linked any polycyclic and substituents,heteroatoms, the alkyl the systemsare that matrix, petroleum the of constituents structural simplicitiesthe of omission such important of causean assumptions other apolycyclic in of rings number condensed the does system. Tobut aromatic is true extent, this an so increases, offraction point apetroleum boiling the as that assumed generally fact, it been has residua is, the or nonvolatile that higher-boiling constituents of the petroleum, in constituents. In (Speight, 1994, of such systems 2014). nature the much determining not successin been has There about is model known compounds weightwhere range little very amolecular into boiling fall and (Speight, fraction asphaltene 1994). polycyclic These complex systems are aromatic molecules that feedstocks. bitumen complexity heavyand oil the into continues side-chain and of number rings the in increase Feedstock Composition Feedstock Of all of the methods applied to determining the types of aromatic systems in petroleum systems petroleum of in aromatic types the determining to applied methods of the all Of py/gc/ms nitro the worthyof point is note that other One not does accommodate program using pyrolysis/gas studies (py/gc/ms)Further chromatography/mass spectrometry showed that from fragments volatile of the thermal nature study to the techniques application ofThe thermal (Chapters is- acontinuum active 12prod petroleum 13)The is that principle and natural has and nonvolatile the in systemsoccur that aromatic presentthe context the in are interest special Of 111 - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 by any particular formula that is construed to be be to is construed formulathat represented by any particular adequately be cannot and studies fractionation con rms that of types compound is acomplex fraction asphaltene the mixture that (Speight, 1986). show investigations about these data the is Butthat what is more perhaps important 3.6)(Figure (Speight, 2014). is considered bitumen sand tar of and heavy oil fractions high-boiling various the in occur that types behavior when case the functional of the the active is especially the sites on acatalyst. This blocking of, on, and orientation wellquently, as structural reactor as a thermal coke formationin subse and, separation phase unanticipated to lead can that reactivity catalytic and thermal in differences substantial subfractions of result in the Moreover, functionality the in differences the tions) few system. per any polycyclic rings contain if three systems having aromatic more than - subfractions (phenolic/carboxylic func subfractions (amides/imino polar functions) neutral and polycyclic acidcontain hand, systemsother system. per the having On aromatic two rings six to 3.4 3.5), (Figures and basicfractions and nitrogen species it species was shown amphoteric that sub of functional Forvarious asphaltenes. systems example, examination petroleum in an from by adetector. separate to more dif cult maywhich may even that provemuch asingle chromatograph peak, narrower approximate much 112 FIGURE FIGURE concept of using an average structure to determine the behavior and properties of the asphaltene fraction. asphaltene of the properties and behavior the determine to average of an structure using concept In all cases, the evidence favored the preponderance of the smaller (one-to-four) evidence the smaller favored of cases, the preponderance all the systemsIn ring polycyclic of provide the distribution ring-size of strong indications data the These aromatic 3.5 3.4

Time Separation of asphaltene constituents based on functionality (polarity). onfunctionality based constituents of asphaltene Separation The complexity of the asphaltene fraction as shown by HPLC—the gure also refutes the the refutes also gure shown as by HPLC—the fraction asphaltene complexityof the The (h ydro response Detector Amphoterics xyquinoline) Ba re sin sic “B ases ” (quinoline) Base s (phenol, benzoic A sphaltenes Ac acid) ids Ion-e re –OH (e.g.,hydroxyquinolines) Alkylated PNAs Pure PNAs, xc =NH (e.g.,carbazole) –OH (e.g.,phenols,acids) sins hydroxyquinolines) N (e.g.,acridines, hange Handbook of Petroleum Refining of Petroleum Handbook Neutral (c arbazone) po lars - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 oil in only a few special cases. The presence of presence derivatives diene only afew The in cases. oil (RCH special may oils Pennsylvania hold crude exceptionalthe present in crude an ole ns position are that and some revision, ole ns it requires that reasonable assume to notis perhaps does contain petroleum up 3% to contained w/w fractions, ole ns. that opinion Hence, the although distillate well all as as oils, showed crude methods the chemical that and spectroscopic obtained; been has oils crude Nevertheless, evidence for of presence considerable of the ole ns Pennsylvanian in proportions process. distillation entirely itto the avoid and dif cult is very fractions, during cracking distilled to refer usually claims fact, these present.In investigators actually ole ns are whoare that there claim Feedstock Composition Feedstock 12-carbon atoms. 12-carbon say,impossible of having members most any isolate one more to than, series in cases, individual not of if number possible it the dif cult, very in makes hydrocarbons isomers for higher the extremely phenomenalincrease fact, an The is, in only complex hydrocarbons, contains mixture. which petroleum, that it oils. Thus, is not surprising crude various in occur that hydrocarbons organic nomenclature of and the previous presentThe somesections types of indication the 3.3.2 of presence ole nsThe (RCH 3.3.1.4 productprecursors. natural derived from systemsare that on identi ablebased structural for must abandoned be lack fraction of asphaltene evidence.the average fraction. asphaltene of the residue yield subfractions for the of carbon spread the is instance this in of note worthy residues—particularly FIGURE derivatives (RC derivatives that hydrocarbon arises is well represented. arises hydrocarbon that which from family to another, oil the one crude from varies hydrocarbon of amount any particular In summary, the premise is that petroleum is a natural product and that the aromatic systems are systems are aromatic the that productand is anatural petroleum is that premise the summary, In In summary, a variety of hydrocarbon compounds occur throughout petroleum. Although the the Although petroleum. throughout occur of compounds hydrocarbon avariety summary, In n

3.6 . Therefore, the concept of a large polycyclic aromatic ring system as the central feature of concept. Therefore, of polycyclic the alarge feature system central the as ring aromatic Unsaturated Hydrocarbons Unsaturated on

Subfractionation of the various fractions of crude oil yield subfractions with different carbon carbon different with yield oil subfractions of crude fractions various of the Subfractionation H ydro ≡ Carbon residue (wt%) CR 80 20 40 60 0 ʹ C ) is considered to be extremely) is considered be to unlikely. 0 ar Saturates B on C ═ on CHR 20 S tituent 1 ) in petroleum has been under dispute for many years because for dispute because under years many been has petroleum ) in Aromatics S 40 % ofCrudeoil 60 Resins 80 ═ Asphaltenes CH ═ CHR 100 ʹ ) and acetylene ) and 113 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 alteration may dictate that that may alteration dictate even and in situ maturation, formation, the conditions during vailing (Table compounds of sulfur 3.2) varieties many are there 2014),although (Speight, 2000, pre the regeneration frequent catalyst of or its the ing expensive the replacement. necessitat thus catalyst, on the compounds nickel) of nitrogen-containing or by chemisorption the (vanadium by deposition of caused the be metals and of catalyst of can traces poisoning the and/or passivation operations, catalytic corrosion. In tives acid derivatives, promote metallic and also can deriva- of acid components, presence such organic mercaptan equipment. The as distillation the in evolution with chlorides ganic problems give corrosion hydrochloric serious to acid can of rise free decomposition of deposited inor thermal operations; the re nery in breakdowns causeserious can crude For example, the in decomposition suspended salts the of inorganic is important. inuence their may quite small, be fractions of certain concentration heteroatomin constituents the Although 3.3.2.1 reservoirs. actual the to rocks source the of from oil migration problems the to related is of help understanding in characteristics surface-active of their knowledge here. Furthermore, some discussion process, on the of inuence is warranted each their ef ciency of nitrogen, and oxygen, Such because process. of are and atoms the nature metals, and on but the products of also the properties and nature not only inuence on the exert asubstantial can atoms context, nonhydrocarbon other current the to respect with carbon) petroleum present in oils. of crude nature elucidation and the in origin of interest the of fundamental also are compounds, related and rins porphy the particularly compounds, quality. nonhydrocarbon of products better The nished in even and methods improved could result in re ning characteristics of their and compounds these additives. It obvious is thus ness amore of antiknock lead extensive organic that knowledge of such products, discoloration,ished effective on as storage, lack of the or areduction stability in regeneration catalyst of or its expensive the replacement. frequent the necessitating thus catalyst, on the compounds of nitrogen-containing chemisorption (vanadium by deposition of nickel) caused the metals be and of catalyst of can ing traces the or by passivation operations, poison catalytic and/or corrosion. In derivatives, promotemetallic also can derivatives of acid components, presence suchacid organic tion mercaptan equipment. and The as evolutionwith - distilla problems give corrosion hydrochloric the serious to acid in can of rise free decomposition chlorides of deposited inorganic thermal operations; the re nery in breakdowns causeserious can crude For example, the in decompositiontant. suspended salts the of inorganic nonvolatilethe residues. in and heavier the fractions in mainly but oil concentrate to tend crude of range the boiling entire the throughout colloidal suspension. solution appear constituents in in salts These inorganic and compounds organometallic amounts, smaller in nitrogen-, and, oxygen-containingcompounds and 3.2) (Figure 2014). increases (Speight,also 2000, complexity molecular but constituents of number the constituents not of the only the the increases, fraction petroleum of point the boiling the as that established it been has Indeed, petroleum. in present types hydrocarbon of the overall of proportions the estimations well as accurate as carbons, isolation identi cation the and/or in lower-molecular-weight of made the been has progress hydro conceived. was Nevertheless, originally even an than considerable as oil more complex mixture 114 Sulfur compounds are among the most important heteroatomic constituents of petroleum, and and of constituents petroleum, heteroatomic most important the among are compounds Sulfur most abundant) the heteroatom (i.e., (certainly nonhydro- most important is the sulfur Although n in objectionable characteristics may ofimpart nonhydrocarbons of presence traces The is impor inuence their may quite small, be fractions certain in concentration their Although sulfur-, constituents, mainly of nonhydrocarbon organic appreciable amounts contain oils Crude Inclusion of of compounds nitrogen, oxygen, only serves present to organic crude sulfur and

Sulfur Compounds Handbook of Petroleum Refining of Petroleum Handbook ------Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock of engine deposits. Although high sulfur content can sometimes be tolerated in industrial fuel oils, industrial in tolerated be sometimes content can sulfur of deposits. high engine Although formation the to contribute can and wear increase compounds diesel fuels, effect. sulfur In harmful However, content 0.2% between 0.5% without used obvious and asulfur with been gasoline has tetraethyllead. to response number octane the to derivatives, thiophene detrimental and which are derivatives, sul de corrosive, derivatives, is color also are and disul de as stability. sulfur Free susceptibility lead affect also and of presence air the in brass of corrosion and copper cause the derivatives solution hydrocarbon mercaptan addition, in In crankcase. the in tion may accumulate combus dioxide- the from conditions, sulfur when winter water-containing under especially parts, believed of corrosion engine are promote to the compounds effects. For example, sulfur gasoline, in geological different in environments. those elds, particularly composition on the of depending newly time, with regions geographic broad varies from discovered bitumen. However, sand 5.0% tar produced oils content and oil for of crude heavy crude sulfur the approximately 0.04% from vary w/w can oil approximately to oil for crude lightcrude the in sulfur total the content and (or oil sulfur the oil) higher crude lower the the the crude of gravity the API the et al., (Thompson oils 1976). crude density of the higher all present in the general, are In or another of compounds one type oil. Nevertheless, crude sulfur exist any particular in types only preferred The presence of sulfur compounds in nished petroleum products often produces harmful harmful produces often products petroleum nished in compounds of presence sulfur The RSSR′ RSR′ RSH Compounds Types and Nomenclature Sulfur of Organic TABLE S S 3.2 S S S S Naphthobenzothiophene Benzothiophene Thiophene Disul des Cyclic sul des Dibenzothiophene Sul des Thiols (mercaptans) 115 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 processing: of during thiols by oxidation formed the generally but oil are of constituents crude true as not regarded are disul des hand, other the On fractions. higher-boiling petroleum the phene present in derivatives usually are of hydrogen properties by having agas sul de. substantial accompanied often is, however, >1% with oils some crude and oils, constituent of acommon crude many are w/w sulfur Hydrogen reached. are sul de do not yieldcompounds hydrogen temperatures higher until sul de at approximately 150°C rapid is very at220°C(430°F), and (300°F) sulfur bound but organically evolution the with areaction, oil, the is present in of elemental hydrogen sulfur If sul de, begins atrelatively reactions undergo thermal low petroleum in compounds temperatures. sulfur of the but some heavy feedstocks, fortunately various well of the oils as between diverse as origin crude among markedly varies compounds of sulfur types various of the distribution The practice. re nery of part conversion or their important compounds is removal an the less to of deleterious types sulfur and products, most in petroleum content considered harmful is generally sulfur High distillation. aresult of as decomposition fractions higher-molecular-weight of the boiling the during compounds higher- than 2014), (Speight, more sulfur distillation 2000, contain may actually fractions middle the deposition lowerto the of solids. oxidation to increases and resistance seems oils lubricating in compounds content situation for ahigh ofthe sulfur is that oils lubricating 116 found to be approximately constant throughout the entire range of distillate and residual fractions. fractions. residual and of range distillate entire the throughout found approximately constant be to nitrogen of was ratio basic the total to Indeed, crude. of the 30 source to ±0.05) of the irrespective (0 nitrogen ofis approximately ratio constant shown basic the has total to that method tion of this a50:50 acid in applica perchloric - with solution The benzene. acid and titrated acetic be of glacial classi ed basic as or nonbasic, are nitrogen compounds can onthey which whether the depending developed been has Amethod phases. in aqueous and oil the between unfavorable partitioning of because weight unextracted ofmolecular strong bases higher acids; remain equally mineral higher-boilingportions. the largely in concentrated which nitrogen effects of compounds, are the harmful the accentuated has cracking for stocks catalytic obtain to crude the into toward deeper years cutting recent in trend domestic such as fuel formation in oil. products The gum to contribute also they and catalysts, responsible be present.Nitrogen can amounts of compounds for poisoning cracking small the the from expected be might than operations re nery in issigni cance of petroleum muchin greater residue. of presence nitrogen carbon The the residue: higher nitrogen content, the the higher the carbon nitrogen the content the and between followscorrelation also approximate is an there that oil. It of gravity crude API nitrogen contentthe the and between exists acorrelation also there 2014), (Speight, oils of gravity crude API 2000, the content and relation sulfur the exists between cor approximate its an nitrogen as higher content. Insofar the oil, the more asphaltic the general However, but in not uncommon, are nitrogen or noeven with detectable oils amounts crude trace 0.9% w/w, up 2% to may oil nitrogen. contain some crude work early that although indicates residua. and higher-boiling fractions the in occur also types, indole, pyrrole, of carbazole nonbasic the usually and which nitrogen compounds, are residua. The have and ranges, higher-boiling fractions boiling tendency existthe to adecided in (Tablepounds the homologues throughout 3.3), of occur pyridine and mainly composed which are basic nonbasic. as and basic nitrogen com The Nitrogen may classi ed petroleum be arbitrarily in 3.3.2.2 Various oils; derivatives ofbenzothio thiophene crude haveavariety isolated from been also during point boiling the with increases of sulfur proportion the that itAlthough true is generally Basic arelatively with nitrogen compounds low dilute with weight molecular extracted be can 0.1%– range the is lowwithin oil nitrogen content falls the of generally general, crude and In

Nitrogen Compounds R–S–S–R +H 2R–SH +[O] →R–S–S–R 2 Handbook of Petroleum Refining of Petroleum Handbook O - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 indole, types. pyrrole and carbazole, of generally the are and petroleum nitrogenof in the part greater the acids contain cyclopentyl or mineral cyclohexyl dilute with extracted be cannot that compounds group. The derivatives substituents, substituent well which as pyridine the in was as alkyl a tives carrying iso derivatives, derivatives, alkyl quinoline and pyridine consistto alkyl of alkyl were found distillates petroleum from acids Nitrogen mineral dilute extractable with compounds Feedstock Composition Feedstock abzl C Carbazole Pyridine Basic Pyrrole Nonbasic Nomenclature and Types of Organic Nitrogen Compounds TABLE Indoline C Quinoline ez()unln C Benzo(f)quinoline Indole ez()abzl C Benzo(a)carbazole 3.3 C C C C 8 9 5 16 12 8 4 13 H H H H H H H H 9 7 5 7 5 N N N 11 9 N N 9 N N N N N H N N N H H H N N H N N H -quinoline deriva 117 - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Francisco, 1990): (>340°C,(Speight of ashing distillation dioxide temperatures and atthe >645°F) during used for carbon decarboxylationand potential ahydrocarbon to high is the there because constituents monocyclic nature; in atC entirely aliphatic begin acids almost molecule per atoms are carbon phenols.carboxylic and acids weight have investigated been considerably with have more and success shown been contain to but of those lower structure, molecular their oxygenthe concerning is known little petroleum, in gen contents up 8% to w/w. high-molecular-weight these Although most of contain compounds nonvolatile fact, the in residua examined; may fractions have point of the boiling the oxywith production. However, or after eitheratmosphere during oxygen the content ofincreases petroleum oxygen prolonged suffered has oil content itexposure the to the is phenomenally high may that be 2% less w/w, than but is usually oil when the crude have amounts reported, larger although been (Speight, petroleum in 2014). occur oxygen-containing compounds oxygen total The content of more common the that group) so it is not aromatic nature, surprising in is an Ar and groups alkyl Oxygen in organic compounds can occur in a variety of forms (ROH, ArOH, ROR of (ROH, forms ArOH, avariety in occur Oxygen can compounds organic in 3.3.2.3 118 Mg, Ca, Cl) or corrosion products gathered in transportation (Fe). transportation in Mg, Cl) gathered Ca, products or corrosion (Na, salts brine coproduced with except petroleum, in when contaminated metals other than higher of orders magnitude generally Vare Ni and metals trace The cracking. such catalytic as processes nitrogen removal and well as other for poison as they problems used catalysts sulfur because lar - causeparticu and processes upgrading many affect fuel. Metals convert transportation to oil the have concentrations to the reduced and oil, be to found every in crude are constituents Metallic 3.3.2.4 substantiated. may heavyor bitumen oil, yet be to crude need virgin existence in their residua, and the molecular-weight blowing air of of products nonvolatile the be to claimed residua. are They higher- the in most of occur because them identi cation is dif cult compounds ofprecise these >C( anhydrides moiety),matic of presence ketones the (>C aro is an phenolic carboxylic (ArOH,where Ar and acids additioncompounds the to In above C predominate and ArCO are to be made. be to are deductions exercise the renders often somewhat meaningful if futile structure molecular their into oxygen with react can constituents oil crude (aerialoxygen or dissolved)the incorporate to functions possible show, and postulate, to such relationships that exist. However, which with some of ease the gravity, API oxygen the as physical the with it same is not properties the oils. It contents is of crude respectively. derivatives monocyclic one prevail, may dicyclic principally expect nd to and acid derivatives, which monocycloparaf n Similarly,in derivatives ranges the dicycloparaf n in predominate. and to may acids expected be aliphatic the of hydrocarbon, type prevailing the are which paraf ns in range the oil. In crude the in associated which with are they hydrocarbons of those the with It has generally been concluded that the carboxylic acids in petroleum with fewer with petroleum carboxylic concluded eight- in acids the been It generally that has than Carboxylic acid derivatives (RCO such nitrogen contents and and sulfur the between made frequently are comparisons Although 2 H, RCO H,

Metallic Constituents Oxygen Compounds 2 R, ArCO R, ═ O)–O–(O 2 14 R, R R, . This indicates that the structures of the carboxylic acids correspond carboxylic of correspond acids the structures the that indicates . This ═ )C<] has been claimed for a variety of crude oils. However,)C<] of for crude claimed avariety been has the 2 C ═ O as well as the cyclic furan derivatives, cyclic wellO as the R as where Rand furan RCO 2 H) may be less detrimental than other heteroatom other than may less be H) detrimental 2 RH +CO H →RH ═ O), [>C( esters 2 ═ Handbook of Petroleum Refining of Petroleum Handbook O)–OR], ethers (R–O–R), and and O)–OR], (R–O–R), ethers ʹ , RCO , ʹ are are 2 H, H, - - 6 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock 3.3.2.5 nickel. and of iron by amounts up the 95% to reductionsin substantial with solvents. removal n Thus, with asphaltenes of the by asphaltenes hydrocarbon along the with may stocks residual precipitated be in copper and iron, nickel, vanadium, of majority the The overhead the increased. in constituents is also oil of metallic amount the is increased, crude of ofbypercentage a reduced overhead vacuum distillation obtained the fact, as In petroleum. the present in compounds bylates organometallic of volatilization the distil the in may constituents occur metallic ofNevertheless, the is evidence aportion there that to entrainment. may part due be in latter but the higher-boiling distillates, the in appear some can occur. also can arelativelycates of exceeds reverse content, nickel, that which usually the vanadium although high indi copper for oil and nickel, of of analyses iron, of anumber vanadium, crude the Examination copper. nickel, haveand compounds magnesium addition iron, to vanadium, and identi ed in been calcium, titanium, zinc, thus, oil-soluble and in of produced, several metals been other formhas content. ash Evidence the in such for ending present in presence form, question in the are metals the that It surmise to is easy materials. source have to animal plant and present in been certain almost of complexing pigment chlorophyll pyrrole derivedwith from compounds hemoglobin and are and capable oil-soluble present as are are class metals adifferent and in These compounds. be to seem However, emulsionas oils stabilizers. found crude iron ofin the copper, nickel, vanadium, part and act water/oil and the in interfaces adsorbed properties soaps surface-active with of organometallic form the in appear magnesium and calcium, of titanium, Zinc, compounds. well-de ned types with nonvolatile (Altgelt oil the in of crude 1994; portion Boduszynski, and Reynolds, 1998). of order is of oils 0.1–100 the found generally crude only desalted are from ash Metals total mg/L. formof complexes, as colloidal suspensions, the soaps, compounds or in the and metallic metallic formof oil-soluble the present in are organo metals Other reduced. substantially be to crude of the content mineral emulsion, the original thereby causingsubsequent the water or by washing breaking 2016).et al., either by operations, removed evaporation desalting are the water of in and These the emulsions oil calcium) water of and phase (Abdel-Aal the crude magnesium, in potassium, sodium, water-soluble inorganic as of which occur ofconstituents, part sulfates and (mainly chlorides salts deterioration. cause their lower to so fusion and linings points their furnace refractory with reacts vanadium especially and sodium combustion may severe.corrosion very the be of from resulting fuels containing ash The by More particularly, damage balance. their disturbing and clearances reducing thus rotors, turbine fuel, may deposits ash to lead the on the in vanadium constituents, particularly ofpresence metallic the power turbines, gas generators, such yields oil- red as high-temperature reduced of gasoline. In coke formationand and gas increased result in catalyst of activity and the the affect cracking lytic forstocks - cata charging the in nickel vanadium and copper, of particularly iron, and amounts present.Even amounts small minute very the from expected be might than industry petroleum precursors. biological corresponding their geosphere and found the compounds between in alink establish could that biomarkers as concept of investigations,result early porphyrins ofthe these arose there oils.a As some crude in occurs also that material organic consideredthey ametallo-containing nor are of constituents petroleum, nitrogen-containing usual considered the among not usually are 1978; (Bonnett, concentrate Reynolds, nonbasic 1998). nitrogen-containing ofthe the portion They in occur usually and existpetroleum in that species chemical occurring anaturally are Porphyrins Distillation concentrates the metallic constituents in the residues the (Reynolds, in constituents 1998), metallic the concentrates Distillation although associated oil crude Two original the in concentrations signi cant of in groups elements appear metallic of presence these is due oil the to of acrude burning residue ash the left after Thus, is of oil the to considerably interest crude in constituents greater of metallic occurrence The

Porphyrins -pentane reduces the vanadium content oil of vanadium the the reduces -pentane 119 - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 (–CH 120 FIGURE FIGURE rin are hydrogenated, a chlorin or a phlorin is the result. Chlorin derivatives components of are result. Chlorin is the or aphlorin hydrogenated, achlorin are rin system formal of one or two the nomenclature. doublemon When usage than of bonds a porphy more1978). com in often are have that or also acronyms names well-known Porphyrins trivial system one to common of according (Bonnet, nomenclature one types into ofcompound various classi cation the porphyrin of aspeci c determines rings substituents of on the porphyrin nature Most have compounds hydrogenof The these carbons. substituentsthan other ring onof many the 3.8). (Figure chelation system such nickel molecule as included allow metals be to the through into porphine the (–NH–) functions in imine the molecule. Furthermore, porphine the to character aromatic increased conjugated larger components, the pyrrole of system the gives character much inherent of the retains ponent nuclei,structure pyrrole resulting system. amore extended the resonance Although forming Porphyrins are derivatives of porphine that consists of that four molecules derivatives pyrrole by joined methine are of porphine Porphyrins A large number of different porphyrin compounds exist in nature or have synthesized. exist nature compounds been in of porphyrin number A large different ═ ) bridges (Figure 3.7). The methine bridges establish conjugated linkages between the com 3.7). the between ) bridges (Figure conjugated bridges establish linkages methine The 3.8 3.7

Porphine—the basic structure of porphyrins. basic structure Porphine—the Nickel chelate of porphine. of chelate Nickel H H H H CC CC C C H H H H C C CC C C CC HH HH H H N N C C CC CC C C H Ni N N N N H C C C C C C N N H H C C CC CC C C CC CC H H H H Handbook of Petroleum Refining of Petroleum Handbook H H H H - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 chlorophyll iso an possess and Composition Feedstock of the petroleum constituents. Such fractions are primarily identi ed by their respective boiling respective by identi ed boiling their primarily constituents. Such are petroleum of the fractions 1978), (in asense) is still petroleum of astronomical. in number compounds potential the possible Welte, (Tissot the and of number permutations isomeric limit might process maturation the derivatives heteroatom derivatives, aromatic included, such and the as are evencompounds though (Table family 3.4). of paraf n the types other within When occur that numbers carbon individual components possible of whenindividual petroleum the of number isomers is considered for the components. other the than point by given is caused the alower component and This vapor having pressure ahigher boiling mixture. given component given of is possible, the the proportion vaporcomponent a higher has the than if of a Distillation mixture. of the properties by chemical the vapor acomposition has the determined components evaporate the such that mixture, the respective vapor In the pressures. in differences (usually compounds liquids) chemical of separating through is ameans Distillation identi ed. and separated be it by as ofcan constituents is insofar amethod which here petroleum the distillation elsewhere (Chapter more detail in 7), is presented mention to it is appropriate distillation Although 3.4 metals. ofconcentrations nonporphyrin small very usually and materials parent the than of concentrations porphyrins smaller contains oil deasphaltened The fraction. asphaltene the chelates) in metal concentrated are nonporphyrin chelates or complexes metal nonporphyrin (Reynolds as to et al.,referred 1987). chelates are metal These not porphyrins. are that is oils chelated ligands with nickel crude and in Currently, some type. investigators vanadium of the believe for porphyrin part as accounted that be oil acrude in nickel vanadium and measured all can rarely Only chelated porphyrins. with be constituents (Reynolds, 1998). to 10% as little appears as oils, w/w some metals crude In of total for porphyrin as accounted be content can metal the it found notconcentrations, all is usually that 1987;Berkel, 1987). Quirke, (Hodgson et al., 1967; Baker, 1969; Palmer, 1978; and Baker 1986; Louda, and Baker Filby Van and have bitumen sand advanced been tar oils, heavy and oils, crude in nickel vanadium and than other chelated metals with of quantities porphyrins for absenceof reasons substantial the Geochemical bitumen. sand tar and oils of number alarge crude in amounts existto chelates signi cant as in derivatives. porphyrin dium derivatives- vana more nickel than porphyrin contain usually origin of oils lacustrine crude sulfur derivatives. nickel Low- porphyrin than derivatives more abundant are porphyrin vanadium origin, of oil marine crude high-sulfur In is chelated oils porphyrins. with crude these in vanadium of the amount Vanadium of asubstantial concentrations over and for oil, known some ppm crude are 1000 derivatives. nickel and of porphyrin vanadium amounts large Heavycompounds. may oils contain of these amounts only small contain usually oils derivatives. crude lighter More mature, porphyrin unit. pyrrole onto a fused or have ahydrogenated ring compounds ring These benzene either abenzene rials. derivatives geological have in identi ed mate been derivatives also tetrahydrobenzoporphyrin and have and no substituents (othermaterials hydrogen) Benzoporphyrin than carbons. methine on the found geological commonly derivatives in also chlorophylls. derived from be to are Etioporphyrin assumed are feature structural this contain that Geological porphyrins carbon. amethine to carbon However, petroleum can be separated into a variety of fractions on the basis of the boiling points points basis boiling of onHowever, the of the fractions a variety into separated be can petroleum the impossible it purify completely to process, of is theoretically and the By nature separate the and (metalloporphyrins constituents metallic the of fractionation petroleum, the Finally, during porphyrin with compared and measured nickel are oils and contents of vanadium crude the If nickel and table, have only vanadium periodic proven the been in de nitely metals the all Of nickel and of vanadium amounts detectable contain bitumen heavyand oil, crude all Almost CHEMICAL COMPOSITION BY DISTILLATION -cyclic ring formed by two methylene groups bridging a pyrrole-type by-cyclic formed two methylene apyrrole-type ring bridging groups 121 - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 122 FIGURE 3.11). system (Figure aromatic derivatives polynuclear the of than kata-condensed rather constituents asphaltene and constituents homologues 3.10) (Figure peri-condensed higher the that resin present in anticipated be be to will it is there derivatives and are systems of petroleum phenanthrene in of aromatic condensed types (Speight, paths) 1994, irrational and maturation 2014). and precursors For example, predominant the of (considering the nature lower-boilingidenti able the the in constituents is unnecessary fractions nonvolatile the those in constituents from different fractions existence ofInvoking the structurally 3.9). achieved be design (Figure higher-boilingcan constituents ofphenomena molecular the that of recognition such the It point. is through boiling in increase the caused substituentsof that the it number and closely is the remains constituents of the similar nature the increase, ranges boiling alesser to extent, composition. and, byranges chemical However, it obvious is often the as that 3.9 Separation of petroleum constituents by distillation. constituents of petroleum Separation 40 30 25 20 15 10 Carbon Atoms Number of Number Each Carbon with Associated of Possible Isomers Number the and PointBoiling n of the TABLE 5 Boiling point (°C) 1000 250 500 750 3.4 0 0 “Vacuum” distillation n-Isomer Boiling Point 550 25 Distillation Empirical methods 525 450 402 344 271 174 36 Cumulative (wt%) -Isomers of the Various of the Paraffins -Isomers Atmospheric distillation

(°C) Arbitrary FBP n-Isomer (°F) Boiling Point 7 62,491,178,805,831 977 841 755 651 519 345 97 5100 75 Handbook of Petroleum Refining of Petroleum Handbook Number of Isomers 4,111,846,763 36,797,588

Positive Molecular design 366,319 identification of constituents 4,347 75 3 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 propane, butane, iso butane, propane, of component ethane, lesser hydrocarbon with ofgases amounts petroleum main is the Methane 3.4.1 FIGURE FIGURE fraction. While naphtha covers the boiling range of range covers most naphtha gasoline, raw of naphtha boiling the petroleum the While fraction. dioxide, hydrogen present. also carbonyl sul de, sul de, are and Feedstock Composition Feedstock Saturated constituents with lesser amounts of mono- and diaromatics dominate the naphtha naphtha the dominate diaromatics of and mono- lesser with constituents amounts Saturated g 3.11 3.10 aSeS

Examples of kata-condensed (cata-condensed) aromatic systems. aromatic (cata-condensed) of kata-condensed Examples Examples of peri-condensed aromatic systems. aromatic of peri-condensed Examples

and n -butane, and some C and -butane, a PH tHa 1,2,5,6-Dibenzanthracene Pi Chrysene cene Pyr ene 4 + hydrocarbons. Other gases, such gases, hydrogen, as Other hydrocarbons. carbon Ov alene Co ronene 123 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 percent. The iso The percent. several reaching oil acrude in compound most may abundant the be low-boilingof these paraf ns ols have been identi ed, including all the isomeric C isomeric ols the have including identi ed, all been derivatives formof mercaptan the (thiol may in be derivatives). sulfur of the thi Over individual 40 (sour) high-sulfur 50%–70% from naphtha petroleum, oil. In crude the in 1%than sulfur total of the 1964; et al.,(Mair, Rall for 1972). accounts less fraction this in Usually,sulfur of the amount total the fraction. mid-distillate the in appear homologues aromatics higher two ring of fused 1- the while 2-methyl and fraction, derivatives naphthalene Naphthalene is included this and in have methyl of isolated along anumber derivatives. with their been tetralin and such indane as neighboring neighboring relative phytane and their to of pristane genesis distribution the to biomarkers, The of petroleum. have of ancient derivatives,prene precursors, relevance fragments as simple believed as arise to are not. are mon, but bicyclic by derivatives naphthene asingle such bond, cyclohexyl as separated cyclohexane, com also are hexahydro-indane and (trans-decalin) (cis-decalin) trans-decahydronaphthalene and Welte,(Tissot and 1978). dicycloalkane derivatives ring Fused such cis-decahydronaphthalene as may present be structures, found unsubstituted levels commonly athigher parent which the are than ve- Methyl rings. or six-carbon derivatives predominantly with of cyclopentane cyclohexane, and analysis.multiple isomers during with dealing in dif culty of may increased isomers grows number, be there rapidly and carbon with methane (CHmethane gasoline. additives and commercial naphtha formulate to process other with molecules have lownumber. However, octane combined and mostfurther raw is processed naphtha 124 C streams. re nery hydroprocessed and cracked from obtained be also which can raw distillate, derived from middle all Kerosene, diesel jet fuel are fuel, and total. of the portion representalarger present and are heterocyclic and compounds rings, which now aromatic include simple up with three to compounds ofbut aromatics, petroleum fraction major mid-distillate the component the in are species Saturated 3.4.2 C isomeric 20 the logues through Welte, present derivatives (Tissot and also are alkylated 1978). homo benzene alkyl of Each the be seen as irregular peaks alongside n the peaks irregular as seen be 2,6,10,14-tetramethylhexadecane) suf cient to in concentration oils crude present in generally are Kayanov, 1980; Skorova, and Freidlina 1980). possible their formationby oxidative coupling of (Aksenova thiols minimized and that analyses in et al., 1972).(Rall oils some presentcrude in be to Methyl ethyl have and disul des con rmed been derivatives have derivatives naphtha in multiple or exist naphthene–thiophene side as short chains cycloalkane content ahigh have to with tend oils content. thiacyclane Typical ahigh thiophene alkyl follow to tends is, naphthenic distribution hydrocarbons; that distribution the structure sulfur The (alkyl sul des) linear ve- formof and both the may or six-ring in be cyclic (thiacyclane) structures. (thioether sul des derivatives) between uted sul des derivatives. the thiophene cases, and these In et al.,plus 1972). thiophenol (Rall low-sulfur from (sweet) naphtha is distrib In sulfur the oil, crude various C various 11 Sulfur-containing compounds are the only heteroatom compounds to be found in this fraction fraction found this be to only heteroatom compounds in the are compounds Sulfur-containing The numerous aromatic constituents in petroleum naphtha begin with benzene, but its benzene, C with begin naphtha petroleum in constituents aromatic numerous The consist constituents of cycloalkanes (naphthenes) molecules, saturated the addition aliphatic to In Within the saturated constituents in petroleum gases and naphtha, every possible paraf n from from every possible naphtha, and gases petroleum paraf n in constituents saturated the Within Within the saturated constituents, the concentration of concentration n constituents, the saturated the Within to C m 20 5 . Two = 2,6,10,14-tetramethylpentadecane isoprenoid (pristane species = phytane and derivatives. derivatives (naphthene Benzene cycloparaf nrings having aromatics) fused iddle n 4 -C ) to n ) to -paraf ns begin atC begin -paraf ns 17 d and n and -decane (normal decane, n (normaldecane, -decane iS tillate -C 18 peaks has been used to aid the identi cation of crude oils and to detect to detect and oils identi cation the of to aid crude used been has peaks S 4 alkyl benzenes has been isolated from crude oil along oil with crude isolated from been has benzenes alkyl 4 with iso with -C 17 and n and -C -butane as the only isomer of the as n -butane 10 H 1 22 to C to -C ) is present. Depending upon the source, one source, upon the ) is present.Depending 18 peaks in a gas chromatogram. These iso These chromatogram. agas in peaks 6 compounds plus compounds some C -paraf ns decreases regularly from from regularly decreases -paraf ns Handbook of Petroleum Refining of Petroleum Handbook -butane. The number number The -butane. 7 and C and 8 isomers 1 –C - - - - - 3 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock anthrene, chrysene, and picene, well and as pyrene, uoranthene, benzo(a)pyrene, as chrysene, anthrene, benzo(ghi) and derivatives show one long multiple and side side short chains. chain of naphthalene steroids. and presentmatization atlower Although benzenes alkyl concentration, aro the from originate is consistentsuggestion species the with these This that compounds. matic on some aro rings show naphthenic of presence up data four to the fused samples.oil Analytical vacuum for gas petroleum account in approximately 50% aromatics of diaromatics the Mono- and range. boiling their with substituents keeping in alkyl and rings naphthene additional may bear et al., 1994). (Prince tion processes bioremedia- during oils of biodegradation crude the for estimating markers internal as used also are involves several methyl ethyl have and identi ed substituents. steranes been and Hopanes also substitution typically alkyl the substitution. by diaromatics, For alkyl and mono- accompanied rings fused six one more to than from contain show naphthenes the techniques that Analytical detected. from <20% to >80%. to <20% most n from samples, In the overallis constituents, but of range the variation saturate of 60% the for approximately two-thirds Generally, source. account constituents naphthene petroleum dependent the upon the highly are or extraction yield to naphtha produce to oil. lubricating cracking Vacuum but oil, by mostit aheating catalytic commonly is as processed used is occasionally oil gas levels. trace now than rather are present atpercentage that constituents polar the ents but more than compounds. quinoline alkylated and pyridine alkylated basic is found the in remainder the nitrogen, while of the foraccount approximately two-thirds belowtions boiling 343°C 1974). et al., (650°F) (Hirsch derivatives indole and derivatives Pyrrole - basic have and nitrogenfrac compounds identi ed in isolatedneutral and been both fractions, crude. the in sulfur total of the fraction forcies account aminimal spe Skorova, sulfur these fractions, 1980). naphtha the with present.As also are Alkylthiophenes derivatives sul de (Aksenova Kayanov, aryl–alkyl and and of diaryl, dialkyl-, 1980; and Freidlina clane derivatives, derivatives derivatives, dibenzothiophene lesser benzothiophene with amounts and of(Speight, petroleum higher-boiling fractions 1994). Welte, (Tissot and the structure 1978), continuethrough to of anthracene that appears this and favored be to over appears structure derivatives.derivatives phenanthrene phenanthrene The and some uorene contains derivatives, naphthalene and mid-distillate the tetralin, of alkylbenzenes, as either naphthene or alkyl homologues C either the or alkyl naphthene as in quantities small present in undoubtedly are aromatics derivatives. two one ring thalene and Other et al., 1981).Lee 1979; (Hunt, oil found crude been in has adamantane by and chromatography gas detected been wellas have onenaphthenes or more methyl as or ethyl Similarly, groups. three-ring substituted Welte, (Tissot and increases 1978), may naphthenes have alkylated asingle the long and side chain number carbon the as concentration in range, decreasing boiling distillate middle the in naphthenes 1979). (Hunt, leum were which petro ancientconverted into in organisms oxidation reductionof environment the and for assessment used the been also has phytane to of ratio onset pristane of The the biodegradation. thene species, although isoprenoid compounds, such as squalane (C isoprenoid although species, such squalane thene compounds, as analysis. chromatographic gas in peaks distinct as detected be to quantity The fused ring aromatic compounds (having three or more rings) include petroleum in phen- three (having compounds aromatic ring fused The that rings aromatic onefused six to vacuum may oil in gas constituents contain aromatic The Within the vacuum gas oil, saturates, distribution of paraf ns, iso of paraf ns, distribution vacuum saturates, oil, gas the Within constitu vacuum less (VGO) oil gas aromatic the to contribute constituents the than saturate The (usually amounts ppm levels) only trace Although distillate middle found the of in nitrogen are thiacy the primarily are range ve-memberedThe heterocyclic mid-distillate the in constituents The most abundant aromatics in the mid-distillate boiling fractions are di- and tri-methyl naph- and di- are fractions boiling mid-distillate the in aromatics most abundant The of the bulk the derivatives dicycloparaf n constitute Mono- and ring ve with per carbons or six The bulk of the saturated constituents in VGO constituents in consists of iso saturated of the bulk The -paraf ns from C from -paraf ns 11 –C 20 range. In addition to these homologues addition these to range. In 20 to C to 30 -paraf ns and especially naph- especially and -paraf ns ) and lycopane) and (C 44 are still present in suf cient present in still are -paraf ns, and naphthenes naphthenes and -paraf ns, 40 ), have been 125 ------Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 compositional detail based on average parameters is of on average questionable based compositional value. parameters detail weight is so complex molecular highest fraction components, most asphaltene but polar and the that however, does, constituents asphaltene of the separation provide asimple way remove to some of the However, by solubility isadsorption. aseparation Kit and type. bynot chemical aseparation the However, classes foradsorption characterization. is method the contrary, spite the to in of claims several into solubility or chromatographically fractionated then residuum ofconstituents the are much 50% as by weight (maltene) or heptane-soluble portion of avacuum pentane- residuum. The may as asphaltenes, be tion or heptane of vacuum insoluble residuum. pentane The the fraction, molecules. single in well of as presence of species multiple as the naphthenic substitution and functionalities of aromatic multi of the because confused and dif cult of becomes vacuumSeparation residua by type group made. be have impossible, whator will claims made no matter been is virtually species individual but of subject dependence). method to mined is so complex characterization fraction the The that weight molecular deter be and (as up range constituents several to ofcan as the thousand near petroleum composition. the in Vacuum originally heteroatoms of majority the the residua contain may cases, even many in in bitumen sand leum and, resemble or orheavytar heavyextra oil oil acids (Seifertacids Teeter, and 1970). identi ed oxygen phenols, carboxylic acids and the collectively are naphthenic compounds called structures. rocks on any intervening not adsorbed are and reservoir moved the to more readily structures (hindered) less which polar the in geochromatography as ized rational been has have This rocks. found present source atequivalent be been to in concentrations structures unhindered and hindered structures, hindered sterically in rich are found petroleum in derivatives(amide derivatives derivatives). carbazole and dibenzo-quinoline and benzo- Although species neutral is present as derivatives, remainder its benzo and the while basic, is, pyridine that are prevalent 1989). especially (Green et al., are Typically, compounds of the approximately one-third that rings molecules twoand with four nitrogen (diaza aromatic atoms and compounds) three with derivatives, derivatives,derivatives, amide indole benzoquinoline derivatives, derivative, carbazole include compounds higher-molecular-weightnitrogen-containing derivatives, pyridine quinoline vacuum range, oil gas the the phene prevalent derivatives In of the forms sulfur. thiophene are derivatives dibenzothio benzothiophene and atom. The one sulfur even moreecules than contain over Some mol sulfur. sul de predominate sulfur thiacyclane and thiophene compounds, sulfur 100:1. derivatives favored chrysene addition, are In over pyrene derivative. derivatives derivatives by muchderivatives. as anthracene as outnumber phenanthrene addition, In three the be to appear compounds phenanthrene individual reported mostperylene. abundant The 126 The vacuum residuumThe ( 3.4.3 sively and several families of related structures have been identi ed. On the other hand, the the hand, other have the sively On identi ed. been of structures related several and families have they exten processes, studied been provide maturation can petroleum insights into rins two forms: (1) (2) and (Reynolds, 1998). nonporphyrins porphyrins metalloporphy the Because (carbazole-type) basic nitrogen, and (quinoline-type) nitrogen. found lower-boiling in functionalities ofpresence the such acids, phenols, as fractions nonbasic the con rm to used are techniques identi cation characterization isand somewhat fruitless tural - struc point, one At heteroatom. this extent more than every the to molecule that fractions contains elements most polar These the of consistently concentration in sulfur. approachto the concentrate For the 565°CFor the Classically, Oxygen most commonly nitrogen the content. levels Thus, the vacuum parallel oil gas the in of terms In vacuum fraction. oil gas the to contributors Heterocyclic signi cant are constituents The nickel and vanadium that are concentrated into the vacuum residuum appear to occur in in occur to vacuum residuum the into appear concentrated are that nickel vanadium The and v aC uum n -pentane or n or -pentane + r (l050°F eS idua vacuum bottoms + ) fractions of petroleum, the levels the of petroleum, ) fractions of oxygen nitrogen and may begin - for step characteriza the initial the as precipitation is used -heptane , typically 950°F , typically + or 1050°F or Handbook of Petroleum Refining of Petroleum Handbook + ) is the most complex) is the of petro ------Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock 3.5 (at questionable) best determine to attempting residuum rather structures. molecular ways the of utilizing determine to it may better task, be insurmountable seemingly ofBecause this low. very aresiduum in are every structure possible, ofcombinations are determining chances the complex incredibly an molecule. how Considering making ferent different many functionalities, 1993). Green, and (Pearson environment (porphyrin-type) existatetra-pyrrole in still compounds these in metals not clearly suggest some studies although identi ed some remain of that the metals nonporphyrin tionation study. This is due, in the main part, to the complexity to the of not the only from petroleum part, tionation study. main is due, the in This - any frac in step rst is the offractionation petroleum requirements the may all satisfy method no one particular Recognition that methods. own particular to,promote, their and rmly adhere However, fractionation. of to petroleum methods inclined are standard laboratories various the haveto devise there attempts feedstocks, many of been re nery nature the in wide variations are employed. be to there although procedures Thus, separation other the with its compatibility and process by effectiveness but oil composition also the and/or crude of of the nature aparticular constituents.of the involve caution that when isusing advised methods Indeed, separation chemical data. resulting the may have unprovoked result in that reactions adverse and fractionation chemical effect an on the but is often notfractionation always oil. This complex of of the crude because successful nature classes of various acidadduct formation. or the Chemical of ole ns interaction sulfuric with the as such reactions, on speci c depend procedures Chemical by materials. surface-active adsorption as solvent and well as of those distillation treatment, are industry petroleum the in used fractionation of physical processes constituents. For various example, the among standard the differentiate to involving physical techniques and those use of chemical the properties especially techniques, grated of several inte utilization involves the but also technique application not only the of one particular type. molecular and size molecular to according constituents segregate the that is employ to procedure general techniques the Thus, state. pure asubstantially in constituents these obtaining and structure molecular without constituents of alteration petroleum their the separating (Speight, 2014, of mixtures of hydrocarbon separation degree 2015). However, problems the are molecule futility some (perhaps questions advisability of the (Speight, other each with 1994; existbalance in that Speight, and 1998). Long mustbe also There includes that awide ofweights compounds range types molecular organic of molecular various and petroleum name the that recognized molecule of every quanti cation have developed techniques been for identi cation analytical of various the and matter.aresult, As compositions as its fractions and amultiplicity to stock led petroleum establish to has of attempts behavior composition the to is related - feed re nery of the Recognition products. that potential and sequences re ning to investigations applyto conceptinterlaboratory of thence predictability the and 3.13). (Figure aromatics and tions: saturates, resins, asphaltenes, it Thus, is possible compare to (on de ned be can arelativeFeedstocks (such processes constituents. other considerable the in whereas in cracking) as changes occur isolated unchanged, feedstock for ofare constituents processes, the the example,the distillation, 3.12) (Figure processes unit some ofcal In generated. of are aresult of products as which avariety involves petroleum Re ning physical chemi of and feedstockintegrated aseries to subjecting the It is more than likely that, in a speci c residuum molecule, the heteroatoms are arranged in dif in arranged residuum aspeci c molecule, are heteroatoms in the likely that, It is more than The order in which the several fractionation methods are used is determined not only by the is determined used are several methods which the fractionation in order The however, It true, is more generally procedure fractionation successof any attempted the that allow areasonably effective available industry petroleum methods the to fractionation The

FRACTIONAL COMPOSITION FRACTIONAL in petroleum. The true focus used. be molecules should what to be endscan these true The petroleum. in in the lower-boiling the in It of is now petroleum. fractions generally does not describe a composition of matter but rather a mixture acomposition amixture but not rather does describe of matter or standard or every every word) describe to is abetter of attempting - orfrac four general basis) of three terms in 127 - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 128 can be isolated and studied. However, studied. isolated and be can nonvolatile the from constitute residuum, which may actually excellent is an Fractionation by ofby volatile which petroleum distillation means the constituents 3.5.1 oxygen, species. sulfur) and heteroatom (nitrogen, of the distribution the from but species also hydrocarbon of the distribution FIGURE Crude S oil 3.12 880/1050°F olvent

Separation Deasphalter Representation of are nery. Representation extraction Vacuum Solvent plant Atm. m pipe Gas pipe still still 320°F 1050°F 650°F et Soluble H 580/650°F 450/580°F odS – + 650/880°F + 320/450°F Insoluble Hydrocracker Hydrocracker Conversion Cat cracker Cat cracker Visbreaker C Coker 4 ’s Hydrotreater Hydrofiner Hydrofiner Hydrofiner Alkylation Reformer Finishing Handbook of Petroleum Refining of Petroleum Handbook Gasoline mid-distillate Kerosene, kerosene Gasoline, diesel oil kerosene, Gasoline, Light ends feedstock petrochemical Kerosene Hydrogen kerosene Naphtha, Fuel oil Fuel oil Heating oil kerosene Naphtha, Aromatic oil Asphalt Coke fuel gas, LPG, grease wax, Lube oil, Products Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 the mixture to such an extent that the ratio of the concentrations of the various components in the the components in various of concentrations of the ratio extent such the to the an that mixture the coef cients components of for may various distribution differ fact, the the components. In other only slightly, of concentration may the vary the and with coef cient constant is atall, usually if Feedstock Composition Feedstock FIGURE decomposition, and as a result, alternative methods of have fractionation methods alternative developed. aresult, decomposition, as been and possibility of without thermal the by distillation 1% fractionated be cannot petroleum, of 60% to the where C K: coef cient distribution over two dissolved phases; the (the the portion extract) nondissolved the (the and portion raf nate). constituents petroleum of the distribution causes formationof two the which This phases. in results residua. offractionation the followed distillation is, rst, petroleum by for virgin procedure recommended hence, the apparent; possibility of losses the last case lower-boiling of butthe the in petroleum, is constituents virgin to higher-molecular-weight vacuum residua. and ofsuch atmospheric petroleum as fractions the to applied is usually process operative. be deasphalting also The might by polarity separation for by extension weight, molecular an separation some is essentially although procedure ofand the 3.14)is solvent (Figure unit adeasphalting precipitation. in Solvent are nery in precipitation occurs re nery well the as in as laboratory weight. the in major weight used molecular The process separation asolventusually phase. oil an and phase however, are, a liquidphase. These physical involve that processes of use two the liquidphases, weight) involves volatility and of of their avapor and phase participation by constituents the virtue The distillation process separates light separates process distillation The The ratio of the concentration of any particular component in the two phases is known as the the as two is known phases component the in of concentration of ratio any particular the The simplestThe application of liquid, solvent another with petroleum extraction consists of mixing even and bitumen, residua, asphalt, cracked to applied be also can techniques fractionation These Solvent basis of on the molecular fractionation have to petroleum applied methods been also Carbon disulfide (insolubles) 3.13 1 or pyridine Carboids and C and

Separation scheme for various feedstocks. for scheme various Separation 2 are the concentrations of the components in the various phases. The distribution distribution The phases. various the components of in concentrations the the are Insolubles (solubles) Carbenes Insolubles Benzene or toluene Asphaltenes (lower-molecular-weight) heavy and K Feedstock = (polars) Resins C C n-Heptane 2 1 3. Benzene methanol Deasphaltened Aromatics oil toluene 2. Benzeneor alumina Silica or (higher-molecular- Saturates 1. Heptane 129 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 and the like, as well as the optimal temperature for the extraction process. Thus, aromatics can be be can aromatics for Thus, extraction process. the temperature optimal well as the as like, the and should relatively be material extracted easy. the from ow (3) allow two to of and easier phases, countercurrent the solvent of separated the be separation (2)stantial, solvent (product) petroleum the the to less than should or denser signi cantly dense be (1) solventria: the solubility in constituents petroleum the of in the should sub differences be the However, consider to following the it crite is necessary before is attempted, any extraction process (Table types selection alarge 3.5). of functional different ofcontains tion fractionation petroleum tercurrent extraction 130 ried out by the movement of the liquids countercurrently through the extraction equipment ( the out by movementried the through countercurrently liquids of the car normally are Such treatments repetitious required. are several treatment and of repetitions the However,fractions. solvent the with one treatment achieved complete, is rarely separation after the higher-molecular-weight homologues (the heavy fraction) by solvent extraction procedures. molecular-weight of(the hydrocarbons a series their light fraction) from may well separated be size. Lower- molecular to according is a separation there series any particular within although solvents. various cies type, to in according solvent Thus, fractions petroleum extraction separates procedures. basis for is the solvent this petroleum; extraction original the solvent in that from differs phase FIGURE It may also be advantageous to consider other properties, such viscosity, as It advantageousconsider to properties, tension, be may other also surface have of that list suggested compounds selective as The been solvents for preferential- extrac the In general, it general, is advisable selectiveIn that employed extraction be range boiling fairly narrow with size, which not is responsible molecular type, It molecular for is generally solubility the of spe 3.14

Placement of a deasphalting unit in the re nery (see also Figure 3.12). (see Figure also re nery the in unit of adeasphalting Placement Cr ), which affords better yields), extractable ofmaterials. better which the affords Atmospheric ude pipe still pipe atmospheric 5° + 650°F re Dea sid sphalt oil ed Dea naphth Kero Atmospheric naphth He Ligh As sphalter gas oi phalt av sene t y Va a a 1050+° cuum resid l Va pipe still cuum F Handbook of Petroleum Refining of Petroleum Handbook Va distillat gas oi Lu cuum Ligh be C l t paraffi 3 e –C 5 n coun - - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 liquid, which can be related to molecular properties (Hildebrand et al., 1970). et al., solvent (Hildebrand The properties molecular to related power be whichliquid, can employed only approximately 1% insoluble. media, precipitating as remains w/w material of the solvent.nonaromatic For example, when cyclopentane, cyclohexane, methyl derivatives or their are any other have from those to effect yield on aremarkable asphaltene give unrelated and totally results Speight, 1973). and (Mitchell paraf ns derivatives Cycloparaf n normal ing (naphthene derivatives) - correspond do ofthe as amount asphaltenes ole ns same do not the precipitate or terminal paraf ns for conventional branched-chain oils, indeed, and, bitumen crude of aWestern ease the Canadian quantitatively 3.13). reproducible (Figure “ called be should correctly which fraction, this and mixture, the from most complex components the with chemical structures (Yan occasionally hexane is used although et al., 1997). of the is aseparation It is no there doubt that or well by addition of volumes 40 the particularly of precipitated n value are of that compounds molecular-weight derivatives. hydrocarbon weight more complex, molecular the The higher the have to which wereselective recognized solvency simply for and relatively hydrocarbons, low- convenientlyfraction—is brought about byof use low-molecular-weight the hydrocarbons, paraf n effectively be by also tions solvent can separated treatment. - frac boiling narrow may existvarious that in rings of numbers aromatic differing with aromatics by ofuse hydrocarbons selective the solvents. paraf nic and naphthene from Furthermore, separated Feedstock Composition Feedstock To consider to solvent the it was differences, explain necessary those power precipitating of the yield. asphaltene Variation solvent changes in For causessigni cant the example, in also in type two (2) into oil fractions—(1) and of fraction crude asphaltene separation the maltene The the n- heptane in the methods generally preferred at present (Speight et al., 1984; atpresent (Speight preferred generally Speight, 1994) methods et al., the in heptane n -pentane asphaltenes” or “ or asphaltenes” -pentane Note: Nitriles Nitrocompounds Amides Amines Ketones A Aldeh Alcohols Esters of Petroleum Extraction Selective Types for the Compound Used TABLE cids ydes matic they mayornotbethesame. and ifbotharealkyl orbotharearo- R and R′are alkyl aromatic radicals, 3.5 R R R R R R R CR C C C O C NH OHR NO CN 2 2 O O O OH O H OR΄ NH n R΄ -heptane asphaltenes,”-heptane is qualitatively and 2 -pentane -pentane 131 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 volumemolar (V): feedstock feedstock solvent addition of it from the was not possible data instance, whole latter the to the obtain to In of (Speight,point solvents of a variety with this asphaltenes 1979). or treatment of illustrates ethers of precipitate. For quantity example, effects of on the aresiduumni cant avariety treatment with function) molecule (heteroatom the solvent group of ofinto the introduction apolar The sig has

pressure of the solvent, that is, the ratio between the surface tension ( solvent, of surface the pressure the between ratio is, the that of ( solvents nonpolar expressedasolubility as parameter been has 132 where Also use of both n use of both The of countries. different organizations now subject preferences the to standard it of the remains even and was not standardized, of separation asphaltenes method the Foris essential. years, many (or solubility) δis quite regular. asphaltene solubility the parameter and for of any one solvents,series parameter; of bility amount precipitate relationship the the between Moreover,tane. solvent the power solvents of derivation various solu the of with the agreement is in cyclopen in complete solubility near materials of the the and pentane insolubility of in asphaltenes solubility,asphaltene solubility the to parameter. related be can of or precipitate, amount the hydrocarbons, the with as Itfeedstock. is that, nevertheless interesting tion Δ tion Alternatively,- of solvents nonpolar or vaporiza energy solubility the to related the be parameter can used are not unanimous in the ratio of feedstock. liquidto ratio hydrocarbon the in not unanimous are used have that methods been several the standard although methods, standard in of liquids hydrocarbon solvent the preference Hence, feedstock. must the the for with most not use react important, the and, suf ciently complete low that point removal effected boiling solvent of be the can fraction the from for preferable It solvents consistent is also separation. the asphaltene that required of amounts to be volumes large that of solventognized effect to areproduciblesimilar separation, may required be it- And must rec liquidof rule. be ahard-and-fast is choice, by deasphalting no means the ing this T is the absoluteT is the temperature constant gas R is the Δ In any method used to isolate asphaltenes as a separate fraction, standardization of the technique technique of the standardization fraction, aseparate isolate to as asphaltenes used any method In for example, anomalies, apparent the allows explanation an of solubility certain parameter The H R v is the heat of heat vaporization is the v and the molar volume: molar the and per se per -pentane and n and -pentane since the majority of the nonhydrocarbon materials were not miscible the with materials nonhydrocarbon of majority the the since ASTM D893(2015) Method ASTM D2007(2015) ASTM D4124(2015) ASTM D3279(2015) -heptane has been widely although been has and advocated, -heptane d 2 d =- eshligLqi Volume (mL/g) Deasphalting Liquid 2 è ç æ δ = D 1 è ç æ = H n-Heptane n-Heptane n-Pentane n-Pentane D v 3 V E √ v RT V ø ÷ ö V 12 / v ö ø ÷ 12 / Handbook of Petroleum Refining of Petroleum Handbook 100 100 δ 10 10 ) and equated to the internal internal the to equated ) and γ ) and the cubic the of root ) and the n -heptane is becom -heptane - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock be determined, equivalent to the resins isolated by adsorption techniques (Speight, techniques isolated by 2014, equivalent resins adsorption the to determined, be 2015). soluble, and can as asphaltenes brown, near amorphous as near-black, which resins, are, semisolid yields insoluble then the solids. pentane with Treatment precipitate amorphous propane of the brown, usually which asphaltenes, are pentane-precipitated the to contrast in material, semisolid much as 50% as byprecipitate weight is ablack, precipitate residuum tacky, of the orThe bitumen. solvent. hydrocarbon of the variation For example, butane, and lique ed such gases, propane as mass. their penetrate to for hydrocarbon the time need also stocks Heavier process. of the - feed nature diffusion-controlled well size of as the a lterable as particles agglomerate to into particles for asphaltene the required time the to which may ascribed 8 hours, be (Speight separation tene et al., 1984). approximately after Yields amaximum reach asphaltenes of the Speight, 1973). and (Mitchell temperature composition the excess, of change and increasing precipitate ofwith precipitate quantity the the lower-molecular-weight the and when addition, pentane In solvents large hydrocarbon in used are of solvent is <35% proportion precipitated. when the tions that mix are or no asphaltenes the little in (Speight 1984).solvent- indica et al., amaximum reaches are then feedstock to fact, and there In range. acertain of (asphaltenes) precipitate amount within accordingly varied be can extent suchto oil of the physical an the that the alter hydrocarbon characteristics of the proportions solvent–heavy resulting the allowing of blend oil solubility. bitumen degree control to the Varying show also effects of blending the data asolvent The itself bitumen and temperature. with the with tive Speight, on amole-fraction 1973) and basis (Mitchell of solubility variation explain the also and n- and benzene case ofphysical twosolvent different this in characteristics types, 1978; Speight et al., 1984; Speight, 2014, 2015). (Corbett Petrossi, ratio and paraf n-to-feedstock the and temperature, the paraf n, of size the the on depends mixture out paraf n/residuum of settles of the that asphalt amount solidto The asphalt. solvents of the both) are of (tacky) productis asemisolid choice or mixtures the liquid butane, and low-molecular-weight re nery, the supercritical In materials. (e.g., hydrocarbons liquidpropane, (Speight, used be can 1979) brown-to-black of as asphaltenes powdery separation causethe and necessary. adjustments and are heavy oil than other However, were some developed methods of that these for it feedstocks must with use recognized be thene derivatives).thene naphthene single-ring derivatives The adsorbent. irreversibly on the be or clay adsorbed may actually and remove earth the from to dif cult usually are they as removal insofar prior is essential asphaltenes ous of section.The the completely be rst asphaltenes removed, previ for the in example, outlined by methods any of the comparatively bed move the rapidly. through moving the (solvent) in than rather bent surface slightly adsorbed but phase, are components that adsor spend considerable on the strongly adsorbed time molecules are those component. that Thus, of the held nature components (adsorbed) orchemical lesser are extent on the agreater to depending of by asuitable means bed solvent. various the the sample bed, movesthrough the the As through ow to induced chromatography); and bed atone end adsorbent ofumn the sample is introduced the (col tube open an in contained is usually adsorbent of The nely adsorbent. bed solid, divided the of a porous preparation the with commences essentially chromatography by adsorption Separation 3.5.2 After removal of the asphaltene fraction, further fractionation of petroleum is also possible of is also fractionation petroleum by further removal fraction, asphaltene of the After role asphal in plays feedstock also the important and an hydrocarbon the between time Contact of ratio increasing the with increases of rst precipitate quantity the temperature, At constant solvents the it one of rarely compound, that note very to was interest also industrial are as Insofar Although By saturate the de nition, fraction the petroleum, the to technique before application adsorption of the that, It the is essential a dSor n -pentane and n and -pentane P tion m et H odS -heptane are the solvents the are of laboratory,-heptane choice solvents the other in consists of paraf ns and cycloparaf n derivatives and (naph consists of paraf ns - cycloparaf n derivatives , or cycloparaf n pentane, are addi are pentane, , present in , present in 133 - - - - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 lene) triaromatics to monoaromatics molecules. higher-molecular-weight complex However, six-membered with predominating. rings rings the present in still ve-membered are rings more condensed contains fraction naphthene weight the molecular the increases, naphthenes of the methyl, substituents. with As ethyl, quite short, isopropyl usually and predominant are the groups cyclopentane cyclohexane alkyl-substituted groups and alkyl The rings. primarily are petroleum 134 in toto consisting in (i.e., side chains ring atoms)aromatic aromatic six-carbon carrying weight molecular as is increased. ring matic aro the to attached naphthene of have ring condensed amounts will increasing type aromatic each penta-aromatics it is reproducible not only in any one laboratory but also between various laboratories. it various between but is reproducible also any one not laboratory only in that and accurately is it described method sition even makes the fractions that of more the essential by solvent produced fractions from techniques. different be separation also will content in and differ will However, byof use adsorbents different the produced fractions the that it must recognized be iso ole ns, aromatics), aromatics), and naphthenes, and naphthenes, PNA PINA (paraf ns, (paraf ns, ole ns, aromatics), and naphthenes, names: iso PONA PIONAthe (paraf ns, (paraf ns, for by identi ed acronyms However, analysis ofis often the petroleum group-type terms, general in real. very compositional of evaluation the are disadvantages the terms of feedstocks different toto in intention recover to productfractions the various reasons, the (Abdel-Aal 2016). et al., advantages when may consequence of it be These little isfor not, various may even and differently react cause irreversible emulsion changes and/or chemical formation acid should caution advocated with only be feedstocks since sulfuric like reactant of achemical may even physical use and instances, constituents. feed of cause The chemical modi cation the tain cer in and, feed same the with differs performance adsorbent that are adsorbents using ill-de ned in disadvantages bitumen) The constituent sand into fractions. feedstocks or polar tar oil, (heavy knowledge compositional to (Speight, studies meaningful 2014, 2015). further added has method when the especially noted, also are methods Other leum fractionation. of petro methods ents (SAPA) standard the representing as used are two methods These method. constitu constituents–asphaltene saturates–aromatics–polar the called also is often method latter (SARA) constituents This constituents–asphaltene method. (2)and saturates–aromatics–resin the (1) (USBM-API) Petroleum Institute method by U.S. method the the of Bureau Mines—American only, with ibility say, recoverable 85% of success. is not material ofacriterion the - reproduc not reproducible only be method but the quantitative that recoveries guaranteed; and be caution with used be procedure the that necessary very It is adsorbent. to also adsorbent from varies employed of productfractions be of ratio adsorbent the the since type fractionation same for future oil. subject of ratio deasphaltened to adsorbent the to are of fraction each proportions the addition, In products. and formof fractions oil clay the of in plant operations crude treatment in present day, commercially the to is used continued by has adsorption separation and procedure subsequent This and ltration. adsorbent solutions the with fraction petroleum ofof the warming consisted procedures Early technique. responsible particular for achieved successes the this with fraction. aromatic the in (i.e., atoms six-carbon atoms) nonaromatic appear six-carbon will more than -paraf ns, naphthenes, and aromatics), or SARA (saturates, aromatics, resins, and asphaltenes). aromatics), and and naphthenes, resins, (saturates, aromatics, or SARA -paraf ns, The The However, employed adsorbent upon the depending having a compound an for separation, the The variety of fractions isolated by these methods and the potential for the differences in compo in for differences the potential the and isolatedmethods by of these fractions variety The differ. might for methods identi cation used various the of the terminology the summary, In heavy feedstocks However, separate to when attempting must taken be that precautions are there have that received two procedures considerable are over these attention There and years the the that established, been has adsorbent using aspeci c advisable,It is also once aprocedure been has adsorbent of the nature the and procedures experimental of the monitoring Careful aromatic fraction (containing one benzene ring in amolecule) in ring one benzene (containing diaromatics to ) are also known but are somewhat but known lower are also less the prevalent systems, ) are than and ring (substituted systems phenanthrene). ( ring condensed Higher consists of those compounds containing an aromatic ring and varies from from varies and ring aromatic an consists containing of compounds those Handbook of Petroleum Refining of Petroleum Handbook or in the original state, but state, in original the or in (substituted naphtha (substituted tetra-aromatics of more than of more than -paraf ns, -paraf ns, ------, Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 separation of the various fractions. various of the separation of amethod than for of designedrather productcleaning amethod whichmore as it was originally conclusion, in left is feedstock dependent be test and, method the fractionation it that would appear emulsionsplex (Speight, dif cult-to-break and sulfates 2014, 2015). Obviously, successof this the formationof due of com bitumen the to fractionation and/or heavy oil the successin limited with but re nery the in applied been also has method this since acid and sulfuric with tions is treatment (Speight, 2014, well as 2015) separation. as productpuri cation to applied often are alkali with solvent treatment such adsorption, and as methods fractionation, to applied treatment, have reactants been using several chemical sections. Although methods preceding the in described methods the from nature in entirely different are reactants of using chemical Methods fractionation 3.5.3 molecular weight distribution can be determined by chromatography. gel permeation Using weight determined be molecular these can distribution The types. molecular of the polarity of the ameasure as parameter by solubility characterized involved separation The such adsorbent clay, use of as coordinates. an the were fractions the and as distribution type molecular weightcompositional the molecular using and map the distribution fraction. aromatics polar the found in normally oxygen the ofare petroleum fractions, heavy fractions the present in compounds aromatic polar the and aromatics naphthene the both in molecules, which appear sulfur-containing the to contrast In decrease. also nitrogen contents fractions of and the sulfur the decreases, fraction weight molecular nitrogen. the As aromatic and of the some sulfur molecules both probably contain one nitrogen atom but also atom or more than one sulfur more than has asphaltenes and resins the in showed every data not onlymolecule can that These exhibited. be also can fraction aromatic polar the in and fraction aromatic the in atoms of sulfur number nitrogen and the elemental analyses, weight molecular Using from and weight of studies type. data molecular other molecular the and 1979, (Long, polarity and 1981; Speight, 1994). weight considered on acomplex molecular based are which of asphaltenes in matter state petroleum of fraction asphaltene the to applied been Such fractions. also four aconcept has as speci c than 3.15).positional (Figure studies acontinuum more as appear then heavy feedstocks Petroleum and 3.13),(Figure itpossible becomes com dimensionto extra develop to an add and map petroleum the fractions bulk by and assiduous original the collection subfractions of from various further step approach one the for used By be compositionpredictions. behavioral petroleum taking can that amore representative ofcomposition. indication petroleum obtain to fractions using subfractionation major of the composition the one further step studies take to It is necessary Speight, 1975), and (Koots of possible predictions feedstock behavior although are using such data. provideto simple avery but convenient feedstock map on a relative compared allows to be feedstocks that basis different and fractionation but on further havestudies focused composition not only on the its fractions major of and petroleum operational investigations have excellent provided an 1984). (Tissot, of heavy feedstocks studying means Later developed composition focused on the behavior techniques and ofthe for asphalt, those primarily by composition dictated of (Speight, any feedstock are 2014, 2015). were studies early Although 3.13) (Figure of separation (Speight, 2014, 2015), behavior properties the and but, more important, by method de ned the is acomposite oil simplest of the are sense, four crude In that major fractions 3.6 Feedstock Composition Feedstock - frac various into oil crude separate to applied commonly separation of chemical method The More recent work (Long and Speight, workMore recent and 1989) (Long involved development the of of type a different viewed be consisting can of as one petroleum two of continuous distributions, Furthermore, it overview is possible an technique, selection of appropriate of obtain to by an Thus, careful Such not does givea map complexof anyfractions indication the various of the interrelationships USE OFTHE DATA C H emi C al m et H odS . 135 - - Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 residue, is shown for for regions map 3.17) on various the asample ofresiduum atmospheric (Figure 136 to concentrate on the map. on the For to concentrate example, the 3.16). (Figure fractions various the to parameters these equating and procedures separation solvents of the solvent solubilityin used the parameters with produced are solubilitythe parameter derived using be simplest can solvents that The maps adsorbent. remove the from that fractions the by values concept have the for elutingof the this estimated solubility focused on the parameter, strength. adsorption and polarity both characterize to used could be fractions different of the solubility the parameter that It was suggested coordinate. for horizontal the polarity in is not acontinuous variation there and yield, plot of on the the is ameasure distance horizontal agiven The in type. of material amounts the not to related are polarity. However, areas the somewhat because be of can map misleading type this of order in increasing ranked yield was maps types the molecular rst of of the their coordinate type molecular the or polarity. reason, For type this molecular in continuum the how characterize to it concept, was unclear original of the time At the adsorbent. on an strength adsorption increasing conversion re ning. and petroleum separation in many insights into used processes for two Such distributions. the plotting acomposition provide coordinates can the map as parameter weight using molecular solubility of amap two and composition prepared distributions, be can FIGURE Thus, a composition map can be used to show where a particular physical or chemical property tends tends physical property or chemical show to used acomposition be Thus, where can aparticular map remove to attempt to developments order more recent ambiguities, In some potential of these by the molecules, of measured the as by polarity the was characterized type molecular The 3.15

A petroleum map A petroleum % of Feedstock 100 10 20 30 40 50 60 70 80 90 0 Asphaltenes Nonvolatile aromatics saturates/ aromatics saturates/ Volatile Resins based onsimple fractionation. based coke-forming propensity coke-forming 02 Saturates 0406 Aromatics wt% Handbook of Petroleum Refining of Petroleum Handbook aromatics , that is, the amount of the carbon carbon of amount the is, the , that 0 Polar 80 100 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 FIGURE FIGURE Feedstock Composition Feedstock 3.17 3.16

Property prediction using a petroleum map apetroleum using prediction Property A petroleum map A petroleum

Molecular weight 10,000 12,000 2,000 4,000 6,000 8,000 0 –3

Saturates Molecular weight (× 10 ) 10 20 30 0 8.0 based on molecular weight and solubility parameter. weight solubility and onmolecular based 0.0 % ofTotalCon.Carb. Saturates Polars Aromatics Saturates Overall solubilityparameter Aromatics Molecular polarity 0.7 97.6 aromatics 2.4 0.0 Polar 9.0 . 39.4 Polars 15.4 47.8 aromatics Polar 10. insolubles insolubles Numbers in insolubles Heptane fractions= Pentane wt% Con. Toluene 0 carbon 137 Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 138 FIGURE solvent distillation, adsorption, precipitation relatively with solvents, nonpolar solvent and extraction or conversionsrations 3.18) of(Figure petroleum Speight, 1998). and (Long are processes These oil. by clay pentane-deasphalted of the obtained adsorption fractions of the show of boundaries solvent-precipitated lines the vertical show the boundaries lines and the fractions, envelope is the line polarity. dashed ofof slanted sample. composition increasing The The total of the Speight, 1998). and (Long plot The shows weight molecular weight against plotted yield percent order in FIGURE A composition map can be very useful for predicting the effectiveness of the sepa- for useful A compositionvery types predicting of be various can map 3.19 3.18

Mapping feedstock processability. feedstock Mapping Separation ef ciency using a petroleum map apetroleum ef ciency using Separation

Molecular weight 10,000 12,000 Molecular weight 10,000 12,000 6,000 8,000 2,000 4,000 6,000 8,000 2,000 4,000 0 0 Hydrogenation Reforming Saturates Saturates 0.0 Aromatics 0.0 Aromatics precipitation Hydrocracking 0.7 Solvent 0.7 Molecular polarity Molecular polarity Polars 21.6 Polars . 21.6 Handbook of Petroleum Refining of Petroleum Handbook Distillation Numbers in Extraction with polar (remove NandS) fractions= Numbers in wt% Con. solvents fractions= wt% Con. Hydrotreating carbon Heat soaking visbreaking carbon Downloaded By: 10.3.98.104 At: 14:57 28 Sep 2021; For: 9781315374079, chapter3, 10.1201/9781315374079-5 Feedstock Composition Feedstock relevant questions about the character of the crude oil. relevant crude of the questions character about the Reynolds,and 1988). is merely answer to method each the used being is Neither incorrect; method 1988; (Green et al., Vogh types compound speci c to de ne order subfractions many in into oil crude the separate to need may the be there hand, other the On fractions. four into bulk separated be oil crude the only that require that needs those For example, are for data. there by need the the Speight, 1998). and (Long 3.19) (Figure another to composition type the sion one molecular movein from processes materials conver processes, by generated separation cut lines the to contrast In rises. residue distillate of the carbon the distillate, included the in are species polar more of As the bottoms. the from materials lower-molecular-weight rejecting and distillate the in species polar more of and the weight materials moves line the upward, including higher-molecular- is raised, distillate of point the boiling the As which above lies bottoms, which line. below and lies the line, dividing distillate, into the map the solventtion, and divides composition for divide the precipitation can distillation line map. The by clay show chromatography.- determined lines extrac how as slanted aromatics The distillation, polar and aromatics show solvents. saturates cut polar between with lines points the vertical The Petroleum and Gas Filed Processing Filed 2016. M.A. Gas H.K., and Abdel-Aal, Aggour, Fahim, M.A., Petroleum and REFERENCES Aksenov, V.S. com Kanayanov, and of native V.F. sulfur structures and composition in 1980. Regularities Compositional Analysis of Heavy Petroleum Analysis 1994. M.M. Fractions Compositional Boduszynski, and Altgelt, K.H. ASTM D1757. ASTM Coke. and Coal from Ash in Test 2015. for Sulfur Method Standard (High-Temperature D1552. ASTM Method). Products Petroleum in Test 2015. for Sulfur Method Standard Method). D1318. Photometric ASTM (Flame Oil Fuel Residual in Test 2015. for Sodium Method Standard Book Annual Method). (Lamp Products Petroleum D1266. in ASTM Test 2015. for Sulfur Method Standard D1018. of Book ASTM Standards. Annual Fractions. 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