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INT-8989, 2001

SUMMARY

Selective Catalytic Steam Cracking (SCSC), better known a tec$nology, i a %roce t$at combine

!"#aconver ion ®

t$ermal cracking an& catalytic water

&i ociation reaction to #%gra&e $eavy cr#&e oil an& vac##m re i&#e by increa ing !'I gravity (1)* 'ro&#ct c$aracteri+ation t#&ie o, mo&el molec#le an& real ,ee& tock $ave $own t$at ome o, t$e c$emical c$ange t$at occ#r &#ring SCSC, involve &ealkylation o, i&e c$ain ,rom alkylaromatic moietie (1-2)* -owever, to get a better #n&er tan&ing o, t$e tr#ct#ral tran ,ormation e.%erimente& by $ig$ molec#lar weig$t ,raction , %ectro co%ic tec$ni"#e an& /#t$eni#m ion cataly+e& o.i&ation (/IC0) reaction $ave been # e& a c$aracteri+ation tool *

T$e %#r%o e o, t$i work i try to %re&ict ,rom %ectro co%ic &ata an& /IC0 in,ormation t$e %roce ability %otential o, two ,ee& tock #n&er SCSC con&ition * T$# , tr#ct#ral "#ality %arameter (S1'), &e,ine& ,rom %ectro co%ic &ata, wa ,o#n& to be $el%,#l to &e cribe ,ee& tock be$avior #n&er !1C con&ition * !t t$e ame time, /IC0 %roce&#re gave val#able in,ormation abo#t ali%$atic gro#% &i trib#tion t$at wa in agreement wit$ t$e calc#late& S1' val#e * !&&itionally, /IC0 re #lt gave ome in ig$t relate& to t$e reactivity o, t$e i&enti,ie& ali%$atic gro#% an& abo#t t$eir contrib#tion to t$e conver ion val#e ac$ieve& by t$e t#&ie& vac##m re i&#e *

'23S!-INT434'

INT-8989, 2001

2

1.

INTRODUCTION !"#aconver ion ®

Selective Catalytic Steam Cracking (SCSC), better known a tec$nology, i a %roce

t$at combine t$ermal cracking an& catalytic water &i ociation

reaction to #%gra&e $eavy cr#&e oil an& vac##m re i&#e by increa ing !'I gravity (1)* 2#ring t$i mo&erate conver ion %roce , water molec#le are catalytically &i ociate& to ,orm $y&rogen ,ree ra&ical * T$e e ra&ical at#rate $y&rocarbon ,ree ra&ical ,orme& by t$ermal cracking o, ,ee& tock com%onent (5ig#re 1)* 6y t$i way, con&en ation reaction are "#enc$e& in #c$ e.ten ion t$at coke ,ormation i con i&erably re&#ce&* ! a re #lt, lig$ter $y&rocarbon %ro&#ct are ,orme& at $ig$er conver ion val#e t$an t$o e ac$ieve& by tra&itional t$ermal cracking %roce e at a imilar %ro&#ct (vac##m re i&#e) tability level (1-2)* 'revio# work relate& to t$e !"#aconver ion ® c$emi try (7-8) $ave %ointe& o#t t$at &ealkylation o, i&e c$ain ,rom alkylaromatic tr#ct#re i one o, t$e c$emical c$ange t$at occ#r &#ring t$e %roce * !ccor&ing to t$e e work , water an& t$e cataly t eem to $ave a %re,erence ,or breaking CS% -CS% bon& locate& in α-%o ition ,rom t$e aromatic ring*
7 2

Con e"#ently, aromatic entitie ric$ in alkyl #b tit#ent are e.%ecte& to give $ig$er conver ion level t$an le alkyl #b tit#te& aromatic one (1-8)* Con i&ering S!/! con tit#ent o, ,ee& tock , aromatic, re in, an& a %$altene ,raction are t$e mo t a,,ecte& beca# e alkylaromatic moietie are concentrate& in #c$ ,raction (9-8)* T$e e ob ervation are an in&icative o, t$e in,l#ence o, t$e carbon ty%e &i trib#tion on t$e SCSC conver ion level* It i im%ortant to kee% in min& t$at ali%$atic carbon are &i trib#te& among everal #b tit#ent in alkylaromatic tr#ct#re * 5or in tance, normal alkyl c$ain , branc$e& alkyl c$ain , %olymet$ylene bri&ge an& na%$t$enic ,#nctionalitie are %re ente& in com%le. ,raction
1

a

re in

an& a %$altene * Con e"#ently, it i

&i,,ic#lt to

t#&y ali%$atic

#b tit#ent &i trib#tion ba e& only on t$e tr#ct#ral average in,ormation given by 17C an& - N:/ tec$ni"#e *

'23S!-INT434'

INT-8989, 2001

7

T$ermal Cleavage

/ /n>
=ater 2i ociation

/ ? /n>

-20
-y&rogen !&&ition

Cataly t

- • ? 0- •

/ ?
0.i&ation

/n> ? 2-

• Cataly t

/ - ? /n -

/n> ? 20-• Cataly t
Con&en ation

/n@-1 ? C02 ? -2

/ ?

/n>

/n> /n> ? / /

Figure 1; SCSC /eaction Se"#ence

To get a more &etaile& an& acc#rate molec#lar &e cri%tion it i nece ary to a&o%t com%lementary c$aracteri+ation %roce&#re * C$emical met$o& $ave been # e& e.ten ively ,or t$i %#r%o e* Some c$emical met$o& $ave t$e %ro%erty o, breaking C-S, C-0, an& C ali%$atic-Caromatic bon& wit$ $ig$ electivity (<-8)* T$e analy i o, re #lting %ro&#ct give inval#able &etaile& in,ormation on t$e tr#ct#ral element , tr#ct#ral #nit an& molec#lar arc$itect#re o, re in an& a %$altene * T$e elective cleavage o, Cali%$atic-Caromatic bon& $a become t$e mo t

'23S!-INT434'

INT-8989, 2001

9

%o%#lar c$emical met$o&* 0ne o, t$e %roce&#re # e& ,or t$i %#r%o e involve /#t$eni#m ion an& it i known a /#t$eni#m Ion Cataly+e& 0.i&ation (/IC0) reaction* /IC0 reaction &oe not cleavage &irectly t$e C ali%$atic-Caromatic bon&* T$i reaction i able to convert aromatic carbon electively to carbon &io.i&e an&Aor carbo.ylic gro#% w$ile leaving ali%$atic tr#ct#re e entially #na,,ecte& (9-21)* T$e reaction %attern i very im%le an& $a been t#&ie& # ing mo&el com%o#n& (9-1B)* T$# , alkyl #b tit#te& aromatic molec#le are o.i&i+e& to C02 e.ce%t at t$e ite o, t$e alkyl attac$ment, w$ic$ i converte& to a carbo.ylic gro#% anc$ore& to t$e alkyl c$ain, wit$ t$e #b e"#ent ,ormation o, an alkanoic aci& (9-21)* T$i it#ation i $owe& in c$eme 1; 0 / /IC0 -0 C /

?

C02

Scheme 1

=$en t$e ali%$atic c$ain i between two aromatic carbon , a &icarbo.ylic aci& re #lt ;

(C-2)n
2

/IC0

-0 0

(C-2)n 0

0-

/IC0
3

-00C -00C

/IC0
4 Scheme 2

-00C -00C

'23S!-INT434'

t$i kin& o.orm &#ring /IC0 reaction* '23S!-INT434' .7.INT-8989. tr#ct#re i %re ente& in re in an& a %$altene . alkane %olycarbo. 2001 8 In t$i ca e.orme& &#ring /IC0 reaction.orme& by t$e o.2.talene (3) or cyclo%ro%ylben+ene (4) &erivative cannot be &i ting#i $e& .i&ation o.ω &i%$enylalkane (2) (9-21)* -owever. 6 9 7 1 ! 0 -0 0 -0 0 -0 5 0 -0 -0 0 -0 0 11 -00C C00C00C00- 12 Scheme 3 I.erre& by t$e analy i o.ylic aci& are . Nom#ra et al (18-1B) $ave %ointe& o#t t$at more com%le. α.%ecte& to be .rom t$o e one .ω-&icarbo. α.i&ation o. na%$t$enic (-y&roaromatic) tr#ct#re can be ea ily in.orme& by t$e o.ylic aci& .9-tetra$y&rona%. alkane %olycarbo. na%$t$enic tr#ct#re a 1.ylic aci& are e.

%ro&#ct * 5or e.i&ation o.am%le. #c$ tr#ct#re i o. w$en one o. t$e latter remain a a ben+ene carbo.. t$e met$yl gro#%) t$e alkyl. a carbo.t#re (18) (Sc$eme 9) C00/IC0 C02 ? C0013 Scheme 4 In contra t.ylic gro#% i . tri.orm by t$e o. tetra an& le ab#n&ant %enta an& $e. t$em remain a ben+ene &i.i&ation o.acarbo. t$e $o t ring. 2001 < !not$er . alkyl gro#% on t$e ben+ene ring $ave an activating e.i&i+e&.ect o. t$e econ& ring* ! a con e"#ence.ylic aci& in t$e /IC0 %ro&#ct mi.ylic gro#% avoi& t$e #b e"#ent o.i&i+e&* I. t$e alkyl #b tit#tion &etermine w$et$er one or bot$ ring will be o.ore (wit$ t$e e. t$e #n #b tit#te& ring will al o be o.#b tit#te& ring i o.ect* T$ere.eat#re o. / C00/IC0 / /IC0 C02 ? -00C / C02 ? -00C / ? C00- 14 15 Scheme 5 '23S!-INT434' .orme& on t$e a&Cacent aromatic ring* T$e &eactivating e. %olyaromatic tr#ct#re yiel& t$i kin& o. /IC0 reaction i t$at aromatic ring are not com%letely o.INT-8989. t$e %o ition o. t$e aromatic ring o..i&i+e& (18) (Sc$eme 8).i&i+e& to C0 2 an& ome o.ce%tion o.i&i+e& to C0 2 * !&&itionally. t$e alkyl #b tit#ent i in a %o ition w$ere a carbo. t$e carbo.ylic gro#% mig$t .ylic aci& (18)* Commonly.

t$e mo t a. /IC0 %ro&#ct toget$er wit$ t$e in. !romatic .INT-8989.ormation %rovi&e& by %ectro co%ic tec$ni"#e can give im%ortant tr#ct#ral &etail o.raction * T$# .or e.or t$e c$aracteri+ation o.. -00C -00C C0016 C00-00C -00C C00- Scheme 6 Table 1 li t common ben+ene %olycarbo.7-triaci& an& t$e 1.ylic aci& .ylic aci& %rovi&e inval#able in ig$t into t$e mo&e o.am%le.2. t$e %re ent work i to # e c$emical an& %ectro co%ic met$o& .ecte& S!/! . in or&er to t#&y an& %re&ict t$eir be$avior #n&er SCSC (!"#aconver ion®) con&ition * '23S!-INT434' . ben+ene %olycarbo.o#n& in /IC0 %ro&#ct mi. 2001 B :o t con&en e& aromatic molec#le wo#l& give more t$an one aci&* T$# . two vac##m re i&#e .9 tetraci&. /e in an& ! %$altene )* T$e co%e o. aromatic y tem containe& in re in an& a %$altene .7. t$e analy i o.t#re an& t$eir %o ible aromatic y tem %rec#r or (18-18)* ! can be een. !rabian lig$t an& Cerro Negro. t$e analy i o. %yrene can yiel& t$e 1. .2. con&en ation an& %o ible tr#ct#re o.raction &#ring SCSC %roce (i*e*.

ben+ene carbo.INT-8989.ylic aci& 6en+ene carbo. 2001 8 T"#$e 1* 'o ible %rec#r or o.ylic aci& 'rec#r or 'o ible 'rec#r or '23S!-INT434' .

an& N#clear :agnetic /e onance %ectro co%y (1.-i. 98G* T$e recycle time wa 8 econ& an& T:S wa # e& a re.li% angle o.erence* Sam%le concentration wa 28 mgAmD in C. "+. C. S#l. carbon an& $y&rogen content &etermine& by elemental analy i .1 %&'%RIM%NTA( SARA Fr"c)i*+")i*+ ! %$altene . Nitrogen (N)). 0. mo&el C-SN-972* S#l. 2.ractionate& into Sat#rate .erence (29)* '23S!-INT434' . 2001 9 2.2Cl2A CS2 1. an& 3'0 molec#lar weig$t were # e& a in%#t &ata to calc#late !verage :olec#lar 'arameter (!:') by t$e met$o&ology re%orte& in re. -. !romatic an& /e in by %re%arative -'DC a in&icate& in re.#rt$er c$aracteri+e& by elemental analy i (Carbon (C).1* 1 . mo&el I/ 972 an& Nitrogen. -y&rogen (-). mo&el 1000* !verage molec#lar weig$t wa &eterminate& in a Fna#er 0 mometer # ing C-2Cl2 an& C-Cl7 a 2. M*$ecu$"r /eigh) De)ermi+")i*+.#r wa &etermine& in a D4C0 !naly+er. 3a%or '$a e 0 mometry (3'0). E*T 6aker) (22)* T$e re #lting maltene %ortion wa ."+. in a 2or$man !naly+er.2 %$eme+)"$ A+"$. A2er"ge M*$ecu$"r '"r"me)er C"$cu$")i*+.N:/ &ata.raction were .erence (27)* S!/! .erence material* 0 NMR S1ec)r*-c*1.orme& in a 6r#ker S%ectrometer !C'-900* 1.N:/ %ectra were ac"#ire& at 900 :-+ wit$ a 12 %%m win&ow an& a .ygen (0). N:/ analy e were %er.N:/ an& 17C N:/)* 2.rom two vac##m re i&#e (!rabian Dig$t (!D) an& Cerro Negro (CN) were obtaine& by %reci%itation wit$ n-$e%tane (-'DC gra&e. an& 0 were &etermine& in a D4C0 !naly+er.INT-8989.3 1 olvent * 6en+il wa # e& a a re.#r (S).

80*0 mD o.ollow.or t$e ot$er en&* T$en.raction . (5ig#re 2)* !ir containe& in t$e reactor wa evac#ate& # ing vac##m an& re%lace& by N2* =it$ a N2 %o itive %re #re an& # ing a gla $ermetically an& . t$e H!ST4C %#m%* C0 2 wa ab orbe& on t$e %ackage a t$e ga %a e& t$ro#g$ t$e H!ST4C &etector t#be* ! color re %on e wa generate& in&icating C02 concentration level* '23S!-INT434' .rom !D an& CN vac##m re i&#e were #bmitte& to /IC0 reaction a . t$e am%le were &i olve& in a Cr (III) acetylacetonate A &e#terate& c$loro. C0 2 . &e igne& to mea #re t$e %re #re o. /#Cl2*7-20.5 RICO Re"c)i*+ 'r*ce. 2001 10 2*9 17 13 C NMR S1ec)r*-c*1. C N:/ analy e were %er.INT-8989.Carbon 2io. an& 9*0 g o. &#ring w$ic$ t$e initial &ark brown color c$ange& to yellow %ale* !t t$i %oint t$e reaction wa to%%e& an& t$e . !bo#t 200*0 mg o. 7*0 % i* T$e $eterogeneo# mi. NaI09. evolve& &#ring t$e reaction. t$e reactor wa clo e& Concentration o. C-7CN an& 10 mD o. <*0 mD o. <*0 mD o.#nnel. were %lace& into a 280 mD .i&e &etector t#be wit$ a mea #ring range o. -20 were a&&e&* T$en..inal %re #re wa mea #re&* CCl9.lat bottom gla reactor %rototy%e. 110 I vAv (Ha tec Cor%oration) wa connecte& to t$e reactor N 2 inlet an& to t$e H!ST4C %#m% . 12*0 mg o. am%le. t$e evolve& C02 wa mea #re& by # ing t$e H!ST4C colorimetric met$o&* H!ST4C No* 2. 8 econ& between eac$ %#l e* 8000 %#l e were acc#m#late& in 12 $o#r * 2.ure "+. t$e ga containe& in t$e reactor were taken by #ction o.or 29 $o#r at room tem%erat#re. re in an& a %$altene .ille& wit$ N2 #% to reac$ a %re #re o.orme& at 100*<19 :-+* !bo#t 900 mg o.om ol#tion (0*01 :)* 17C N:/ %ectra were ac"#ire& # ing a ingle %#l e tec$ni"#e (70G %#l e ) wit$ a %erio& o.t#re wa magnetically tirre& . CO2 Me"-ureme+)* !romatic.

INT-8989.or a 29 $ %erio&.ormer wa . t$e NaI09 e.ilter an& t$e %reci%itate wa wa $e& wit$ &iet$ylet$er* T$e a"#eo# an& t$e organic %$a e were e%arate& an& t$e . C-2Cl2* =a $ing were combine& wit$ t$e original organic layer* !bo#t 180 mD o. 2001 11 N2 're #re Ha#ge 3ac##m :agnetic Stirrier Figure 2* /IC0 /eactor %rototy%e !.ce * !.ter C02 mea #rement.iltere& tro#g$ a 0*2 µm %ore i+e Nylon-<< .#rt$er e.in met$anol ol#tion were a&&e& to t$e a"#eo# layer to ne#trali+e aci&ic %ro&#ct an& to in&#ce t$e %reci%itation o. t$e reaction mi.ter tan&ing .tracte& wit$ 10.t#re wa . a 0*1m: Na0.2 mD o. a"#eo# an& organic %$a e were .iltere&* !"#eo# %$a e wa eva%orate& at B0JC to &ryne * 0rganic %$a e& wa Coine& to t$e eva%orate& a"#eo# %$a e an& concentrate& # ing a N2 tream* '23S!-INT434' .

an& t$e cataly t* T$e reaction wa to%%e& w$en %ro&#ct reac$e& a critical '-val#e o.erence. 65 7 in met$anol ('ierce C$emical) to t$e %ro&#ct ol#tion* T$e re #lting mi. HC-:S analy e were %er.ure.orme& in a -'8890 Serie II Ha C$romatogra%$ e"#i%%e& wit$ a %lit inCector an& a 62-1B01 ca%illary col#mn (70m . /IC0 %ro&#ct wa carrie& o#t by a&&ing 8.i.erence (28))* '23S!-INT434' . 'ilot %lant te t were %er.ter a&&ing t$e e teri.!. a 19I ol#tion o. 4 teri. 1*20 ('-val#e wa &etermine& a in&icate& in re. t$e %ro&#ct ol#tion c$ange& to re& beca# e o. 'i$*) '$"+) Te-)-. abo#t 100 mg o.(21)* T$en. an& concentrate& to 1*0 mD by rotary eva%oration at 70GC an& N2 tream* T$e met$yle ter ol#tion wa . . 2001 12 2. 0*28mm coate& wit$ 0*8 µm 26-1) connecte& to a -'89B0 ma &etector* -eli#m ga # e& a carrier ga * Ty%ically o%erating c$romatogra%$ic con&ition are li te& in Table 2 T"#$e 26 0%erating c$romatogra%$ic con&ition in HC-:S analy i Initial T (GC) InCector Col#mn 280 78 5inal T (GC) 280 700 700 T /am% (GCAmin) 0 B nA 5inal T 2.#rt$er analy+e& by HC-:S* 2. t$e mi.e& tem%erat#re an& .0 mD o.e& wit$ t$e !rabian Dig$t or t$e Cerro Negro vac##m re i&#e. team.INT-8989.t#re wa tirre& at room tem%erat#re .t#re wa &rie& over Na2S09.7 4C5MS A+"$.ication o. t$e yellow %ale color o.-i-.iltrate&.ier reagent.orme& in a one barrelA&ay ca%acity %ilot %lant o%erate& at a .or 12 $o#r * !.6 %-)eri3ic")i*+ 'r*ce. Kinc %ow&er wa a&&e& to re&#ce I 2 to I. io&ine liberation* To eliminate t$i inter.

!rabian Dig$t an& Cerro 3. Cerro Negro re i&#e (CN) re #lte& $eavier t$an t$e !rabian Dig$t re i&#e (A() (7*8 G !'I an& B.. %%m Nickel 3ana&i#m 'ota i#m 20*07 B<*00 1*<2 198*20 <19*80 7*08 B*0 1079 187 19*9 B*8 89*B 10*<1 0*72 0*82 9*10 Cerr* Negr* Re-i."+. carbon an& $y&rogen %re ent in Cerro Negro re i&#e* '23S!-INT434' .-i. Ar"#i"+ (igh) Re-i. Selecte& 'ro%ertie o.0 G !'I re %ectively)* T$i ten&ency i a re.lect o. R%SU(TS Negro vac##m re i&#e # e& a !1C an& 3i core&#ction . c$aracteri+ation o.ue 7*8 902<9 2070 22*0 18*B 87*89 10*22 0*97 0*8< 9*27 !ccor&ing to !'I gravity val#e . electe& %ro%ertie o. /e i&#e * 'r*1er). !rabian lig$t an& Cerro Negro re i&#e were &etermine&* T$e e re #lt are %re ente& in Table 7* T"#$e 3. ! a . I wt* ! %$altene (n-$e%tane in ol#ble ). 2B8 G5 Conra& on Carbon /e i&#e. !1C an& 3i breaking %ro&#ct will be %re ente&* T$e . I wt 4lemental Com%o ition. 210 G5 Finematic vi co ity cSt.1 %$eme+)"$ A+"$. Se$ec)e.ollowing %artial re #lt corre %on& to t$e c$aracteri+ation o. I wt C N 0 S :etal . %ara.ee& tock * In a econ& i #e.in .ue !'I Hravity Finematic vi co ity cSt. toget$er wit$ t$e lower content o. $eteroatom an& metal . a %$altene . t$e $ig$er content o.ir t c$aracteri+ation te%. 2001 17 3.INT-8989. 'r*1er)ie-.

icient to &e cribe t$em in a tr#ct#ral . it eem t$at CN re i&#e co#l& $ow a $ig$er conver ion val#e beca# e it $a a maCor yiel& o.7 I wt (aromatic ?re in ?a %$altene ) t$at can be converte&. were a&o%te& to reac$ t$i goal* 3.7I $ig$er)* ! a .eat#re o. SARA Di-)ri#u)i*+-. at#rate (19*B I wt) t$an CN re i&#e (<*1I wt)* !ccor&ing to t$e #gge te& mec$ani m . re i&#e . 10-7 9*<0 B*<9 SAC . t$ey are in #.raction in SCSC* '23S!-INT434' . A( an& CN re i&#e * A( re i&#e $a a maCor content o. ba e& #%on S!/! . CN re i&#e co#l& %otentially .2. 5ig#re 7 $ow S!/! &i trib#tion o..9 I wt* (8.INT-8989.ormation abo#t %$y icoc$emical . w$erea CN re i&#e $a a 97.ir t a%%ro. 10-7 7*29 9*80 0AC . A( re i&#e $a a 88.orm $ig$er coke amo#nt t$an A( re i&#e* Table 9 $ow atomic ratio o. cr#&e oil an& t$eir &erivative (2<)* !ccor&ing to t$i . alternative c$aracteri+ation trategie .a $ion an& to %re&ict t$eir be$avior #n&er SCSC con&ition * Con e"#ently.. CN re i&#e $a a $ig$er Conra& on carbon val#e t$an A( re i&#e* Conra& on carbon re i&#e i con i&ere& a a %arameter to eval#ate coke . t$e t#&ie& re i&#e * CN %re ente& a lower -AC ratio an& $ig$er NAC. 10-2 1*82 1*89 4ven t$o#g$ t$e mi cellaneo# %ro%ertie &etermine& give im%ortant in.or SCSC. t$e mainly a. 0AC. 2001 19 0n t$e ot$er $an&.imation. !rabian Dig$t an& Cerro Negro re i&#e /e i&#e A( CN -AC 1*80 1*9< NAC .ecte& . an& SAC ratio com%are& to t$e A( re i&#e* T$e e re #lt are in agreement wit$ t$e low !'I val#e $owe& by t$i re i&#e* T"#$e 46 !tomic ratio o.ractionation an& %ectro co%y tec$ni"#e .ormation ten&encie o.

7 14. t$i i not a g#arantee to en #re $ig$ conver ion level . S!/! . re in an& a %$altene #.. w$ic$ o. '23S!-INT434' .1 !rabian Dig$t Cerro Negro Figure 3. 2001 18 100% 7.3 S)ruc)ur"$ 7u"$i).er t$e mo t im%ortant c$emical c$ange in SCSC (9-8)* !mong t$em.7 6. it i &i. A( re i&#e i ric$er in aromatic .. beca# e in SCSC. tran .-i-. t$e aromatic . *3 SARA 3r"c)i*+-6 13C NMR A+"$.raction. A( an& CN re i&#e * ! tate& be.5 90% 80% 70% 60% % Wt 50% 40% 30% 20% 10% 0% 18.INT-8989. w$erea CN re i&#e i in %olar (re in ? a %$altene )* 4ven t$o#g$ A( re i&#e %re ent a $ig$er content in aromatic .ormation co#l& be a ociate& not only to weig$t yiel& o. t$e t#&ie& re i&#e will $ow t$e $ig$e t conver ion level* 3.raction .ic#lt to e tabli $ .ecte& t$e mo t* ! ob erve& in 5ig#re 7.7 Asphaltenes Resins 23. S!/! &i trib#tion o.rom S!/! &i trib#tion . b#t al o to t$e tr#ct#ral c$aracteri tic o.9 36.9 38. aromatic .raction wa t$at a. t$em (8)* In con e"#ence.5 Aromatics Saturates 53.ore..raction.

raction t$at can be # e& to C N:/ %ectra o. 6 9 3 7 1 4 . 2 3 7 1 7 0 1 6 0 1 5 0 14 0 13 0 12 0 11 0 10 0 9 0 ! p p m " 8 0 7 0 6 0 5 0 4 0 3 8 . 9 99 6 29 . . .o#n& to im%rove #c$ %re&iction * It i believe& t$at alkyl #b tit#ent in aromatic tr#ct#re can $ave a igni. 6 8 3 5 1 9 .a L 0*<12 r al 6 1 . 8 8 1 1 3 0 1 2 0 1 1 0 1 0 0 9 0 ! p p m " 8 0 7 0 6 0 5 0 4 0 3 0 I n t e 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 11 0 1 0 0 9 0 ! pp m " 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0 1 7 0 1 6 0 1 5 0 1 4 0 0 3 7 .rom A( re i&#e '23S!-INT434' . 9 0 5 7 2 9 . .raction o. 4 8 9 6 8 . 7 26 9 19 . Re-i+- . 1 4 1 5 31 . it i nece ary to eval#ate t$eir relative ab#n&ance in or&er to e tabli $ t$i in.icant in.l#ence on t$e conver ion val#e (1-8).a L 0*981 r a l 4 5 .a L 0*718 r a l 3 1 .ee& tock an& to %re&ict it be$avior #n&er SCSC con&ition * e timate t$i %arameter* 5ig#re 9 an& 8 $ow 17 17 C N:/ &ata give in. 7 94 8 2 0 A-1h"$)e+e- .l#ence* T$# . 1 6 9 1 1 0 0 Figure 4. 6 9 0 8 1 9 . 0 7 6 5 3 1 . 1 1 9 5 4 . 6 9 3 7 2 0 1 4 . ot$er %arameter m# t be . . S!/! . 2001 1< It $a been &i c# e& $ow S!/! &i trib#tion &o not give eno#g$ in.ore.INT-8989. A( an& CN re i&#e re %ectively* 8 1 7 6 9 2 2 . a SCSC . . t$e ratio alkyl #b tit#entAaromatic ring can be # e& a a %arameter to e timate t$e tr#ct#ral "#ality o. 1 4 7 4 0 7 9 6 0 5 0 0 8 5 4 0 5 8 9 3 7 . 1 5 4 6 1 0 Ar*m")ic- 3 3 3 2 2 7 2 1 9 7 .ormation abo#t carbon ty%e &i trib#tion (aromatic an& ali%$atic carbon ) o.ormation to %re&ict relative conver ion level in SCSC* In con e"#ence. 5 1 1 I n t e . 6 8 8 6 2 2 . T$ere. 7 10 3 22 . 7 6 3 I n t e 3 0 1 4 . 17C N:/ %ectra o. .raction .

3 3 6 6 1 2 6 . 1 4 7 4 1 0 3 3 3 2 7 2 1 9 .a L 0*777 r a l 3 3 .raction .raction beca#/e e o.7 B0 are #mmari+e& in Table 8* eac$ .raction $ave a maCor aromatic c$aracter t$an t$e ame CN . .9 9 0 Str#ct#ral 1#ality 80 'arameter (S1'). 6 9 0 8 1 9 . 6 6 9 1 1 9 . CAtotal C) in aromatic.raction . 3 6 8 6 5 9 9 7 0 2 1 4 0 A-1h"$)e+e- . 3 2 0 6 5. 4 3 2 0 # 0 . 6 8 8 6 2 2 .INT-8989.rom bot$ re i&#e * 5rom t$i &i trib#tion. A( re in an& a %$altene .B 9 C !romatic C !li%$atic 80 90 70 20 10 0 !D CN !D CN !D CN <8. 6 93 7 2 0 Ar*m")ic- Re-i+- .ine& a 2C a%li$aticACaromatic ratio.1 77.raction* /e #lt <0 % %t 2 <1. 3 0 0 6 6 .%re e& a ty%e o.rom CN re i&#e !ccor&ing to t$e e re #lt .B 0 89. 7 1 2 9 3 7 .B < '23S!-INT434' .8 1 <<. aromaticity . 17C N:/ %ectra o. . 68 0 1 8 0 1 6 0 1 4 0 1 2 0 1 0 0 ! p p m 8 0 " 6 0 4 0 2 0 0 I n t e 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 12 0 1 1 0 1 0 0 9 0 ! pp m " 8 0 7 0 6 0 5 0 4 0 3 0 14 . 7 4 2 4 7 .actor (. 7 0 1 0 1 4 .or 98. 9 1 2 9 2 9 . wa calc#late& . 7 0 0 I n t e . 2001 1B 1 3 9 . 7 1 4 6 3 1 . 1 5 4 6 1 1 .a L 0*82B r a l 5 2 . &e. 3 5 0 9 3 2 . .a L 0*797 r a l 3 4 . a 71.2 9 82.8 8 <8. re in 90 an& a %$altene . 2 5 8 1 3 0 1 2 0 1 1 0 1 0 0 9 0 ! p p m " 8 0 7 0 6 0 5 0 4 0 3 0 I n t e 1 7 0 1 6 0 1 5 0 1 4 0 2 0 1 0 0 Figure 5.< 8 47$26 78. . 0 0 0 0 9 9 3 2 22 .7 79.a) val#e* !romatic in t$eir $ig$er ! %$altene 100 5ig#re < $ow aromatic an& ali%$atic carbon &i trib#tion (e.

com%are& to t$o e calc#late& .raction are e.or t$e SCSC %roce * 2i.INT-8989. 2001 18 Figure 6.raction . re in an& an& a %$altene . A( /e i&#e an& CN 3ac##m /e i&#e A( CN !romatic 2*18 2*00 S1'L Ca%li$aticACaromatic /e in 1*21 1*91 ! %$altene 0*<7 0*90 ! mall &i.ten ion #n&er SCSC con&ition * S1' val#e o. !romatic .or re in are ob erve& re %ectively* !ccor&ing to t$e e re #lt . Str#ct#ral 1#ality 'arameter (S1') o. !li%$atic an& aromatic carbon &i trib#tion o.rom a tr#ct#ral %oint o.raction i ob erve&* T$i mean t$at #c$ . 0*B0 an& 0*77 in S1' val#e . re in '23S!-INT434' .%ecte& to be c$emically tran ..or A( . S!/! .rom A( an& CN re i&#e obtaine& by 17C N:/ analy i * T"#$e 5. aromatic .. re in an& a %$altene were $ig$er in CN re i&#e. T$i in&icate an& a %$altene a better tr#ct#ral "#ality o.erence between S1' val#e o.erence o.raction .orme& at a imilar e.raction $ave ome . bot$ aromatic . /e in an& ! %$altene o.eat#re t$at make t$em imilar . view* Con e"#ently.

B2I a ali%$atic carbon an& 29.0B I.INT-8989.7< 98.%ecte& to $ave a more im%ortant contrib#tion to t$e conver ion o. CN re i&#e t$an in t$e ca e o.l#ence on t$e conver ion val#e* T$ere.raction to t$e total carbon content in A( an& CN re i&#e * T$# . t$e e tr#ct#re . an& 17C N:/ &ata* T$e re #lt are %lotte& in 5ig#re B* <0 80 A( CN 99. A( re i&#e* Total alkyl #b tit#ent an& total aromatic tr#ct#re containe& in eac$ re i&#e can be e timate& too* To &o t$i . eac$ . CN re i&#e %re ent a 97.B2 90 I wt (CA am%le wt*) 70 2B.78I a aromatic carbon* 0n t$e ot$er $an&. 2001 19 a %$altene . re in an& a %$altene) .ollow. it i nece ary to con i&er aromatic.78 I C aromatic I C !li%$atic Figure 7. 98.erence in alkyl #b tit#ent t$at co#l& $ave a marke& in. =eig$t contrib#tion o.7 I wt o. &i trib#te& a . B8..ore. ali%$atic an& aromatic carbon in t$e combine& (aromatic.raction are e.raction (.rom S!/! e%aration ) toget$er wit$ carbon content o.7 I wt o.rom CN re i&#e $ow a noticeable &i. A( re i&#e $a 88. t$e e .10 20 10 0 29. re in an& a %$altene yiel& (.rom elemental analy i ). w$ere carbon re%re ent B1*9< I wt com%ri ing 99*7<I ali%$atic an& 2B*10I aromatic carbon * '23S!-INT434' . tr#ct#re t$at can %otentially be converte& #n&er SCSC con&ition (!romatic ?/e in ?! %$altene )* T$i convertible %ortion $a a total carbon content o.

t$em* 4ac$ com%onent will $ave yiel& o. Total Str#ct#ral 1#ality 'arameter Calc#late& . t$e carbon ty%e &i trib#tion among aromatic .erence in TS1' val#e wa ob erve&. t$e aromatic '23S!-INT434' . ! "#ality com%onent an& a ma yiel& com%onent* 1#ality com%onent i relate& to t$e yiel& in&ivi&#al S1' val#e o.ue IC !li%$atic IC!romatic 71*01 10*89 2*9< 99*7< 19*28 8*9< 7*89 2B*10 I CTotal 72*90 29*99 18*<8 B8*0B CN Re-i.. w$ile t$e ma an& im%ortant contrib#tion to t$e TS1' val#e* 5or in tance.raction converte& &#ring t$e SCSC %roce * I CTotal !romatic /e in ! %$altene Total 98*2< 19*88 <*78 B1*9< A( Re-i. re in . Total carbon ty%e &i trib#tion in A( an& CN re i&#e an& t$e in&ivi&#al contrib#tion o.%lain t$i re #lt.or A( re i&#e.or eac$ re i&#e con i&ering total ali%$atic an& aromatic carbon content in !romatic. a Total Str#ct#ral 1#ality 'arameter (TS1') wa calc#late& .or A( an& CN /e i&#e * /e i&#e A( CN TS1'L (ΣCali%$atic)A(ΣCaromatic)* 1*<9 1*<< T$# .INT-8989. /e in an& ! %$altene .raction . t$e mainly a. ma com%onent i relate& to t$e relative weig$t %ercentage o. 2001 20 In Table <.ue IC !li%$atic IC!romatic 21*<1 19*B0 B*91 98*B2 10*B9 10*29 8*2B 29*78 Con i&ering t$e e re #lt .ecte& S!/! . To e..raction ((ΣCali%$atic)A(ΣCaromatic))* /e #lt are li te& in Table B* T"#$e 7. an& a %$altene are li te&* T"#$e 6. a #btle &i. CN re i&#e TS1' val#e i a little bit $ig$er com%are& to t$e one obtaine& . we $ave to con i&er t$at TS1' val#e $a two main com%onent . main S!/! .

raction in bot$ re i&#e are e. an& total carbon content a in&icate& in re.raction in A( re i&#e* T$e global e.raction were &etermine& among t$e e %arameter * !&&itionally.C"$cu$")e..%erience more c$emical c$ange t$an re i&#e A( re i&#e SCSC con&ition * 3. 2001 21 .INT-8989. t$e aromatic .4 S)ruc)ur"$ 7u"$i). it i $o#l& &i.erence (29)* !li%$atic an& aromatic carbon content o. A( re i&#e will $ave a more im%ortant contrib#tion t$an t$e one corre %on&ing to re in an& a %$altene * In contra t.erence wa be con i&ere& in tea&* ! tate& be. aromatic.raction o.%ecte& to #n&ergo c$emical mall* In con e"#ence. t$e re #lting &i..ten ion beca# e t$ey $ave almo t t$e ame S1' val#e* -owever.N:/ 2ata !romatic /e i&#e A( CN I Cali%$atic I Caromatic I /e in I Caromatic I ! %$altene I Caromatic S1' 2B*82 2B*90 2*89 2*88 Cali%$atic S1' 98*29 91*01 1*21 1*99 Cali%$atic S1' 79*9< 78*2< 1*80 1*<1 B2*18 B2*10 89*B1 88*99 <0*01 <1*B7 '23S!-INT434' .. 3r*m 10 NMR D")".ore. 3'0 molec#lar weig$t.erence between two TS1' val#e will be bigger or maller* In t$i ca e.icant contrib#tion to t$e TS1' val#e t$an t$e aromatic one* 2e%en&ing on t$e contrib#tion o. '"r"me)er. S1' val#e Calc#late& .rom 1. t$e &i.rom 1. eac$ com%onent to TS1'. re in an& a %$altene .ic#lt to make a %re&iction ba e& only on t$i %arameter* In&ivi&#al S1' val#e c$ange at t$e ame e.ormation . S1' val#e were calc#late& too* /e #lt are #mmari+e& in Table 8* T"#$e !. !verage molec#lar %arameter were calc#late& # ing in. re in an& a %$altene in CN re i&#e $o#l& be more a.ect i t$at CN re i&#e $o#l& e. re in an& a %$altene . ma yiel& o..rom CN re i&#e will $ave a igni.N:/ %ectra.ecte& t$an t$e ame ..

N:/ &ata. CN re i&#e $owe& a &i.rom t$o e calc#late& .raction o.rom 'ilot 'lant Te t * '23S!-INT434' .orce& by 1 . A( an& CN re i&#e $ave almo t t$e ame tr#ct#ral "#ality im%lie t$at t$ey $o#l& be converte& at t$e ame e. re in an& a %$altene o.rom 17C N:/ &ata* T$e &i.raction * T$ere.or t$e e . t$e ten&ency i t$e ame.or t$e conver ion val#e ac$ieve& by t$i re i&#e. bot$ re i&#e * T$ere. 're&iction were con.erence in conver ion o. S1' val#e o. 17*2 I re %ect to A( re i&#e.er .orme& # ing A( an& CN re i&#e a .. /e #lt .act t$at aromatic . %re&iction ma&e #%on 17C N:/ &ata are rein. '-val#e wa # e& a a %ro&#ct tability criterion (a '-val#e #n&er 1*18 in&icate t$at %ro&#ct are #n table an& oli& &e%o ition (a %$altene ) can occ#r (1))* Table 9 $ow re #lt obtaine& .ore.5 'i$*) '$"+) )e-)-.irme& &#ring SCSC %ilot %lant te t* T$e e te t were %er.rom %ilot %lant te t * ! %re&icte&. re in an& a %$altene .or re in an& a %$altene . 1*20).or ro#tine analy i * 3.ee& tock * T$e reaction wa %ro&#ct to%%e& at t$e conver ion level w$ere $owe& a minimal '-val#e o.or t$e aromatic . T"#$e 9. -ig$er S1' val#e .rom 1. CN re i&#e $owe& $ig$er conver ion level t$an A( re i&#e* S#r%ri ingly. at t$e ame critical %ro&#ct tability level ('-val#e o.ore. 1. &i.%ecte& con i&ering general %ro%ertie o.rom CN re i&#e an& almo t t$e ame S1' val#e .N:/ re #lt * De &eman&ing analytical re"#irement o. t$i re i&#e* T$e . w$ic$ wa #ne. S1' val#e &etermine& . 2001 22 ! can be een. t$ey are believe& to be t$e main re %on ible . t$e total tr#ct#ral "#ality %arameter (TS1')* T$i remarkable re #lt i believe& to &e%en& on t$e tr#ct#ral "#ality o.ten ion* 0n t$e ot$er $an&.erence i attrib#te& to t$e con i&eration ma&e &#ring average molec#lar %arameter (!:') calc#lation* -owever. 1*20* In t$i ca e..N:/ #gge t t$i o%tion a a better alternative .INT-8989..rom CN re i&#e %re&icte& $ig$er conver ion .raction o.

1 N*rm"$ A$8.orm a erie o. RICO 'r*. met$yl. normal an& branc$e& alkyl c$ain &i trib#tion tart in C< com%onent .ormation relate& to t$e e %eci. %olymet$ylene bri&ge an& $y&roaromatic (na%$t$enic) tr#ct#re * /emark abo#t t$e e re #lt are &i c# e& a .i+ SARA Fr"c)i*+-.ic#lt to analy+e a e ter &erivative beca# e o. N*rm"$ A$8. !lkyl i&e c$ain attac$e& to aromatic carbon in aromatic.ie&.raction . t$i met$o&ology not a&o%te& in t$e %re ent work. ali%$atic #b tit#ent were i&enti.6.i+ Ar*m")ic Fr"c)i*+-. t$eir $ig$ volatility.e Ch"i+-.ollow.6 S)ruc)ur"$ De)"i$. /IC0 reaction wa %er.-i-. t$e n-alkyl i&e c$ain . t$ey are lo t &#ring t$e eva%oration %roce&#re %er.INT-8989.rom t$e t#&ie& re i&#e .1. 3. 2001 27 5ee& tock A( CN 'ro&#ct '-val#e 1*20 1*20 Conver ion (I) 19*8 72*B 3.or all .ort#nately.6. To get a &ee%er knowle&ge abo#t ali%$atic &i trib#tion in aromatic. n-alkanoic aci& * T$e e %ro&#ct were "#anti. '23S!-INT434' . Normal alkyl i&e c$ain .rom C 2 to C28 an& #% to C77 (19-21)* -owever. $orter c$ain (.orme& a wa a %revio# te% to t$e HC-:S analy i (11-21)* Ion C$romatogra%$ic o t$e in. re in an& a %$altene .*3 A$i1h")ic Su#-)i)ue+).ic tec$ni"#e $a been # e& to olve t$i %roblem (18-20)* Mn.1. t$en t$e re #ltant aci& .uc) A+"$. t$e / gro#% are normal alkyl gro#% .$ Si. #b tit#ent wa lo t* ! a con e"#ence.orm o.ragment ion* !#t$or $ave re%orte& lengt$ o.raction analy+e&* 3.rom C2 to C8) are &i.e ter by t$e mA+ B9 . branc$e& alkyl i&e c$ain . re in an& a %$altene molec#le can be converte& to alkanoic aci& by /IC0 a $own i c$eme 1 (9-21)* I.$ Ch"i+.orme&* 5o#r kin& o.ie& by HC-:S in t$e ..

re in an& a %$altene (9-21)* =ork relate& to t$e c$aracteri+ation o.raction o. '23S!-INT434' C27 .i&ation $a been #cce .#lly # e& in t$e c$aracteri+ation o.2 N*rm"$ A$8. ma.INT-8989. 2001 29 /IC0 o.raction* /e #lt are &i c# e& in t$e ne. t$e alkyl c$ain* 5or A( re i&#e.6. w$ic$ &ecline wit$ increa ing lengt$ o.imi+ing at C9.raction o. C1< (t$e mo t ab#n&ant) an& C18 com%onent * 12 AL 10 Relative Area (%) 8 6 4 2 0 C7 C10 C11 C13 C14 C15 C18 C19 C22 CN C25 C26 C6 C8 C9 C12 C16 C17 C20 C21 C23 C24 Figure !6 Normal-alkyl c$ain &i trib#tion in t$e aromatic . A( aromatic molec#le are enric$e& in longer b#t le ab#n&ant n-alkyl c$ain * 3.raction by t$i c$emical met$o& $a not been re%orte& #% to now* It i im%ortant to %oint o#t t$at t$i i t$e . n-alkyl c$ain &i trib#tion tart in C< an& en& in C2B.$ Ch"i+. CN re i&#e. aromatic . A( an& CN re i&#e In t$e ca e o.ir t work &one on t$i .1. &i trib#tion begin in C< an& en& in C28N $owing %ick at C8 (mo t ab#n&ant) an& C1<* In t$i latter ca e.t %aragra%$ * 5ig#re 8 $ow n-alkyl c$ain &i trib#tion in t$e aromatic . A( an& CN re i&#e * ! bimo&al &i trib#tion wa ob erve& in bot$ ca e .i+ Re-i+ Fr"c)i*+-. &i trib#tion &ecline almo t monotonically an& it i ob erve& enric$ment in $orter c$ain (C < to C11)* In contra t.

'23S!-INT434' C26 C10 C11 C12 C13 C16 C17 C18 C19 C23 C24 C6 C7 C8 C9 . C9.6. A( re in molec#le com%onent .3 N*rm"$ A$8. Normal alkyl c$ain &i trib#tion in A( an& CN re in .raction * -owever. C1< an& C18 com%onent in bot$ .$ Ch"i+.INT-8989. C1< an& t$e le e.raction #tie&* It i ob erve& a m#ltimo&al &i trib#tion t$at tart in C< an& en& in C28 .ce%t in C<.raction .i+ A-1h"$)e+e Fr"c)i*+-. C19. 3. normal alkyl i&e c$ain in t$e re in . e.or t$e A( ca e an& in C2< .1.or t$e CN ca e* -ig$er %ick are reac$e& at C9. 2001 28 5ig#re 9 $ow &i trib#tion o.$ibit a mall enric$ment in almo t all ab#n&ant b#t longer C22 to C2< #b tit#ent * 16 14 Relative Area (%) 12 10 8 6 4 2 0 C14 C15 C20 C21 AL CN C22 C25 Figure 9.

A$8.y . α-branc$e& n-alkyl #b tit#ent .orm branc$e& alkanoic aci& #n&er /IC0 con&ition (Sc$eme 1)* -owever.or α-met$yl &erivative . (9-21) 6ranc$e& alkyl c$ain .or α-%ro%yl &erivative .raction 3. mA+L 11< .rom C17 to C29)* 20 18 16 Relative Area (%) 14 12 10 8 6 4 2 0 C14 C15 C20 C21 C26 C10 C11 C12 C13 C16 C17 C18 C19 C22 C23 C24 C25 C6 C7 C8 C9 AL CN Figure 1 6 Normal alkyl c$ain &i trib#tion in A( an& CN a %$altene . 2001 2< !lkyl c$ain &i trib#tion in a %$altene . w$erea CN a %$altene molec#le $ave a m#ltimo&al &i trib#tion .ie& a met$yle ter by t$e mA+L 88 . w$ere t$e α-%e&ant gro#% were met$yl.amilie &erive . an& mA+L 170 .rom α-branc$e& alkyl aromatic tr#ct#re %re ente& in re in an& a %$altene .ragment ion . b#t A( a %$altene are in longer com%onent ( .raction (5ig#re 11)* !n& are "#anti. et$yl..6.erent in bot$ re i&#e (5ig#re 10)* A( a %$altene molec#le e.or α-b#tyl &erivative * I o%renoi& #b tit#ent were i&enti.e Ch"i+-. CN a %$altene are enric$e& in $orter alkyl c$ain (.ie& too* '23S!-INT434' .#nctionalitie * T$e e .2 9r"+che. a#t$or %oint o#t t$at t$ey are %re ent in re in an& a %$altene molec#le in low concentration (9-21)* Stra# + an& co-worker (18) $ave i&enti. n-%ro%yl an& n-b#tyl .$ Si.amilie o.o#r .raction were "#ite &i. mA+ L102 α-et$yl &erivative .rom C< to C28 wit$ $ig$er %ick locate& at C9 an& C1< re %ectively* !&&itionally.$ibit a ga# ian n-alkyl c$ain &i trib#tion w$ic$ begin in C< an& en& in C28 reac$ing t$e $ig$e t %ick at C1<.rom C < to C11).INT-8989.

INT-8989. only α-met$yl alkyl c$ain were i&enti.orm A( aromatic .raction * It i ob erve& a bimo&al &i trib#tion .raction molec#le are in $orter b#t more ab#n&ant one '23S!-INT434' .6.or CN aromatic . molec#le . 'rec#r or tr#ct#re o.amilie were in #c$ low concentration t$at it wa im%o ible to analy+e t$em #n&er t$e # e& in tr#mental con&ition * 3.e Ch"i+. b#t it &ecline are enric$e& in longer b#t le (.raction ab#n&ant branc$e& #b tit#ent (C 19-C28)N w$erea t$e corre %on&ing CN aromatic .or A( aromatic i longer t$an t$e one ob erve& in CN (. t$e t#&ie& aromatic . 2001 2B ( )n 17 1! ( )n ( )n 1! 19 ( )n Figure 11. α-met$yl alkyl c$ain &i trib#tion . α-et$yl.2.1 9r"+che. t$e ot$er .ie&. α-met$yl. A$8.i&ation o.i+ Ar*m")ic Fr"c)i*+-.raction t$at tart in C< an& en& in C1B* -ig$er %ick are reac$e& at C8 an& C17* In contra t. α-n-%ro%yl an& α-n-b#tyl alkyl c$ain * In t$e %re ent work. 5ig#re 12 $ow α-met$yl alkyl c$ain &i trib#tion obtaine& #n&er /IC0 o.$ Si.rom C< to C28).rom C< to C17)* moot$ly wit$ lengt$ c$ain* -ig$er %ick are ob erve& at CB an& C17* !&&itionally.

i+ Re-i+ Fr"c)i*+-* In t$e ca e o. A( an& CN re in .2 9r"+che. 2001 28 18 Area Relativa (%) 16 14 12 10 8 6 4 2 MeC10 MeC11 MeC14 MeC15 MeC17 MeC18 MeC19 MeC20 MeC21 MeC22 MeC25 MeC25 AL CN MeC12 MeC13 MeC16 MeC23 MeC23 Figure 12.ce%t in CB.ten&e& .$ Si.raction '23S!-INT434' MeC24 MeC6 MeC7 MeC8 MeC9 0 . A( an& CN aromatic . re in .INT-8989.e Ch"i+.raction i bimo&al an& t$e ame incl#&e C< to C29 #b tit#ent * !not$er . α-met$yl alkyl c$ain &i trib#tion o.2.raction : A( re i&#e $owe& an almo t a# ian &i trib#tion e.raction 3.eat#re ob erve& i t$at A( re in . C8 an& C17 #b tit#ent (5ig#re 17)* 16 Area Relativa (%) 14 12 10 8 6 4 2 MeC10 MeC11 MeC12 MeC13 MeC14 MeC15 MeC16 MeC17 MeC18 MeC19 MeC20 MeC21 MeC22 MeC24 MeC6 MeC7 MeC8 MeC9 0 AL CN Figure 13.raction molec#le are enric$e& in almo t all it com%onent in com%ari on wit$ CN $omolog#e e.6. A$8.rom C< to C22* 2i trib#tion in CN re in . α-met$yl alkyl c$ain &i trib#tion o.

%olymet$ylene bri&ge ranging .raction 3. ω- 'olymet$ylene bri&ge na%$t$enic tr#ct#re a &icarbo. A$8.$e+e 9ri.$ Si. a %$altene .6.i&i+e& to C0 2 (17.3 9r"+che.raction i enric$e& in all it α-met$yl alkyl c$ain #b tit#ent com%are& to t$e corre %on&ing CN .erence were ob erve& in t$e α-met$yl alkyl c$ain &i trib#tion o.INT-8989.2..e Ch"i+.rom C< to C22* ! a remark. branc$e& c$ain m#ltimo&al &i trib#tion o.me)h.geconnecte& to two aromatic y tem are o. branc$e& c$ain in A( a %$altene molec#le i concentrate& in t$e C12-C20 region* In ot$er $an&. 2001 29 3.raction* 20 Area Relativa (%) 18 16 14 12 10 8 6 4 2 MeC11 MeC12 MeC13 MeC14 MeC16 MeC17 MeC18 MeC21 MeC22 MeC10 MeC15 MeC19 MeC20 MeC9 MeC6 MeC7 MeC8 0 AL CN Figure 13. α-met$yl alkyl c$ain &i trib#tion o. C9-C< &iaci& can ari e .i+ A-1h"$)e+e Fr"c)i*+:ore &ramatic &i. CN a %$altene .rom $own in c$eme 2 (9-20)* Stra# + an& co-worker $ave re%orte& &i trib#tion o.6.raction %rea& .raction (5ig#re 19)* :onomo&al &i trib#tion o. A( an& CN ! %$altene .rom C 9 to C77* C2 an& C7 &iaci& are #n table #n&er /IC0 con&ition an& t$ey are . A( a %$altene .#rt$er o.i&i+e& to α.3 '*$.ylic aci& #n&er /IC0 con&ition * -owever.1<)* In t$e '23S!-INT434' .

me)h.i+ Ar*m")ic Fr"c)i*+-.ylic aci& (%olymet$ylene bri&ge ) were analy+e& by HC-:S a met$yl-e ter # ing mA+ L 89 .ragment ion wit$ lengt$ c$ain* In longer c$ain . t$e &ecrea ing inten ity o.3. mA+L 98 .$e+e 9ri.ge.ragment ion . mA+ L 89 .raction '23S!-INT434' .raction S$orter C$ain (C9-C9) 50 Relative Area (%) 45 40 35 30 25 20 15 10 5 0 C4 C5 C6 C7 C8 C9 AL CN Donger C$ain (C10-C19) 25 Relative Area (%) 20 AL 15 10 5 0 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 CN C 18 C 19 Figure 15.ragment ion ignal became more inten e* 3. t#&ie&* 5ig#re 18 $ow %olymet$ylene bri&ge &i trib#tion .or t$e aromatic .1 '*$.or longer com%onent (C10-C20)* 2i trib#tion were %lit beca# e o. 'olymet$ylene bri&ge &i trib#tion in A( an& CN aromatic .ragment ion to t$e $orter com%onent (C9-C9) an& mA+L 98 .INT-8989. 2001 70 %re ent work.6. &icarbo.

3.raction* '23S!-INT434' . C8. CN aromatic molec#le are enric$e& in C8.raction in com%ari on wit$ t$e ame A( .raction e.raction molec#le * -owever. an& C1B-C19 com%onent wa ob erve& in t$e CN re in .$e+e 9ri. relative ab#n&ance. enric$ment in C 9. C 12.ten& #% to C1B* Concerning to t$e relative ab#n&ance. A( re i&#e.rom C9 to C19.raction . Similar monomo&al $a%e were . C1< an& C1B c$ain * 3.raction i %rea& #% to C19 wit$ %rominent %ick at C8 an& C12 re %ectively* In term o. 2001 71 In bot$ aromatic .rom C9 to C1B wit$ $ig$er %ick at C8 an& C11N w$erea &i trib#tion in CN re in .o#n& in %olymet$ylene bri&ge &i trib#tion o. CB. CB. C12.ge. C8 $orter com%onent an& in almo t all t$e longer #b tit#ent wit$ t$e e.raction molec#le e. re in .6.rom A( an& CN re i&#e (5ig#re 1<)* A( re in .INT-8989.raction .$ibit a total &i trib#tion . C11 an& C12 #b tit#ent * Similar $ig$er %ick are ob erve& in CN aromatic . wit$ $ig$er %ick locate& at C8. t$e &i trib#tion e.ce%tion o.2 '*$. $ort %olymet$ylenic c$ain &i trib#tion $a%e t$at &ecline $owe& a monomo&al moot$ly wit$ increa ing lengt$ c$ain* ! imilar tren& i ob erve& in longer %olymet$ylenic #b tit#ent * In t$e ca e o.Fr"c)i*+-. C18.me)h. aromatic .$ibit a &i trib#tion ranging .i+ Re-i+.

2001 72 S$orter C$ain (C9-C9) 40 Relative Area (%) 35 30 25 20 15 10 5 0 C4 C5 C6 C7 C8 C9 AL CN Relative Area (%) Donger C$ain (C10-C19) 25 20 15 10 5 0 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 A( CN Figure 16.raction * 5ig#re 1B $ow t$e re #lt obtaine&* 'rominent Nevert$ele .raction 3.$e+e 9ri.rom C9 to C18.i+ A-1h"$)e+e Fr"c)i*+-.ge. %olymet$ylenic bri&ge &i trib#tion in A( a %$altene range& .INT-8989. &i..raction %ick are reac$e& at C8 an& C12 com%onent ob erve& in aromatic an& re in .me)h.3 '*$. $owe& t$e ame monomo&al %attern a well a in aromatic an& re in * 'olymet$ylenic bri&ge in a %$altene .6. 'olymet$ylene bri&ge &i trib#tion in A( an& CN re in .3.erence in relative ab#n&ance an& lengt$ c$ain were ob erve&* T$# . w$ere t$e C8 '23S!-INT434' .

C8.icant ab#n&ance in C9. C19.raction '23S!-INT434' . 2001 77 an& C12 com%onent were t$e mo t im%ortant* 4nric$ment in C <-C9 an& C17.raction* It en& at C1< wit$ $ig$er %ick in C8 an& C12 an& a igni. 'olymet$ylene bri&ge &i trib#tion in A( an& CN a %$altene . C10-C12 an& C18-C1< #b tit#ent * S$orter C$ain (C9-C9) 40 Relative Area(%) 35 30 25 20 15 10 5 0 C4 C5 C6 C7 C8 C9 AL CN Donger C$ain (C10-C18) 30 Relative Area (%) 25 20 15 10 5 0 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 AL CN Figure 17.ten&e& a in A( $omolog#e . C1B an& C18 #b tit#ent wa ob erve& in contra t wit$ t$e ame com%onent in CN a %$altene * 'olymet$ylenic bri&ge &i trib#tion in CN a %$altene i not o e.INT-8989.

t$e o. 6.i+ Ar*m")ic "+.#lly ($y&roaromatic tr#ct#re )* T$# .i&ation o. w$ic$ mean t$at tr#ct#re a !.raction . Re-i+ Fr"c)i*+- Tren& in $y&roaromatic tr#ct#re &i trib#tion in aromatic an& re in .yb#tane (C9 triaci&) an& 1.o#n&.y-b#tane (C9-tetraaci&) were i&enti. 1.2.raction * '23S!-INT434' /e in .7.#b tit#te& alkyl bri&ge an& t$e o.raction .2.ragment ion* C9 tetraaci& wa not ob erve& in all t$e t#&ie& ca e * 3. an& 7 $owe& in Sc$eme 7* /elate& to t$e A( aromatic an& re in .7-tricarbo.1 0.rom t$e latter %rec#r or #cce . an& 1 (Sc$eme 7) &ominate in t$e e . %artially at#rate& con&en e& tr#ct#re (Sc$eme 7)* It i believe wit$ $ig$ %robability t$at t$e e %ro&#ct ari e .y %ro%ane (C7 triaci&)..raction o.ie& by t$e mA+ L12B .i&ation o. t$e $ig$ concentration o.r*"r*m")ic S)ruc)ure-. CN re i&#e t$at are imilar to t$e tr#ct#re 5.ie& ome alkyl %olycarbo.raction o.tetracarbo.lect o.. 2#ring /IC0 reaction e.6.9-tricarbo.%erience .ragment in aromatic an& re in . only C7 an& C9 triaci& were i&enti.4.r*"r*m")ic S)ruc)ure. 2001 79 3. $y&roaromatic . Nom#ra an& co-worker (18-1B) i&enti. 1. bot$ re i&#e were very imilar (5ig#re 18)* In t$e e .4 0.INT-8989. t$ree or more aryl.ie& by HC-:S a met$yle ter * In t$e %re ent work. 9.ylic aci& a %o ible %ro&#ct o.6. an enric$ment in C 9 triaci& wa .2. CN re i&#e $owe& $ig$er content in C7-triaci& %ro&#ct com%are& to t$e C9 $omolog#e* T$i re #lt i a re.9.

2i trib#tion o..raction wa &i.ylic aci& a re%re entative %ro&#ct o. A( a %$altene molec#le $y&roaromatic %ortion $owe& a $ig$er content in imilar to t$e 5.. t$e relative ab#n&ance C 7-triaci&A C9-triaci& ratio c$ange& in bot$ re i&#e* T$# .i+ A-1h"$)e+e Fr"c)i*+-y&roaromatic &i trib#tion in a %$altene .4.6. $y&roaromatic tr#ct#re in A( an& CN aromatic an& re in .!romatic INT-8989.2 0. an& 7 tr#ct#re (Sc$eme 7)* T$i concl# ion i #%%orte& by t$e $ig$er concentration o.raction 3.raction* '23S!-INT434' . 2001 78 80 Relative Area (%) 70 60 50 40 30 20 10 0 /e in CN AL C3 C4 55 Relative Area (%) 54 53 52 51 50 49 48 47 46 45 CN AL C3 C4 Figure 1!. 6. C7-triaci& ob erve& in t$i a %$altenic .erent t$an t$o e ob erve& in aromatic an& re in (5ig#re 19)* In t$i ca e. C7 an& C9 tricabco.r*"r*m")ic S)ruc)ure.

INT-8989.ylic aci& a re%re entative %ro&#ct o. 2i trib#tion o. w$ic$ mean t$at in t$i .raction* 5ig#re 20 '23S!-INT434' .ollowe& by %olymetylene bri&ge .7 4r*u1 Di-)ri#u)i*+To get a better knowle&ge o.raction o. bot$ re i&#e * ! %$altene CN AL 56 Relative Area (%) 54 52 50 48 46 44 42 C3 C4 Figure 19. in all . ali%$atic gro#% to t$e conver ion val#e o.raction normal alkyl c$ain are t$e mo t ab#n&ant ali%$atic gro#%.raction 3.l#ence o. 9 an& 1 %re&ominate over tr#ct#re 5. 2001 7< In t$e ot$er $an&. CN a %$altene $owe& a $ig$er content in C4 triaci&. C7 an& C9 tricarbo. an& t$e le $y&roaromatic tr#ct#re * ab#n&ant branc$e& alkyl c$ain an& t#&ie& . $y&roaromatic tr#ct#re in A( an& CN a %$altene . . an& 7 (Sc$eme 7)* T$e o%%o ite re #lt wa obtaine& in aromatic an& re in . global &i trib#tion were con i&ere& in eac$ $ow t$e e re #lt * ! can be een. SCSC %roce . t$e in.raction tr#ct#re !. 6.

raction .INT-8989.rom A( an& CN re i&#e '23S!-INT434' . re in an& a %$altene . 2001 7B 100 90 Relative Area (%) 80 70 60 50 40 30 20 10 0 n-alkyl chains Bridges Branched Chains Hydroaromatics Ar*m")ic- CN AL 80 70 Relative Area (%) 60 50 40 30 20 10 0 n-alkyl chains Bridges Branched Chains Hydroaromatics Re-i+- CN AL 80 70 Relative Area (%) 60 50 40 30 20 10 0 n-alkyl chains Bridges Branched Chains Hydroaromatics A-1h"$)e+e- CN AL Figure 2 . !li%$atic Hro#% Contrib#tion in aromatic.

raction * -owever.ir t ob ervation t$at ari e .raction* In contra t.rom A( an& CN re i&#e e timate& . re in an& a %$altene .raction ..rom %ectro co%ic &ata* 110 105 Relative Area (%) 100 95 90 85 80 Aromatics Resins Asphaltenes CN AL Figure 21.rom /IC0 re #lt * '23S!-INT434' ..erence wa ob erve& in a %$altene . Total ali%$atic gro#% content in aromatic.raction . re in an& a %$altene .raction relative concentration wa almo t t$e ame in bot$ re i&#e * ! noticeable &i. A( aromatic . #b tit#ent * Concerning to $y&roaromatic tr#ct#re .raction %re ente& a very low ab#n&ance in com%ari on wit$ re in an& a %$altene .raction in A( re i&#e* T$e e tren& can be ob erve& in 5ig#re 21 an& t$ey are in agreement wit$ t$e S1' val#e calc#late& .$ibit a maCor content in t$i kin& o. ali%$atic tr#ct#re .rom CN re i&#e are more enric$e& in #c$ tr#ct#re t$an t$e ame . 2001 78 T$e . aromatic . w$erea . A( a %$altene were more enric$e& in t$i com%onent t$an t$e CN $omolog#e .raction .rom bot$ re i&#e $ave almo t t$e ame content o. in t$e ca e o.INT-8989.ect i t$at aromatic . n-alkyl c$ain . re in an& a %$altene .raction in A( re i&#e* -owever.rom CN re i&#e are enric$e& in %olymet$ylenic bri&ge an& branc$e& c$ain com%are& to t$e ame .rom t$e e re #lt i t$at aromatic. CN re in an& a %$altene e. in re in .raction $owe& $ig$er ab#n&ance t$an t$e corre %on&ing CN .raction* T$e global e.

orm more con&en e& aromatic y tem t$at co#l& be re %on ible .! 4r*u1 C*+)ri#u)i*+!ccor&ing to t$e SCSC %ilot %lant te t re #lt an& to t$e /IC0 in.INT-8989. we can %ec#late abo#t reactivity tren& . normal alkyl c$ain are believe& to contrib#te t$e mo t to t$e conver ion toget$er wit$ %olymet$ylene bri&ge an& branc$e& alkyl c$ain (in le e. attack (5ig#re 22)* -y&roaromatic tr#ct#re are t$o#g$t to $ave a lower contrib#tion beca# e t$ey can eit$er e.or coke .ormation.ten ion)* 'olymet$ylene bri&ge are believe& to be t$e mo t reactive gro#% among t$e e #b tit#ent beca# e t$ey $ave two %o ible %oint o. 2001 79 3.%eriment &ealkylation to . 'o ible alkyl gro#% contrib#tion to t$e conver ion o.ormation (5ig#re 22)* Figure 22.or eac$ ali%$atic gro#% an& it contrib#tion to t$e conver ion val#e* T$# . SCSC %roce '23S!-INT434' .orm lig$ter $y&rocarbon %ro&#ct or &e$y&rogenation to .

ali%$atic gro#% t$at co#l& e.raction * /IC0 re #lt rein.ee& tock be$avior #n&er SCSC con&ition * -owever.INT-8989. CONC(USION Str#ct#ral c$aracteri+ation o. ali%$atic #b tit#ent . w$erea .#l %re&ictive tool .raction ric$ in alkylaromatic tr#ct#re .N:/ &ata. b#t al o by t$e "#ality o.ormation obtaine&.rom 1 .orce& t$e %ectro co%ic in. #c$ #b tit#ent * T$# . w$ic$ i in agreement wit$ t$e S1' val#e calc#late& .%lain t$e ob erve& be$avior o. normal alkyl c$ain an& %olymet$ylene bri&ge were t$e mo t ab#n&ant alkyl #b tit#ent . S!/! . t$em in term o.or Selective Catalytic Steam Cracking (SCSC)* It $a been &emon trate& t$at SCSC conver ion level are in.or ro#tine analy i &#e to t$e le /elate& to t$e tr#ct#ral &etail o. 2001 90 4. /IC0 %ro&#ct analy i gave ome in ig$t abo#t reactivity o.rom /:N &ata* !&&itionally. S1' val#e .l#ence& not only by t$e ab#n&ance o. are more acc#rate t$an t$o e calc#late& .raction . S!/! . ince no a #m%tion . calc#late& . beca# e re in an& a %$altene . t$e t#&ie& re i&#e #n&er SCSC con&ition * '23S!-INT434' .raction . a tr#ct#ral "#ality %arameter (S1') wa &e. branc$e& alkyl tr#ct#re $owe& lower concentration in all t$e t#&ie& .N:/ %arameter are analytical &eman& involve&* a viable alternative .rom CN re i&#e were ric$er in ali%$atic tr#ct#re t$an t$e ame A( .rom 17C N:/ &ata.ormation abo#t &i trib#tion c$ain an& $y&roaromatic o. Cali%$aticACaromatic ratio * 6a e& #%on 17C an& 1.ine&* T$i %arameter co#l& be # e& to %re&ict . /IC0 reaction gave val#able in.N:/.or !:' calc#lation are re"#ire&* 1.rom vac##m re i&#e i a # e.

INT-8989. t$e in. aromatic y tem an& t$e ma balance t$at incl#&e C0 2 mea #rement (com%lementary /IC0 in.ormation %re ente& in t$i work corre %on& to t$e %artial c$aracteri+ation o. 2001 91 5.ee& tock * In t$i i #e. vi breaking an& !"#aconver ion® %ro&#ct * '23S!-INT434' . SCSC . t$e re #lt &i c# ion. tate& at t$e beginning o.ormation) are in %rogre an& will be %re ente& in a econ& i #e toget$er wit$ c$aracteri+ation o. ! FINA( COM%NTS. we $ave only &i c# e& ali%$atic #b tit#ent &i trib#tion * In.ormation regar&ing to t$e con&en ation mo&e o.

i&ation an& 2ecarbo. I*N Salerno.i&e in 'etrole#m* 0rg* Heoc$em* 9. 4*N an& 5eint#c$. %%. 'etrole#m C$emi try. Illinoi No* < :onterey Coal* 5#el* 89.or t$e St#&y o. D*N DP%e+. <9-<8* (8) -ig#erey. /* 3i iPn TecnolPgica* <* No* 1. 2001. I*N !n&riollo. !%ril 1-8. 1998* 'ereira. D*N :ar+On.icacione 1#Omica y 4 tr#ct#rale In&#ci&a %or el 3a%ocra"#eo TermocatalOtico &e Cr#&o 'e a&o y /e i&#o * :emoria &el I3 Congre o 3ene+olano &e 1#Omica* :Rri&a* 4&o* :Rri&a. 0* '* S#l. 1987 '23S!-INT434' . I*N 'ereira. C*N 2#"#e. I*N -ernQn&e+. 11.tra%e a&o en '23S!-INT434'. '*N :ac$in. 11B1-118B. 2001 92 R%F%R%NC%S (1) (2) 'ereira. '*N KacarOa . E*N S+eoke. H*N Cotte. Deon :* !n& T e. S#l. E*N 5lore . E*N an& Solari.i&e. 98B-99B.ore t$e 2ivi ion o. /*N /iva . 9B9-9B<. '*N :ar+in. -ogg. C!. 78B-7<9. San 2iego. '*. 98-87.ylation* ! reaction Se"#ence . E* 2*. 0* '* :olec#lar Str#ct#re o. /*N KacarOa . 8-19. Deon :* an& 0beg :arc# * 0. Fwok-t#en* /#t$eni#m Tetro. !t$aba ca ! %$altene .i&e Cataly+e& 0.i&ation o. 3* Sym%o i#m on Cr#&e 0il M%gra&ing . :orale -I+"#ier&o. 4*N -ig#erey.INT-8989.i&ation o. Deon :* !n& T e. !"#aconver iPn®* !cta CientO. E*N KacarOa . 1980* Stock. 5*N CPr&ova.ica 3ene+olana* 3ol* 80 S#%lemento 1. I*N an& 'ereira. Fwok-t#en* /#t$eni#m Tetro. !*.i&e Cataly+e& 0. '* :o&i. H* Da Inve tigaciPn y 2e arrollo en :eCoramiento &e Cr#&o 4. <99-<98.rom /e ervoir to /e.inery 're ente& 6e. 2* S* !n& Stra# +. 1999* (7) (9) 'ereira. D*N -#o&e. 199B* (8) Stock. -* 'etrole#m Tec$nology 1"#artarly* =inter 1998-1999N %% 29-7B -ig#erey. 4t$er an& 4 ter Dinkage * 4nergy S 5#el * 11. Stra# +. '*N an& DePn. 3ene+#ela* B-11 5ebrero. :ontgomery. Illinoi No* < Coal an& Some /e%re entative -y&rocarbon * 5#el* <2. !*N CPr&ova. 199B (9) (10) Stock. Inc* 221 t !CS :eeting. !*. 198<* 'eng. 1999* <80-<82* (<) (B) 'ay+ant. !romatic Str#ct#ral 4lement in 'oca$onta No* 7 Coal* 4nergy S 5#el . %%.

:#rata. 6o can an& 2#ri ! %$altene * 4nergy S 5#el * 17. 2. 0* '*N :oCel ky. 12<8-12B1. :*N !rtok. 1B17-1B1B. 17B9-1787. :*. 5*N Down 4* :*N an& 'eng. 2* S*. :#rata. D*N :#rata. 2*2*. :* St#&ie on !li%$atic 'ortion o. 1988* (12) :oCel ky. 1999* (20) Stra# +.i&e Cataly+e& 0. 2001 97 (11) Stock. S*. T* =*N an& Down. !*N Down. K*. 0* '* Str#ct#ral 5eat#re o. 1998* S#. an& =ang S* /#t$eni#m Tetro. Stra# +. T* =*. S*N M-e aka. T* =*N 5araCi. D*. !t$aba ca 0il San& 6it#men* !0ST/! E* /e *. 791-798. :ontgomery. an& Nom#ra.INT-8989. 2* S*. Kao K$#ang Coal* 4nergy S 5#el * 12. !rtok. D*.i&ation* 4nergy S 5#el * 8. :*. '* !&&itional Str#ct#ral 2etail o. 1999* (21) 'eng. Stra# +. 1998* Nom#ra. !n Mn. 0* '*N :oCel ky. Coal 0rganic :aterial 6a e& on /#t$eni#m Ion Cataly+e& 0. ! %$altene. 1999 (18) (1<) (1B) !rtok. I*N an& 6e$ar. Illinoi No* < Coal* T$e 5ormation o. 4* :*N an& Stra# + 0* '* C$emical Str#ct#re an& 6iomarker Content o. T*.ication * 4nergy S 5#el * 17. 1998* (18) (19) Stra# +. t$e ! %$altene 5raction o. Igna iak. 0* '* /#t$eni#m (3III) Cataly+e& 0. 4* :*. -*N an& Fi&ena F* Str#ct#ral 4val#ation o.amination o. Sato$. T* =*. F*N Ino-#e. :cIntyre. !lberta 0il San& 6it#men an& -eavy 0il ! %$altene * 4nergy S 5#el * <. '*N :orale -I+"#ier&o. !*N -ama. 87-9<.t#re by a /#t$eni#m-Ion-Cataly+e& 0. S*N Tamamoto. 1992* Stra# +.ol&ing Story* 5#el* B1.i&ation o. !t$aba ca ! %$altene an& T$eir /ami. Eing$an ! %$altene an& Ferogen * 4nergy S 5#el * 17. T* :*. 5rakman. T* /ee. 1999* '23S!-INT434' . t$e /IC0 :et$o&* 4nergy S 5#el * 12. S*. an !rabian :i. 1.ylic aci& * 5#el* <9. Down. 298-2<8. 171-17B. :ontgomery. D*. -ig$ :olec#lar =eig$t Com%onent o. -*N an& Nom#ra.i&ation /eaction* 4nergy S 5#el * 12. 1988* (17) :oCel ky. 4* :* T$e :olec#lar Str#ct#re o. 20B-22B. :* Str#ct#ral !naly i o.i&ation o. T* =*N Down 4* :*N Fowalew ki. -*N Hao. 1788-17<7. 1991 (19) :#rata. 5* Str#ct#ral 5eat#re o. 228-29B. an& Nom#ra. 3olatile :onocarbo. 0* '*N :oCel ky. 812-827.

288-289. E* H* T$e C$emi try an& Tec$nology o. I+"#ier&o !* 're%arative an& !#tomate& Com%o#n& Cla e%aration o. N*T* C$a%ter 8N %%. 1991* '23S!-INT434' . 3* !verage :olec#lar =eig$t o. 1989* (29) (28) (2<) DePn. 'etrole#m* Don&on. 1987* S%eig$t. 0il 5raction /e onance* 5#el.INT-8989. ! %$altene in 0il* '-3al#e* 10<<-87. 3ene+#elan 3ac##m /e i&#a by -ig$ 'er. 799-908. 'e%ti+ation o. D*. << (10)N 1998-199<. 198B* by N#clear :agnetic S$ell :ete& Serie * State o. 2001 99 (22) (27) I'-197A90* ! %$altene (-e%tane In ol#ble ) in 'etrole#m 'ro&#ct * In tit#te o.ormance Di"#i& C$romatogra%$y* Eo#rnal o. C$romatogra%$y* 989. 1990* Carbognani. 'etrole#m* 2J 4&ition* :arcel 2ekker.