SUMMARY
Selective Catalytic Steam Cracking (SCSC), better known a tec$nology, i a %roce t$at combine
!"#aconver ion
&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 *
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1.
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 $ave a %re,erence ,or breaking CS% -CS% bon& locate& in -%o ition ,rom t$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
re in
&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$ni"#e *
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T$ermal Cleavage
/ /n>
=ater 2i ociation
/ ? /n>
-20
-y&rogen !&&ition
Cataly t
- ? 0-
/ ?
0.i&ation
/n> ? 2-
Cataly t
/ - ? /n -
/n@-1 ? C02 ? -2
/ ?
/n>
/n> /n> ? / /
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
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%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
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In t$i ca e, ,-&icarbo.ylic aci& are ,orme& by t$e o.i&ation o, na%$t$enic tr#ct#re a 1,2,7,9-tetra$y&rona%,talene (3) or cyclo%ro%ylben+ene (4) &erivative cannot be &i ting#i $e& ,rom t$o e one ,orme& by t$e o.i&ation o, , &i%$enylalkane (2) (9-21)* -owever, Nom#ra et al (18-1B) $ave %ointe& o#t t$at more com%le. na%$t$enic (-y&roaromatic) tr#ct#re can be ea ily in,erre& by t$e analy i o, alkane %olycarbo.ylic aci& ,orme& &#ring /IC0 reaction;
6 9 7 1 !
0 -0 0 -0 0 -0
0 -0 -0 0 -0 0
11
-00C
C00C00C00-
12
Scheme 3
I, t$i kin& o, tr#ct#re i %re ente& in re in an& a %$altene , alkane %olycarbo.ylic aci& are e.%ecte& to be ,orm &#ring /IC0 reaction*
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<
!not$er ,eat#re o, /IC0 reaction i t$at aromatic ring are not com%letely o.i&i+e& to C0 2 an& ome o, t$em remain a ben+ene &i, tri, tetra an& le ab#n&ant %enta an& $e.acarbo.ylic aci& (18)* Commonly, %olyaromatic tr#ct#re yiel& t$i kin& o, %ro&#ct * 5or e.am%le, w$en one o, t$e aromatic ring o, #c$ tr#ct#re i o.i&i+e&, a carbo.ylic gro#% i ,orme& on t$e a&Cacent aromatic ring* T$e &eactivating e,,ect o, t$e carbo.ylic gro#% avoi& t$e #b e"#ent o.i&ation o, t$e econ& ring* ! a con e"#ence, t$e latter remain a a ben+ene carbo.ylic aci& in t$e /IC0 %ro&#ct mi.t#re (18) (Sc$eme 9) C00/IC0 C02 ? C0013 Scheme 4
In contra t, alkyl gro#% on t$e ben+ene ring $ave an activating e,,ect* T$ere,ore (wit$ t$e e.ce%tion o, t$e met$yl gro#%) t$e alkyl- #b tit#te& ring i o.i&i+e& to C0 2 * !&&itionally, t$e %o ition o, t$e alkyl #b tit#tion &etermine w$et$er one or bot$ ring will be o.i&i+e&* I, t$e alkyl #b tit#ent i in a %o ition w$ere a carbo.ylic gro#% mig$t ,orm by t$e o.i&ation o, t$e $o t ring, t$e #n #b tit#te& ring will al o be o.i&i+e& (18) (Sc$eme 8);
14
15 Scheme 5
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:o t con&en e& aromatic molec#le wo#l& give more t$an one aci&* T$# , ,or e.am%le, %yrene can yiel& t$e 1,2,7-triaci& an& t$e 1,2,7,9 tetraci&; -00C -00C C0016
Scheme 6
Table 1 li t common ben+ene %olycarbo.ylic aci& ,o#n& in /IC0 %ro&#ct mi.t#re an& t$eir %o ible aromatic y tem %rec#r or (18-18)* ! can be een, t$e analy i o, ben+ene %olycarbo.ylic aci& %rovi&e inval#able in ig$t into t$e mo&e o, con&en ation an& %o ible tr#ct#re o, aromatic y tem containe& in re in an& a %$altene ,raction * T$# , t$e analy i o, /IC0 %ro&#ct toget$er wit$ t$e in,ormation %rovi&e& by
%ectro co%ic tec$ni"#e can give im%ortant tr#ct#ral &etail o, t$e mo t a,,ecte& S!/! ,raction &#ring SCSC %roce (i*e*, !romatic , /e in an& ! %$altene )* T$e co%e o, t$e %re ent work i to # e c$emical an& %ectro co%ic met$o& ,or t$e c$aracteri+ation o, two vac##m re i&#e ; !rabian lig$t an& Cerro Negro, in or&er to t#&y an& %re&ict t$eir be$avior #n&er SCSC (!"#aconver ion) con&ition *
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T"#$e 1* 'o ible %rec#r or o, ben+ene carbo.ylic aci& 6en+ene carbo.ylic aci& 'rec#r or 'o ible 'rec#r or
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2. 2.1
! %$altene ,rom two vac##m re i&#e (!rabian Dig$t (!D) an& Cerro Negro (CN) were obtaine& by %reci%itation wit$ n-$e%tane (-'DC gra&e, E*T 6aker) (22)* T$e re #lting maltene %ortion wa ,ractionate& into Sat#rate , !romatic an& /e in by %re%arative -'DC a in&icate& in re,erence (27)* S!/! ,raction were ,#rt$er c$aracteri+e& by elemental analy i (Carbon (C), -y&rogen (-), 0.ygen (0), S#l,#r (S), Nitrogen (N)), 3a%or '$a e 0 mometry (3'0), an& N#clear :agnetic /e onance %ectro co%y (1- N:/ an& 17C N:/)* 2.2 %$eme+)"$ A+"$,-i- "+. M*$ecu$"r /eigh) De)ermi+")i*+.
C, -, an& 0 were &etermine& in a D4C0 !naly+er, mo&el C-SN-972* S#l,#r wa &etermine& in a D4C0 !naly+er, mo&el I/ 972 an& Nitrogen, in a 2or$man !naly+er, mo&el 1000* !verage molec#lar weig$t wa &eterminate& in a Fna#er 0 mometer # ing C-2Cl2 an& C-Cl7 a 2.3
1
N:/ analy e were %er,orme& in a 6r#ker S%ectrometer !C'-900* 1- N:/ %ectra were ac"#ire& at 900 :-+ wit$ a 12 %%m win&ow an& a ,li% angle o, 98G* T$e recycle time wa 8 econ& an& T:S wa # e& a re,erence* Sam%le concentration wa 28 mgAmD in C- 2Cl2A CS2 1;1*
1
- N:/ &ata, carbon an& $y&rogen content &etermine& by elemental analy i , an& 3'0
molec#lar weig$t were # e& a in%#t &ata to calc#late !verage :olec#lar 'arameter (!:') by t$e met$o&ology re%orte& in re,erence (29)*
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10
2*9
17
13
C NMR S1ec)r*-c*1,.
C N:/ analy e were %er,orme& at 100*<19 :-+* !bo#t 900 mg o, t$e am%le were
&i olve& in a Cr (III) acetylacetonate A &e#terate& c$loro,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, 8 econ& between eac$ %#l e* 8000 %#l e were acc#m#late& in 12 $o#r * 2.5 RICO Re"c)i*+ 'r*ce.ure "+. CO2 Me"-ureme+)*
!romatic, re in an& a %$altene ,raction ,rom !D an& CN vac##m re i&#e were #bmitte& to /IC0 reaction a ,ollow; !bo#t 200*0 mg o, am%le, 12*0 mg o, /#Cl2*7-20, an& 9*0 g o, NaI09, were %lace& into a 280 mD ,lat bottom gla reactor %rototy%e, &e igne& to mea #re t$e %re #re o, C0 2 ,#nnel, <*0 mD o, evolve& &#ring t$e reaction, (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 $ermetically an& ,ille& wit$ N2 #% to reac$ a %re #re o, 7*0 % i* T$e $eterogeneo# mi.t#re wa magnetically tirre& ,or 29 $o#r at room tem%erat#re, &#ring w$ic$ t$e initial &ark brown color c$ange& to yellow %ale* !t t$i %oint t$e reaction wa to%%e& an& t$e ,inal %re #re wa mea #re&* CCl9, <*0 mD o, C-7CN an& 10 mD o, -20 were a&&e&* T$en, t$e reactor wa clo e&
Concentration o, t$e evolve& C02 wa mea #re& by # ing t$e H!ST4C colorimetric met$o&* H!ST4C No* 2- Carbon 2io.i&e &etector t#be wit$ a mea #ring range o, 110 I vAv (Ha tec Cor%oration) wa connecte& to t$e reactor N 2 inlet an& to t$e H!ST4C %#m% ,or t$e ot$er en&* T$en, 80*0 mD o, t$e ga containe& in t$e reactor were taken by #ction o, t$e H!ST4C %#m%* C0 2 wa ab orbe& on t$e %ackage a t$e ga %a e& t$ro#g$ t$e H!ST4C &etector t#be* ! color re %on e wa generate& in&icating C02 concentration level*
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11
!,ter C02 mea #rement, t$e reaction mi.t#re wa ,iltere& tro#g$ a 0*2 m %ore i+e Nylon-<< ,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 ,ormer wa ,#rt$er e.tracte& wit$ 10.2 mD o, C-2Cl2* =a $ing were combine& wit$ t$e original organic layer* !bo#t 180 mD o, a 0*1m: Na0- in met$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 NaI09 e.ce * !,ter tan&ing ,or a 29 $ %erio&, 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# %$a e an& concentrate& # ing a N2 tream*
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2.6
%-)eri3ic")i*+ 'r*ce.ure.
4 teri,ication o, /IC0 %ro&#ct wa carrie& o#t by a&&ing 8,0 mD o, a 19I ol#tion o, 65 7 in met$anol ('ierce C$emical) to t$e %ro&#ct ol#tion* T$e re #lting mi.t#re wa tirre& at room tem%erat#re ,or 12 $o#r * !,ter a&&ing t$e e teri,ier reagent, t$e yellow %ale color o, t$e %ro&#ct ol#tion c$ange& to re& beca# e o, io&ine liberation* To eliminate t$i inter,erence, abo#t 100 mg o, Kinc %ow&er wa a&&e& to re&#ce I 2 to I- (21)* T$en, t$e mi.t#re wa &rie& over Na2S09, ,iltrate&, an& concentrate& to 1*0 mD by rotary eva%oration at 70GC an& N2 tream* T$e met$yle ter ol#tion wa ,#rt$er analy+e& by HC-:S* 2.7 4C5MS A+"$,-i-.
HC-:S analy e were %er,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 . 0*28mm coate& wit$ 0*8 m 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%$ic con&ition in HC-:S analy i Initial T (GC) InCector Col#mn 280 78 5inal T (GC) 280 700 700 T /am% (GCAmin) 0 B nA 5inal T
2.!.
'ilot %lant te t were %er,orme& in a one barrelA&ay ca%acity %ilot %lant o%erate& at a ,i.e& tem%erat#re an& ,e& wit$ t$e !rabian Dig$t or t$e Cerro Negro vac##m re i&#e, team, an& t$e cataly t* T$e reaction wa to%%e& w$en %ro&#ct reac$e& a critical '-val#e o, 1*20 ('-val#e wa &etermine& a in&icate& in re,erence (28))*
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3.
R%SU(TS Negro vac##m re i&#e # e& a !1C an& 3i core&#ction ,ee& tock * In a econ& i #e, c$aracteri+ation o, !1C an& 3i breaking %ro&#ct will be %re ente&*
T$e ,ollowing %artial re #lt corre %on& to t$e c$aracteri+ation o, !rabian Dig$t an& Cerro
3.1
! a ,ir t c$aracteri+ation te%, electe& %ro%ertie o, !rabian lig$t an& Cerro Negro re i&#e were &etermine&* T$e e re #lt are %re ente& in Table 7*
!ccor&ing to !'I gravity val#e , 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,0 G !'I re %ectively)* T$i ten&ency i a re,lect o, t$e $ig$er content o, a %$altene , $eteroatom an& metal , toget$er wit$ t$e lower content o, %ara,,in , carbon an& $y&rogen %re ent in Cerro Negro re i&#e*
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19
0n t$e ot$er $an&, CN re i&#e $a a $ig$er Conra& on carbon val#e t$an A( re i&#e* Conra& on carbon re i&#e i con i&ere& a a %arameter to eval#ate coke ,ormation ten&encie o, cr#&e oil an& t$eir &erivative (2<)* !ccor&ing to t$i , CN re i&#e co#l& %otentially ,orm $ig$er coke amo#nt t$an A( re i&#e* Table 9 $ow atomic ratio o, t$e t#&ie& re i&#e * CN %re ente& a lower -AC ratio an& $ig$er NAC, 0AC, 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"#$e 46 !tomic ratio o, !rabian Dig$t an& Cerro Negro re i&#e /e i&#e A( CN -AC 1*80 1*9< NAC . 10-7 7*29 9*80 0AC . 10-7 9*<0 B*<9 SAC . 10-2 1*82 1*89
4ven t$o#g$ t$e mi cellaneo# %ro%ertie &etermine& give im%ortant in,ormation abo#t %$y icoc$emical ,eat#re o, re i&#e , t$ey are in #,,icient to &e cribe t$em in a tr#ct#ral ,a $ion an& to %re&ict t$eir be$avior #n&er SCSC con&ition * Con e"#ently, alternative c$aracteri+ation trategie , ba e& #%on S!/! ,ractionation an& %ectro co%y tec$ni"#e , were a&o%te& to reac$ t$i goal* 3.2. SARA Di-)ri#u)i*+-.
5ig#re 7 $ow S!/! &i trib#tion o, A( an& CN re i&#e * A( re i&#e $a a maCor content o, at#rate (19*B I wt) t$an CN re i&#e (<*1I wt)* !ccor&ing to t$e #gge te& mec$ani m ,or SCSC, A( re i&#e $a a 88,7 I wt (aromatic ?re in ?a %$altene ) t$at can be converte&, w$erea CN re i&#e $a a 97,9 I wt* (8,7I $ig$er)* ! a ,ir t a%%ro.imation, it eem t$at CN re i&#e co#l& $ow a $ig$er conver ion val#e beca# e it $a a maCor yiel& o, t$e mainly a,,ecte& ,raction in SCSC*
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18
100%
7,5
90% 80% 70% 60% % Wt 50% 40% 30% 20% 10% 0%
18,7
Asphaltenes Resins
23,9
36,5
Aromatics Saturates
53,9 38,7
14,7
6,1
!rabian Dig$t
Cerro Negro
c$ange in SCSC (9-8)* !mong t$em, t$e aromatic ,raction wa t$at a,,ecte& t$e mo t* ! ob erve& in 5ig#re 7, A( re i&#e i ric$er in aromatic ,raction, w$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 ,raction, t$i i not a g#arantee to en #re $ig$ conver ion level , beca# e in SCSC, tran ,ormation co#l& be a ociate& not only to weig$t yiel& o, S!/! ,raction , b#t al o to t$e tr#ct#ral c$aracteri tic o, t$em (8)* In con e"#ence, it i &i,,ic#lt to e tabli $ ,rom S!/! &i trib#tion , w$ic$ o, t$e t#&ie& re i&#e will $ow t$e $ig$e t conver ion level*
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1<
It $a been &i c# e& $ow S!/! &i trib#tion &o not give eno#g$ in,ormation to %re&ict relative conver ion level in SCSC* In con e"#ence, ot$er %arameter m# t be ,o#n& to im%rove #c$ %re&iction * It i believe& t$at alkyl #b tit#ent in aromatic tr#ct#re can $ave a igni,icant in,l#ence on t$e conver ion val#e (1-8), T$ere,ore, it i nece ary to eval#ate t$eir relative ab#n&ance in or&er to e tabli $ t$i in,l#ence* T$# , t$e ratio alkyl #b tit#entAaromatic ring can be # e& a a %arameter to e timate t$e tr#ct#ral "#ality o, a SCSC ,ee& tock an& to %re&ict it be$avior #n&er SCSC con&ition * e timate t$i %arameter* 5ig#re 9 an& 8 $ow
17 17
&i trib#tion (aromatic an& ali%$atic carbon ) o, S!/! ,raction t$at can be # e& to
Ar*m")ic-
3 3 3 2 2
7 2 1 9 7
. . . . .
Re-i+-
,a L 0*718
r a l 3 1 . 4 8 9 6 8 . 5 1 1 I n t e
,a L 0*981
r a l 4 5 . 1 1 9 5 4 . 8 8 1 1 3 0 1 2 0 1 1 0 1 0 0 9 0 ! p p m " 8 0 7 0 6 0 5 0 4 0 3 0 I n t e
1 7 0
1 6 0
1 5 0
1 4 0
1 3 0
1 2 0
11 0
1 0 0
9 0 ! pp m "
8 0
7 0
6 0
5 0
4 0
3 0
2 0
1 0
1 7 0
1 6 0
1 5 0
1 4 0
3 7 . 1 4 1 5
31 . 9 99 6 29 . 7 10 3
22 . 7 26 9 19 . 7 94 8 2 0
A-1h"$)e+e-
,a L 0*<12
r al
6 1 . 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 . 7 6 3
I n t e
3 0
1 4 . 1 6 9 1 1 0
'23S!-INT434'
INT-8989, 2001
1B
1 3 9 . 3 3 6 6
1 2 6 . 7 1 2 9
3 7 . 3 5 0 9 3 2 . 7 1 4 6 3 1 . 9 1 2 9 2 9 . 6 8 8 6
2 2 . 6 9 0 8 1 9 . 7 0 1 0
1 4 . 1 5 4 6 1 1 . 4 3 2 0
# 0 . 0 0 0 0
9 9 3 2
22 . 6 6 9 1 1 9 . 6 93 7 2 0
Ar*m")ic-
Re-i+-
,a L 0*777
r a l 3 3 . 3 0 0 6 6 . 7 0 0 I n t e
,a L 0*797
r a l 3 4 . 3 2 0 6 5. 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
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 . 1 4 7 4 1 0
3 3 3 2
7 2 1 9
. . . .
3 6 8 6
5 9 9 7
0 2 1 4
A-1h"$)e+e-
,a L 0*82B
r a l 5 2 . 7 4 2 4 7 . 2 5 8 1 3 0 1 2 0 1 1 0 1 0 0 9 0 ! p p m " 8 0 7 0 6 0 5 0 4 0 3 0 I n t e 1 7 0
1 6 0
1 5 0
1 4 0
2 0
1 0
!ccor&ing to t$e e re #lt , A( re in an& a %$altene ,raction $ave a maCor aromatic c$aracter t$an t$e ame CN ,raction beca#/e e o, aromaticity ,actor (,a) val#e* !romatic in t$eir $ig$er ! %$altene
100 5ig#re < $ow aromatic an& ali%$atic carbon &i trib#tion (e.%re e& a ty%e o, CAtotal C)
in aromatic, re in 90 an& a %$altene ,raction ,rom bot$ re i&#e * 5rom t$i &i trib#tion, a
71,9 9 0 Str#ct#ral 1#ality 80 'arameter (S1'), &e,ine& a 2C a%li$aticACaromatic ratio, wa calc#late& ,or 98,1 77,7 79,7
<1,2 9
82,B 9
C !romatic C !li%$atic
80 90 70 20 10 0 !D CN !D CN !D CN
<8,8 1 <<,B 0 89,8 8 <8,< 8
47$26
78,B <
'23S!-INT434'
INT-8989, 2001
18
Figure 6; !li%$atic an& aromatic carbon &i trib#tion o, S!/! ,raction ,rom A( an& CN re i&#e obtaine& by 17C N:/ analy i *
an& CN
3ac##m /e i&#e A( CN
! mall &i,,erence between S1' val#e o, aromatic ,raction i ob erve&* T$i mean t$at #c$ ,raction $ave ome ,eat#re t$at make t$em imilar ,rom a tr#ct#ral %oint o, view* Con e"#ently, bot$ aromatic ,raction are e.%ecte& to be c$emically tran ,orme& at a imilar e.ten ion #n&er SCSC con&ition * S1' val#e o, re in an& a %$altene were $ig$er in CN re i&#e, com%are& to t$o e calc#late& ,or A( ,raction . T$i in&icate an& a %$altene a better tr#ct#ral "#ality o, re in an& an& a %$altene ,or t$e SCSC %roce * 2i,,erence o, 0*B0 an& 0*77 in S1' val#e ,or re in are ob erve& re %ectively* !ccor&ing to t$e e re #lt , re in
'23S!-INT434'
INT-8989, 2001
19
a %$altene ,rom CN re i&#e $ow a noticeable &i,,erence in alkyl #b tit#ent t$at co#l& $ave a marke& in,l#ence on t$e conver ion val#e* T$ere,ore, t$e e ,raction are e.%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, 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$i , it i nece ary to con i&er aromatic, re in an& a %$altene yiel& (,rom S!/! e%aration ) toget$er wit$ carbon content o, eac$ ,raction (,rom elemental analy i ), an& 17C N:/ &ata* T$e re #lt are %lotte& in 5ig#re B*
<0
80
A( CN
99,7<
98,B2
I C aromatic
I C !li%$atic
Figure 7; =eig$t contrib#tion o, ali%$atic an& aromatic carbon in t$e combine& (aromatic, re in an& a %$altene) ,raction to t$e total carbon content in A( an& CN re i&#e *
T$# , CN re i&#e %re ent a 97,7 I wt o, tr#ct#re t$at can %otentially be converte& #n&er SCSC con&ition (!romatic ?/e in ?! %$altene )* T$i convertible %ortion $a a total carbon content o, B8,0B I, &i trib#te& a ,ollow; 98,B2I a ali%$atic carbon an& 29,78I a aromatic carbon* 0n t$e ot$er $an&, A( re i&#e $a 88,7 I wt o, t$e e tr#ct#re , 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'
INT-8989, 2001
20
In Table <, t$e carbon ty%e &i trib#tion among aromatic , re in , an& a %$altene are li te&* T"#$e 6; Total carbon ty%e &i trib#tion in A( an& CN re i&#e an& t$e in&ivi&#al
contrib#tion o, main S!/! ,raction converte& &#ring t$e SCSC %roce *
A( Re-i.ue IC !li%$atic IC!romatic 71*01 10*89 2*9< 99*7< 19*28 8*9< 7*89 2B*10
CN Re-i.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 , a Total Str#ct#ral 1#ality 'arameter (TS1') wa calc#late& ,or eac$ re i&#e con i&ering total ali%$atic an& aromatic carbon content in !romatic, /e in an& ! %$altene ,raction ((Cali%$atic)A(Caromatic))* /e #lt are li te& in Table B*
T"#$e 7; Total Str#ct#ral 1#ality 'arameter Calc#late& ,or A( an& CN /e i&#e * /e i&#e A( CN TS1'L (Cali%$atic)A(Caromatic)* 1*<9 1*<<
T$# , a #btle &i,,erence in TS1' val#e wa ob erve&; CN re i&#e TS1' val#e i a little bit $ig$er com%are& to t$e one obtaine& ,or A( re i&#e. To e.%lain t$i re #lt, we $ave to con i&er t$at TS1' val#e $a two main com%onent ; ! "#ality com%onent an& a ma yiel& com%onent* 1#ality com%onent i relate& to t$e yiel& in&ivi&#al S1' val#e o, t$e mainly a,,ecte& S!/! ,raction , w$ile t$e ma an& im%ortant contrib#tion to t$e TS1' val#e* 5or in tance, ma
com%onent i relate& to t$e relative weig$t %ercentage o, t$em* 4ac$ com%onent will $ave yiel& o, t$e aromatic
'23S!-INT434'
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21
,raction 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, ma yiel& o, re in an& a %$altene ,rom CN re i&#e will $ave a igni,icant contrib#tion to t$e TS1' val#e t$an t$e aromatic one* 2e%en&ing on t$e contrib#tion o, eac$ com%onent to TS1', t$e re #lting &i,,erence between two TS1' val#e will be bigger or maller* In t$i ca e, t$e &i,,erence wa be con i&ere& in tea&* ! tate& be,ore, t$e aromatic ,raction in bot$ re i&#e are e.%ecte& to #n&ergo c$emical mall* In con e"#ence, it i $o#l& &i,,ic#lt to make a %re&iction ba e& only on t$i %arameter* In&ivi&#al S1' val#e
c$ange at t$e ame e.ten ion beca# e t$ey $ave almo t t$e ame S1' val#e* -owever, re in an& a %$altene in CN re i&#e $o#l& be more a,,ecte& t$an t$e ame ,raction in A( re i&#e* T$e global e,,ect i t$at CN re i&#e $o#l& e.%erience more c$emical c$ange t$an re i&#e A( re i&#e SCSC con&ition * 3.4 S)ruc)ur"$ 7u"$i), '"r"me)er- C"$cu$")e. 3r*m 10 NMR D")". !verage molec#lar %arameter were calc#late& # ing in,ormation ,rom 1- N:/ %ectra, 3'0 molec#lar weig$t, an& total carbon content a in&icate& in re,erence (29)* !li%$atic an& aromatic carbon content o, aromatic, re in an& a %$altene ,raction were &etermine& among t$e e %arameter * !&&itionally, S1' val#e were calc#late& too* /e #lt are #mmari+e& in Table 8*
/e in
I Caromatic I
! %$altene
I Caromatic
Cali%$atic
Cali%$atic
B2*18 B2*10
89*B1 88*99
<0*01 <1*B7
'23S!-INT434'
INT-8989, 2001
22
! can be een, S1' val#e &etermine& ,rom 1- N:/ &ata, &i,,er ,rom t$o e calc#late& ,rom 17C N:/ &ata* T$e &i,,erence i attrib#te& to t$e con i&eration ma&e &#ring average molec#lar %arameter (!:') calc#lation* -owever, t$e ten&ency i t$e ame; -ig$er S1' val#e ,or re in an& a %$altene ,rom CN re i&#e an& almo t t$e ame S1' val#e ,or t$e aromatic ,raction o, bot$ re i&#e * T$ere,ore, %re&iction ma&e #%on 17C N:/ &ata are rein,orce& by
1
- N:/ re #lt * De
're&iction were con,irme& &#ring SCSC %ilot %lant te t* T$e e te t were %er,orme& # ing A( an& CN re i&#e a ,ee& tock * T$e reaction wa %ro&#ct to%%e& at t$e conver ion level w$ere $owe& a minimal '-val#e o, 1*20* In t$i ca e, '-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 $ow re #lt obtaine& ,rom %ilot %lant te t * ! %re&icte&, at t$e ame critical %ro&#ct tability level ('-val#e o, 1*20), CN re i&#e $owe& $ig$er conver ion level t$an A( re i&#e* S#r%ri ingly, CN re i&#e $owe& a &i,,erence in conver ion o, 17*2 I re %ect to A( re i&#e, w$ic$ wa #ne.%ecte& con i&ering general %ro%ertie o, t$e total tr#ct#ral "#ality %arameter (TS1')* T$i remarkable re #lt i believe& to &e%en& on t$e tr#ct#ral "#ality o, re in an& a %$altene o, t$i re i&#e* T$e ,act t$at aromatic ,raction o, 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.ten ion* 0n t$e ot$er $an&, S1' val#e o, re in an& a %$altene ,rom CN re i&#e %re&icte& $ig$er conver ion ,or t$e e ,raction * T$ere,ore, t$ey are believe& to be t$e main re %on ible ,or t$e conver ion val#e ac$ieve& by t$i re i&#e.
'23S!-INT434'
INT-8989, 2001
27
5ee& tock A( CN
3.6 S)ruc)ur"$ De)"i$- *3 A$i1h")ic Su#-)i)ue+)- i+ SARA Fr"c)i*+-. RICO 'r*.uc) A+"$,-i-. To get a &ee%er knowle&ge abo#t ali%$atic &i trib#tion in aromatic, re in an& a %$altene ,raction ,rom t$e t#&ie& re i&#e , /IC0 reaction wa %er,orme&* 5o#r kin& o, ali%$atic #b tit#ent were i&enti,ie&; Normal alkyl i&e c$ain , branc$e& alkyl i&e c$ain , %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 ,ollow; 3.6.1. N*rm"$ A$8,$ Si.e Ch"i+-. !lkyl i&e c$ain attac$e& to aromatic carbon in aromatic, re in an& a %$altene molec#le can be converte& to alkanoic aci& by /IC0 a $own i c$eme 1 (9-21)* I, t$e / gro#% are normal alkyl gro#% , t$en t$e re #ltant aci& ,orm a erie o, n-alkanoic aci& * T$e e %ro&#ct were "#anti,ie& by HC-:S in t$e ,orm o, met$yl- e ter by t$e mA+ B9 ,ragment ion* !#t$or $ave re%orte& lengt$ o, t$e n-alkyl i&e c$ain ,rom C 2 to C28 an& #% to C77 (19-21)* -owever, $orter c$ain (,rom C2 to C8) are &i,,ic#lt to analy+e a e ter &erivative beca# e o, t$eir $ig$ volatility, t$ey are lo t &#ring t$e eva%oration %roce&#re %er,orme& a wa a %revio# te% to t$e HC-:S analy i (11-21)* Ion C$romatogra%$ic o t$e in,ormation relate& to t$e e %eci,ic tec$ni"#e $a been # e& to olve t$i %roblem (18-20)* Mn,ort#nately, t$i met$o&ology not a&o%te& in t$e %re ent work, #b tit#ent wa lo t* ! a con e"#ence, normal an& branc$e& alkyl c$ain &i trib#tion tart in C< com%onent ,or all ,raction analy+e&* 3.6.1.1 N*rm"$ A$8,$ Ch"i+- i+ Ar*m")ic Fr"c)i*+-.
'23S!-INT434'
INT-8989, 2001
29
/IC0 o.i&ation $a
been
#cce ,#lly
an&
a %$altene (9-21)* =ork relate& to t$e c$aracteri+ation o, aromatic ,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 ,ir t work &one on t$i ,raction* /e #lt are &i c# e& in t$e ne.t %aragra%$ * 5ig#re 8 $ow n-alkyl c$ain &i trib#tion in t$e aromatic ,raction o, A( an& CN re i&#e * ! bimo&al &i trib#tion wa ob erve& in bot$ ca e , w$ic$ &ecline wit$ increa ing lengt$ o, t$e alkyl c$ain* 5or A( re i&#e, n-alkyl c$ain &i trib#tion tart in C< an& en& in C2B, ma.imi+ing at C9, C1< (t$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 ,raction o, A( an& CN re i&#e
In t$e ca e o, CN re i&#e, &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, &i trib#tion &ecline almo t monotonically an& it i ob erve& enric$ment in $orter c$ain (C < to C11)* In contra t, A( aromatic molec#le are enric$e& in longer b#t le ab#n&ant n-alkyl c$ain *
'23S!-INT434'
C27
INT-8989, 2001
28
5ig#re 9 $ow &i trib#tion o, normal alkyl i&e c$ain in t$e re in ,raction
#tie&* It i
ob erve& a m#ltimo&al &i trib#tion t$at tart in C< an& en& in C28 ,or t$e A( ca e an& in C2< ,or t$e CN ca e* -ig$er %ick are reac$e& at C9, C19, C1< an& C18 com%onent in bot$ ,raction * -owever, A( re in molec#le com%onent , e.ce%t in C<, C9, C1< an& t$e le e.$ibit a mall enric$ment in almo t all ab#n&ant b#t longer C22 to C2< #b tit#ent *
AL
CN
C22
C25
'23S!-INT434'
C26
C10
C11
C12
C13
C16
C17
C18
C19
C23
C24
C6
C7
C8
C9
INT-8989, 2001
2<
!lkyl c$ain &i trib#tion in a %$altene ,raction were "#ite &i,,erent in bot$ re i&#e (5ig#re 10)* A( a %$altene molec#le e.$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<, w$erea CN a %$altene molec#le $ave a m#ltimo&al &i trib#tion ,rom C< to C28 wit$ $ig$er %ick locate& at C9 an& C1< re %ectively* !&&itionally, CN a %$altene are enric$e& in $orter alkyl c$ain (,rom C < to C11), b#t A( a %$altene are in longer com%onent ( ,rom C17 to C29)*
20 18 16 Relative Area (%) 14 12 10 8 6 4 2 0 C14 C15 C20 C21 C26 C10 C11 C12 C13 C16 C17 C18 C19 C22 C23 C24 C25 C6 C7 C8 C9
AL
CN
3.6.2
6ranc$e& alkyl c$ain ,orm branc$e& alkanoic aci& #n&er /IC0 con&ition
(Sc$eme 1)* -owever, a#t$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) $ave i&enti,y ,o#r ,amilie o, -branc$e& n-alkyl #b tit#ent , w$ere t$e -%e&ant gro#% were met$yl, et$yl, n-%ro%yl an& n-b#tyl ,#nctionalitie * T$e e ,amilie &erive ,rom -branc$e& alkyl aromatic tr#ct#re %re ente& in re in an& a %$altene ,raction (5ig#re 11)* !n& are "#anti,ie& a met$yle ter by t$e mA+L 88 ,ragment ion ,or -met$yl &erivative , mA+ L102 -et$yl &erivative , mA+L 11< ,or -%ro%yl &erivative , an& mA+L 170 ,or -b#tyl &erivative * I o%renoi& #b tit#ent were i&enti,ie& too*
'23S!-INT434'
INT-8989, 2001
2B
( )n
17 1!
( )n
( )n
1! 19
( )n
Figure 11; 'rec#r or tr#ct#re o, -met$yl, -et$yl, -n-%ro%yl an& -n-b#tyl alkyl c$ain *
In t$e %re ent work, only -met$yl alkyl c$ain were i&enti,ie&, t$e ot$er ,amilie were in #c$ low concentration t$at it wa im%o ible to analy+e t$em #n&er t$e # e& in tr#mental con&ition * 3.6.2.1 9r"+che. A$8,$ Si.e Ch"i+- i+ Ar*m")ic Fr"c)i*+-. 5ig#re 12 $ow -met$yl alkyl c$ain &i trib#tion obtaine& #n&er /IC0 o.i&ation o, t$e t#&ie& aromatic ,raction * It i ob erve& a bimo&al &i trib#tion ,or CN aromatic ,raction t$at tart in C< an& en& in C1B* -ig$er %ick are reac$e& at C8 an& C17* In contra t, -met$yl alkyl c$ain &i trib#tion ,or A( aromatic i longer t$an t$e one ob erve& in CN (,rom C< to C28), b#t it &ecline are enric$e& in longer b#t le (,rom C< to C17)* moot$ly wit$ lengt$ c$ain* -ig$er %ick are ob erve& at CB an& C17* !&&itionally, molec#le ,orm A( aromatic ,raction ab#n&ant branc$e& #b tit#ent (C 19-C28)N w$erea t$e corre %on&ing CN aromatic ,raction molec#le are in $orter b#t more ab#n&ant one
'23S!-INT434'
INT-8989, 2001
28
18 Area Relativa (%) 16 14 12 10 8 6 4 2 MeC10 MeC11 MeC14 MeC15 MeC17 MeC18 MeC19 MeC20 MeC21 MeC22 MeC25
MeC25
AL
CN
MeC12
MeC13
MeC16
MeC23
MeC23
Figure 12; -met$yl alkyl c$ain &i trib#tion o, A( an& CN aromatic ,raction
3.6.2.2 9r"+che. A$8,$ Si.e Ch"i+- i+ Re-i+ Fr"c)i*+-* In t$e ca e o, re in ,raction : A( re i&#e $owe& an almo t a# ian &i trib#tion e.ten&e& ,rom C< to C22* 2i trib#tion in CN re in ,raction i bimo&al an& t$e ame incl#&e C< to C29 #b tit#ent * !not$er ,eat#re ob erve& i t$at A( re in ,raction molec#le are enric$e& in almo t all it com%onent in com%ari on wit$ CN $omolog#e e.ce%t in CB, 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
'23S!-INT434'
MeC24
MeC6
MeC7
MeC8
MeC9
INT-8989, 2001
29
3.6.2.3 9r"+che. A$8,$ Si.e Ch"i+- i+ A-1h"$)e+e Fr"c)i*+:ore &ramatic &i,,erence were ob erve& in t$e -met$yl alkyl c$ain &i trib#tion o, a %$altene ,raction (5ig#re 19)* :onomo&al &i trib#tion o, branc$e& c$ain in A( a %$altene molec#le i concentrate& in t$e C12-C20 region* In ot$er $an&, branc$e& c$ain m#ltimo&al &i trib#tion o, CN a %$altene ,raction %rea& ,rom C< to C22* ! a remark, A( a %$altene ,raction i enric$e& in all it -met$yl alkyl c$ain #b tit#ent com%are& to t$e corre %on&ing CN ,raction*
20 Area Relativa (%) 18 16 14 12 10 8 6 4 2 MeC11 MeC12 MeC13 MeC14 MeC16 MeC17 MeC18 MeC21 MeC22 MeC10 MeC15 MeC19 MeC20 MeC9 MeC6 MeC7 MeC8 0
AL
CN
Figure 13; -met$yl alkyl c$ain &i trib#tion o, A( an& CN ! %$altene ,raction
3.6.3
&i trib#tion o, %olymet$ylene bri&ge ranging ,rom C 9 to C77* C2 an& C7 &iaci& are #n table #n&er /IC0 con&ition an& t$ey are ,#rt$er o.i&i+e& to C0 2 (17,1<)* In t$e
'23S!-INT434'
INT-8989, 2001
70
%re ent work, &icarbo.ylic aci& (%olymet$ylene bri&ge ) were analy+e& by HC-:S a met$yl-e ter # ing mA+ L 89 ,ragment ion to t$e $orter com%onent (C9-C9) an& mA+L 98 ,ragment ion ,or longer com%onent (C10-C20)* 2i trib#tion were %lit beca# e o, t$e &ecrea ing inten ity o, mA+ L 89 ,ragment ion wit$ lengt$ c$ain* In longer c$ain , mA+L 98 ,ragment ion ignal became more inten e* 3.6.3.1 '*$,me)h,$e+e 9ri.ge- i+ Ar*m")ic Fr"c)i*+-. t#&ie&*
5ig#re 18 $ow %olymet$ylene bri&ge &i trib#tion ,or t$e aromatic ,raction
AL
CN
AL
15 10 5 0 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17
CN
C 18
C 19
'23S!-INT434'
INT-8989, 2001
71
In bot$ aromatic ,raction , $ort %olymet$ylenic c$ain &i trib#tion $a%e t$at &ecline
$owe& a monomo&al
in longer %olymet$ylenic #b tit#ent * In t$e ca e o, A( re i&#e, aromatic ,raction molec#le e.$ibit a total &i trib#tion ,rom C9 to C19, wit$ $ig$er %ick locate& at C8, C11 an& C12 #b tit#ent * Similar $ig$er %ick are ob erve& in CN aromatic ,raction molec#le * -owever, t$e &i trib#tion e.ten& #% to C1B* Concerning to t$e relative ab#n&ance, CN aromatic molec#le are enric$e& in C8, CB, C8 $orter com%onent an& in almo t all t$e longer #b tit#ent wit$ t$e e.ce%tion o, C 12, C1< an& C1B c$ain *
3.6.3.2
Similar monomo&al $a%e were ,o#n& in %olymet$ylene bri&ge &i trib#tion o, re in ,raction ,rom A( an& CN re i&#e (5ig#re 1<)* A( re in ,raction e.$ibit a &i trib#tion ranging ,rom C9 to C1B wit$ $ig$er %ick at C8 an& C11N w$erea &i trib#tion in CN re in ,raction i %rea& #% to C19 wit$ %rominent %ick at C8 an& C12 re %ectively*
In term o, relative ab#n&ance, enric$ment in C 9, C8, CB, C12, C18, an& C1B-C19 com%onent wa ob erve& in t$e CN re in ,raction in com%ari on wit$ t$e ame A( ,raction*
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AL
CN
A(
CN
3.6.3.3
'*$,me)h,$e+e 9ri.ge- i+ A-1h"$)e+e Fr"c)i*+-. $owe& t$e ame monomo&al %attern a well a in aromatic an& re in *
'olymet$ylenic bri&ge in a %$altene ,raction %ick are reac$e& at C8 an& C12 com%onent
ob erve& in aromatic an& re in ,raction * 5ig#re 1B $ow t$e re #lt obtaine&* 'rominent Nevert$ele , &i,,erence in relative ab#n&ance an& lengt$ c$ain were ob erve&* T$# , %olymet$ylenic bri&ge &i trib#tion in A( a %$altene range& ,rom C9 to C18, w$ere t$e C8
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an& C12 com%onent were t$e mo t im%ortant* 4nric$ment in C <-C9 an& C17, C19, 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.ten&e& a in A( $omolog#e ,raction* It en& at C1< wit$ $ig$er %ick in C8 an& C12 an& a igni,icant ab#n&ance in C9, C8, C10-C12 an& C18-C1< #b tit#ent *
AL
CN
AL
CN
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3.6.4
0,.r*"r*m")ic S)ruc)ure-.
2#ring /IC0 reaction e.%erience , Nom#ra an& co-worker (18-1B) i&enti,ie& ome alkyl %olycarbo.ylic aci& a %o ible %ro&#ct o, t$e o.i&ation o, t$ree or more aryl- #b tit#te& alkyl bri&ge an& t$e o.i&ation o, %artially at#rate& con&en e& tr#ct#re (Sc$eme 7)* It i believe wit$ $ig$ %robability t$at t$e e %ro&#ct ari e ,rom t$e latter %rec#r or #cce ,#lly ($y&roaromatic tr#ct#re )* T$# , 1,2,7-tricarbo.y %ro%ane (C7 triaci&), 1,2,9-tricarbo.yb#tane (C9 triaci&) an& 1,2,7,9- tetracarbo.y-b#tane (C9-tetraaci&) were i&enti,ie& by HC-:S a met$yle ter * In t$e %re ent work, only C7 an& C9 triaci& were i&enti,ie& by t$e mA+ L12B ,ragment ion* C9 tetraaci& wa not ob erve& in all t$e t#&ie& ca e *
3.6.4.1
Tren& in $y&roaromatic tr#ct#re &i trib#tion in aromatic an& re in ,raction o, bot$ re i&#e were very imilar (5ig#re 18)* In t$e e ,raction , 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,lect o, t$e $ig$ concentration o, $y&roaromatic ,ragment in aromatic an& re in ,raction o, CN re i&#e t$at are imilar to t$e tr#ct#re 5, 6, an& 7 $owe& in Sc$eme 7* /elate& to t$e A( aromatic an& re in ,raction , an enric$ment in C 9 triaci& wa ,o#n&, w$ic$ mean t$at tr#ct#re a !, 9, an& 1 (Sc$eme 7) &ominate in t$e e ,raction *
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!romatic
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/e in
CN AL
C3
C4
CN
AL
C3
C4
Figure 1!; 2i trib#tion o, C7 an& C9 tricabco.ylic aci& a re%re entative %ro&#ct o, $y&roaromatic tr#ct#re in A( an& CN aromatic an& re in ,raction
3.6.4.2 0,.r*"r*m")ic S)ruc)ure- i+ A-1h"$)e+e Fr"c)i*+-y&roaromatic &i trib#tion in a %$altene ,raction wa &i,,erent t$an t$o e ob erve& in aromatic an& re in (5ig#re 19)* In t$i ca e, t$e relative ab#n&ance C 7-triaci&A C9-triaci& ratio c$ange& in bot$ re i&#e* T$# , A( a %$altene molec#le $y&roaromatic %ortion $owe& a $ig$er content in imilar to t$e 5, 6, an& 7 tr#ct#re (Sc$eme 7)* T$i concl# ion i
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in t$i ,raction tr#ct#re !, 9 an& 1 %re&ominate over tr#ct#re 5, 6, an& 7 (Sc$eme 7)* T$e o%%o ite re #lt wa obtaine& in aromatic an& re in ,raction o, bot$ re i&#e * ! %$altene
CN AL
C3
C4
Figure 19; 2i trib#tion o, C7 an& C9 tricarbo.ylic aci& a re%re entative %ro&#ct o, $y&roaromatic tr#ct#re in A( an& CN a %$altene ,raction
3.7 4r*u1 Di-)ri#u)i*+To get a better knowle&ge o, t$e in,l#ence o, ali%$atic gro#% to t$e conver ion val#e o, SCSC %roce , global &i trib#tion were con i&ere& in eac$ $ow t$e e re #lt * ! can be een, in all ,raction normal alkyl c$ain are t$e mo t ab#n&ant ali%$atic gro#%, ,ollowe& by %olymetylene bri&ge , an& t$e le $y&roaromatic tr#ct#re * ab#n&ant branc$e& alkyl c$ain an& t#&ie& ,raction* 5ig#re 20
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100 90 Relative Area (%) 80 70 60 50 40 30 20 10 0 n-alkyl chains Bridges Branched Chains Hydroaromatics
Ar*m")ic-
CN
AL
Re-i+-
CN
AL
A-1h"$)e+e-
CN
AL
Figure 2 ; !li%$atic Hro#% Contrib#tion in aromatic, re in an& a %$altene ,raction ,rom A( an& CN re i&#e '23S!-INT434'
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T$e ,ir t ob ervation t$at ari e ,rom t$e e re #lt i t$at aromatic, re in an& a %$altene ,raction ,rom CN re i&#e are enric$e& in %olymet$ylenic bri&ge an& branc$e& c$ain com%are& to t$e ame ,raction in A( re i&#e* -owever, in t$e ca e o, n-alkyl c$ain , A( aromatic ,raction $owe& $ig$er ab#n&ance t$an t$e corre %on&ing CN ,raction* In contra t, CN re in an& a %$altene e.$ibit a maCor content in t$i kin& o, #b tit#ent * Concerning to $y&roaromatic tr#ct#re , aromatic ,raction %re ente& a very low ab#n&ance in com%ari on wit$ re in an& a %$altene ,raction * -owever, in re in ,raction relative concentration wa almo t t$e ame in bot$ re i&#e * ! noticeable &i,,erence wa ob erve& in a %$altene ; A( a %$altene were more enric$e& in t$i com%onent t$an t$e CN $omolog#e ,raction* T$e global e,,ect i t$at aromatic ,raction ,rom bot$ re i&#e $ave almo t t$e ame content o, ali%$atic tr#ct#re , w$erea , re in an& a %$altene ,rom CN re i&#e are more enric$e& in #c$ tr#ct#re t$an t$e ame ,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$e S1' val#e calc#late& ,rom %ectro co%ic &ata*
CN
AL
Figure 21; Total ali%$atic gro#% content in aromatic, re in an& a %$altene ,raction ,rom A( an& CN re i&#e e timate& ,rom /IC0 re #lt *
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3.! 4r*u1 C*+)ri#u)i*+!ccor&ing to t$e SCSC %ilot %lant te t re #lt an& to t$e /IC0 in,ormation, we can %ec#late abo#t reactivity tren& ,or eac$ ali%$atic gro#% an& it contrib#tion to t$e conver ion val#e* T$# , normal alkyl c$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$ain (in le e.ten ion)* 'olymet$ylene bri&ge are believe& to be t$e mo t reactive gro#% among t$e e #b tit#ent beca# e t$ey $ave two %o ible %oint o, attack (5ig#re 22)* -y&roaromatic tr#ct#re are t$o#g$t to $ave a lower contrib#tion beca# e t$ey can eit$er e.%eriment &ealkylation to ,orm lig$ter $y&rocarbon %ro&#ct or &e$y&rogenation to ,orm more con&en e& aromatic y tem t$at co#l& be re %on ible ,or coke ,ormation (5ig#re 22)*
Figure 22; 'o ible alkyl gro#% contrib#tion to t$e conver ion o, SCSC %roce
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4.
CONC(USION
Str#ct#ral c$aracteri+ation o, S!/! ,raction ,rom vac##m re i&#e i a # e,#l %re&ictive tool ,or Selective Catalytic Steam Cracking (SCSC)* It $a been &emon trate& t$at SCSC conver ion level are in,l#ence& not only by t$e ab#n&ance o, S!/! ,raction ric$ in alkylaromatic tr#ct#re , b#t al o by t$e "#ality o, t$em in term o, Cali%$aticACaromatic ratio * 6a e& #%on 17C an& 1- N:/ &ata, a tr#ct#ral "#ality %arameter (S1') wa &e,ine&* T$i %arameter co#l& be # e& to %re&ict ,ee& tock be$avior #n&er SCSC con&ition * -owever, S1' val#e , calc#late& ,rom 17C N:/ &ata, are more acc#rate t$an t$o e calc#late& ,rom
1
- N:/, ince no a #m%tion ,or !:' calc#lation are re"#ire&* 1- N:/ %arameter are analytical &eman& involve&*
/elate& to t$e tr#ct#ral &etail o, ali%$atic #b tit#ent , /IC0 reaction gave val#able in,ormation abo#t &i trib#tion c$ain an& $y&roaromatic o, #c$ #b tit#ent * T$# , normal alkyl c$ain an& %olymet$ylene bri&ge were t$e mo t ab#n&ant alkyl #b tit#ent , w$erea , branc$e& alkyl tr#ct#re $owe& lower concentration in all t$e t#&ie& ,raction * /IC0 re #lt rein,orce& t$e %ectro co%ic in,ormation obtaine&, beca# e re in an&
a %$altene ,rom CN re i&#e were ric$er in ali%$atic tr#ct#re t$an t$e ame A( ,raction , w$ic$ i in agreement wit$ t$e S1' val#e calc#late& ,rom /:N &ata* !&&itionally, /IC0 %ro&#ct analy i gave ome in ig$t abo#t reactivity o, ali%$atic gro#% t$at co#l& e.%lain t$e ob erve& be$avior o, t$e t#&ie& re i&#e #n&er SCSC con&ition *
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5. !
FINA( COM%NTS. tate& at t$e beginning o, t$e re #lt &i c# ion, t$e in,ormation %re ente& in t$i work
corre %on& to t$e %artial c$aracteri+ation o, SCSC ,ee& tock * In t$i i #e, we $ave only &i c# e& ali%$atic #b tit#ent &i trib#tion * In,ormation regar&ing to t$e con&en ation mo&e o, aromatic y tem an& t$e ma balance t$at incl#&e C0 2 mea #rement (com%lementary /IC0 in,ormation) are in %rogre an& will be %re ente& in a econ& i #e
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R%F%R%NC%S (1) (2) 'ereira, '*N :ar+in, /*N KacarOa , D*N DP%e+, I*N -ernQn&e+, 5*N CPr&ova, E*N S+eoke, E*N 5lore , C*N 2#"#e, E*N an& Solari, /* 3i iPn TecnolPgica* <* No* 1, 8-19, 1998* 'ereira, '*N :ac$in, I*N Salerno, H*N Cotte, 4*N -ig#erey, I*N !n&riollo, !*N CPr&ova, E*N KacarOa , D*N :ar+On, /*N /iva , H* Da Inve tigaciPn y 2e arrollo en :eCoramiento &e Cr#&o 4.tra%e a&o en '23S!-INT434'; !"#aconver iPn* !cta CientO,ica 3ene+olana* 3ol* 80 S#%lemento 1, %%; 98-87, 1999* (7) (9) 'ereira, '*N KacarOa , D*N -#o&e, 4*N an& 5eint#c$, -* 'etrole#m Tec$nology 1"#artarly* =inter 1998-1999N %% 29-7B -ig#erey, I*N 'ereira, '*N an& DePn, 3* Sym%o i#m on Cr#&e 0il M%gra&ing ,rom /e ervoir to /e,inery 're ente& 6e,ore t$e 2ivi ion o, 'etrole#m C$emi try, Inc* 221 t !CS :eeting, San 2iego, C!, !%ril 1-8, 2001, %%; <9-<8* (8) -ig#erey, I*N an& 'ereira, '* :o&i,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, 3ene+#ela* B-11 5ebrero, 1999* <80-<82* (<) (B) 'ay+ant, E* 2*, :ontgomery, 2* S* !n& Stra# +, 0* '* S#l,i&e in 'etrole#m* 0rg* Heoc$em* 9, 78B-7<9, 198<* 'eng, '*, :orale -I+"#ier&o, !*, -ogg, !*, Stra# +, 0* '* :olec#lar Str#ct#re o, !t$aba ca ! %$altene ; S#l,i&e, 4t$er an& 4 ter Dinkage * 4nergy S 5#el * 11, 11B1-118B, 199B* (8) Stock, Deon :* an& 0beg :arc# * 0.i&ation an& 2ecarbo.ylation* ! reaction Se"#ence ,or t$e St#&y o, !romatic Str#ct#ral 4lement in 'oca$onta No* 7 Coal* 4nergy S 5#el , 11, 98B-99B, 199B (9) (10) Stock, Deon :* !n& T e, Fwok-t#en* /#t$eni#m Tetro.i&e Cataly+e& 0.i&ation o, Illinoi No* < :onterey Coal* 5#el* 89, <99-<98, 1980* Stock, Deon :* !n& T e, Fwok-t#en* /#t$eni#m Tetro.i&e Cataly+e& 0.i&ation o, Illinoi No* < Coal an& Some /e%re entative -y&rocarbon * 5#el* <2, 9B9-9B<, 1987
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(11)
Stock, D*, :*, an& =ang S* /#t$eni#m Tetro.i&e Cataly+e& 0.i&ation o, Illinoi No* < Coal* T$e 5ormation o, 3olatile :onocarbo.ylic aci& * 5#el* <9, 1B17-1B1B, 1988*
(12)
:oCel ky, T* =*, :ontgomery, 2* S*, Stra# +, 0* '* /#t$eni#m (3III) Cataly+e& 0.i&ation o, -ig$ :olec#lar =eig$t Com%onent o, !t$aba ca 0il San& 6it#men* !0ST/! E* /e *, 2, 171-17B, 1988*
(17)
:oCel ky, T* =*, Igna iak, T* :*, 5rakman, K*, :cIntyre, 2*2*, Down, 4* :*, :ontgomery, 2* S*, Stra# +, 0* '* Str#ct#ral 5eat#re o, !lberta 0il San& 6it#men an& -eavy 0il ! %$altene * 4nergy S 5#el * <, 1, 87-9<, 1991
(19)
:#rata, S*N M-e aka, F*N Ino-#e, -*N an& Nom#ra, :* St#&ie on !li%$atic 'ortion o, Coal 0rganic :aterial 6a e& on /#t$eni#m Ion Cataly+e& 0.i&ation* 4nergy S 5#el * 8, 17B9-1787, 1999
!rtok, D*, :#rata, S*, an& Nom#ra, :*, Sato$, T* /ee.amination o, t$e /IC0 :et$o&* 4nergy S 5#el * 12, 791-798, 1998* Nom#ra, :*N !rtok, D*N :#rata, S*N Tamamoto, !*N -ama, -*N Hao, -*N an& Fi&ena F* Str#ct#ral 4val#ation o, Kao K$#ang Coal* 4nergy S 5#el * 12, 812-827, 1998* S#, T*, !rtok, D*, :#rata, S*, an& Nom#ra, :* Str#ct#ral !naly i o, t$e ! %$altene 5raction o, an !rabian :i.t#re by a /#t$eni#m-Ion-Cataly+e& 0.i&ation /eaction* 4nergy S 5#el * 12, 12<8-12B1, 1998*
(18) (19)
Stra# +, 0* '*N :oCel ky, T* =*N an& Down, 4* :* T$e :olec#lar Str#ct#re o, ! %$altene; !n Mn,ol&ing Story* 5#el* B1, 1788-17<7, 1992* Stra# +, 0* '*N :oCel ky, T* =*N 5araCi, 5*N Down 4* :*N an& 'eng, '* !&&itional Str#ct#ral 2etail o, !t$aba ca ! %$altene an& T$eir /ami,ication * 4nergy S 5#el * 17, 20B-22B, 1999*
(20)
Stra# +, 0* '*N :oCel ky, T* =*N Down 4* :*N Fowalew ki, I*N an& 6e$ar, 5* Str#ct#ral 5eat#re o, 6o can an& 2#ri ! %$altene * 4nergy S 5#el * 17, 228-29B, 1999*
(21)
'eng, '*N :orale -I+"#ier&o, !*N Down, 4* :*N an& Stra# + 0* '* C$emical Str#ct#re an& 6iomarker Content o, Eing$an ! %$altene an& Ferogen * 4nergy S 5#el * 17, 298-2<8, 1999*
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(22) (27)
I'-197A90* ! %$altene (-e%tane In ol#ble ) in 'etrole#m 'ro&#ct * In tit#te o, 'etrole#m* Don&on, 1990* Carbognani, D*, I+"#ier&o !* 're%arative an& !#tomate& Com%o#n& Cla e%aration o, 3ene+#elan 3ac##m /e i&#a by -ig$ 'er,ormance Di"#i& C$romatogra%$y* Eo#rnal o, C$romatogra%$y* 989, 799-908, 1989*
DePn, 3* !verage :olec#lar =eig$t o, 0il 5raction /e onance* 5#el, << (10)N 1998-199<, 198B*
by N#clear :agnetic
S$ell :ete& Serie * State o, 'e%ti+ation o, ! %$altene in 0il* '-3al#e* 10<<-87, 1987* S%eig$t, E* H* T$e C$emi try an& Tec$nology o, 'etrole#m* 2J 4&ition* :arcel 2ekker, N*T* C$a%ter 8N %%; 288-289, 1991*
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