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New Cor r el at i ons Bet ween t he Wat son Characteri zat i on Fact or (K)and Pr opert i es of Coal - Der i ved Mater i al s

MB. Per r y and C. M Whi t e

Di vi si on of Coal Sci encePi t t sbur gh Energy Technol ogy Cent er

P. O Box 10940Pi t t sbur gh, PA 15236

I nt r oduct i on

Coal l i quef act i on pr oduct s, l i ke petr ol eum ar e l ar gel y composed of hydr o-car bons t hat are hi ghl y var i abl e i n pr opert i es dependi ng on t he f eedst ocks usedand the pr ocessi ng condi t i ons. I n 1933, Wat son and Nel son [ l ] emphasi zed t hat t heval ue of physi cal pr oper t y dat a on pet r ol eum f r act i ons i s ". . l i m t ed by thedi f f i cul ty of corr el at i ng them i nto r el at i onshi ps of general appl i cabl i t y. "Pet r ol eum sci ent i st s and engi neer s have def i ned a set of mathemati cal andgr aphi cal expr essi ons, or cor r el at i ons, t hat per m t t he est i mat i on of propert i esof t hese compl ex m xt ur es. Among t hese is a parameter t ermed t he char act er i zat i onf act or ( Kw) , i nt r oduced by Watson and Nel son i n 1933 [ l ] t o denot e the"par af f i ni ci t y" of pet r ol eum hydr ocar bon f r act i ons. The Wat son char act er i zat i onf actor is def i ned as f ol l ows:

wher e Tb i s t he m d- boi l i ng poi nt i n degr ees Ranki ne (OR) andS i s t he speci f i c gr avi t y at 60degr ees Fahrenhei t (OF).

I n addi t i on to char acteri zi ng t he "par af f i ni ci t y, " K has been used t o est i mat eother pr opert i es. Wat son and Nel son [ I ] demonst r at ed t hat K was usef ul f orest i mat i ng t he mol ecul ar wei ght and speci f i c heat of pet r ol eum f r act i ons. Wat sonet al . [ 2 ] r el at ed Kw to per cent hydr ogen, ki nemat i c vi scosi t y, and cr i t i calt emper at ur e of pet r ol eum deri ved pr oduct s. Sm t h and Wat son [ 31 f ound Kw t o obeym xi ng rul es. Mor e r ecent l y, W l son et al . [41 demonst r at ed t hat K was usef ulf or est i mat i ng the cri t i cal pressur e of coal l i qui ds.

I ni t i al l y, coal sci ent i st s and engi neer s used t he bank of cor r el at i ons

devel oped f or pet r ol eum t o est i mate the pr oper t i es of coal l i quef act i on pr oduct s;however , i t i s now accept ed t hat est i mat i on of pr oper t i es of coal l i qui ds f r omexi sti ng pet rol eum data can i nt r oduce l ar ge er r or s [51. The devi at i ons ofpr oper t i es f r om est i mat ed val ues ar e bel i eved t o be caused by t he hi gher con-cent r at i on of pol ar compounds and by t he more ar omat i c nat ure of coal l i qui dsr el at i ve t o pet r ol eum Si nce t he Wat son char act eri zati on f actor was or i gi nal l yi nt r oduced t o denot e " paraf f i ni ci t y, " a hi gh cor r el ati on w t h per cent hydr ogen andt he atomic-hydrogen,to-carbon r at i o is expect ed. That i s, t he cont r i but i on ofar omat i c const i t uent s t o t he pr opert i es of t he m xtur e shoul d be cont ai ned i n thi schar act er i zat i on f actor . At t empt s t o account f or t he cont r i but i on of pol ar con-sti t uent s to t he pr oper t i es of compl ex m xt ures are more di f f i cul t .

An assessment of t he r ol e of pol ar const i t uent s in a coal l i qui d shoul di deal l y begi n w t h a physi cal separ at i on of t he sampl e i nt o f unct i onal l y si m l arf ract i ons. Methods used f or t he physi cal separat i on of coal - deri ved mat eri al si nt o chemcal cl ass f r act i ons ar e numerous and var i ed, maki ng t he compar i sons ofdat a f rom t he l i t erat ur e di f f i cul t . Because of t he rel at i vel y hi gh cont ent ofpol ar materi al s, Sampl e component s f r om coal - der i ved pr oduct s may be adsorbedi r r ever si bl y Ont o l i qui d chr omatogr aphi c st ati onary phase mat er i al s. Al t houghspeci f i c det ect or s are necessar y f or maki ng t he f r act i on cut s, no sui t abl e non-

E

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dest r ucti ve met hod i s avai l abl e f or obt ai ni ng quant i t at i ve r esul t s f or chem calcl ass f r acti ons usi ng exi st i ng chr omat ogr aphi c det ect ors. Ther ef ore, t he f r ac-t i ons t hat ar e to be subj ect ed to f ur t her character i zati on must be col l ect ed, t hesol vent s removed, and t he r esul t i ng f r act i ons wei ghed t o obt ai n quant i t at i ver esul t s f or t he recover y of chem cal cl ass f r act i ons. Thi s i s manpower - i ntensi veand expensi ve, and can l ead t o i mpr eci se r esul t s. Hi gh perf ormance l i qui dchromatogr aphy ( HPLC) el i m nat es some of t he probl ems ci t ed above. The speed andease w t h whi ch sampl es can be anal yzed make HPLC appear as an at t r act i veal t ernat i ve t o the more cl assi cal methods. Some maj or pr obl ems, however , st i l lexi st . To escape t he need t o pack t he chromat ogr aphi c col umn w t h new adsor bentaf t er each separ at i on, many HPLC met hods r equi r e t hat onl y hexane- sol ubl emater i al s are subj ect ed to t he chem cal cl ass separat i on; hexane i nsol ubl es ar egr ouped i nt o a br oad, var i ed, and chem cal l y undef i ned f r act i on cal l ed

"asphal t enes. " Asphal t enes f r om coal - der i ved mater i al s may cont ai n a hi ghper cent age of pol ar const i t uent s t hat are not account ed f or i n pol ar cl assf r act i ons. As ment i oned pr evi ousl y, quant i t at i on of t he cl ass f r acti ons i n thesemat er i al s i s di f f i cul t w t h most exi sti ng HPLC det ectors. I f cor r el at i ons ar ef ound t o be a f unct i on of t he pol ar cont ent of coal - der i ved mat eri al s, t hen i t i snecessar y to char acteri ze these const i t uent s as car ef ul l y as possi bl e i f exi st i ngcorr el at i ons ar e to be i mpr oved or new ones ar e t o be devel oped.

Thi s manuscr i pt i nt r oduces a cor r el at i on between t he Watson charact er i zat i onf act or and wei ght per cent of pol ar const i t uent s of narr ow- boi l i ng (50°F)di s t i l l at e cut s of a coal - der i ved mat er i al f r om t he H- Coal pr ocess. Si m l ar cor -r el at i ons have been f ound f o r data previ ousl y r eport ed by Gr ay et al . 151 f orcoal - deri ved di st i l l ate f ract i ons f rom an SRC- I 1 process. F i nal l y, mul t i pl el i near l east - squar es t r eat ment of t he combi ned dat a f r om t he H- Coal and SRC- I 1

di st i l l at es cor r el at es Kw w t h wei ght per cent pol ar s, at om c H/ C, and m d- boi l i ngpoi nt of t he di st i l l at es. These new cor r el at i ons r el at i ng t he pol ar cont ent ofcoal - der i ved l i qui ds t o t he Wat son char act er i zat i on f actor may be par t i cul ar l ysi gni f i cant because, as not ed by Gr ay et al . [51, devi at i ons of t he obser vedpr oper t i es of coal l i qui ds f rom val ues predi cted by cor r el at i ons based onpet r ol eumdat a are, i n par t , due to t he hi gher concent r at i on of pol ar mat er i al s i ncoal l i qui ds. Theref ore, any i nsi ght i nt o t he r el at i onshi p bet ween the pol ar con-t ent of coal l i qui ds and ot her pr oper t i es i s val uabl e.

Exper i ment al

The H- Coal l i qui d was produced at t he Cat l et t sbur g H- Coal Pi l ot Pl ant onSept ember 25, 1981, whi l e pr ocessi ng I l l i noi s No. 6 coal i n the synf uel mode ofoperat i on. A bl end of "l i ght oi l " and "heavy oi l " pr oducts (1:1.5) was di st i l l edby Chevr on i nt o narr ow- r ange di st i l l at es (50°F), or pseudocomponent s.Speci f i cal l y, 50°F boi l i ng- r ange f r act i ons wer e obt ai ned over t he boi l i ng r angef r om 400°F t o 850°F; the start to 400°F f r act i on and the 850°F vacuum bott oms wer eal so obt ai ned. The pr epar ati ve l i qui d chromat ogr aphi c separat i on pr ocedur eappl i ed t o t he H- Coal sampl es was a modi f i cat i on of met hods t hat have beenr eport ed previ ousl y [6,7,8,91. Br i ef l y, bases were f i r st r emoved by a nonaqueousi on- exchange pr ocedur e [ 7 ] , and t he r emai ni ng aci d- neut r al f r act i on was separat edby col umn chromat ogr aphy w t h al umna [E ] . Thi s separat i on scheme pr oducedf r act i ons cor r espondi ng to sat ur at es, neut r al ar omati cs, neut r al ni t r ogen compounds, ni t r ogen bases, and aci ds. I n addi t i on t o t he f unct i onal cl asssepar at i ons, several chem cal and physi cal measur ement s were made on t hesedi st i l l at es.

Deter m nati on of Bul k Pr oper t i esThe m d- boi l i ng poi nt was det erm ned by ASTM Met hod D-2887 [lo]. Wat er was

det erm ned by t he Karl Fi scher method [ll] usi ng sodi um t ar t r at e di hydr at e forst andardi zat i on. El ement al anal yses f or carbon and hydr ogen wer e perf ormed asdescr i bed by Houde et al . [12]. Speci f i c gr avi t y at 6OoF was det erm ned usi ng a

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pycnometer standardized w i t h boil ed dei oniz ed wat er. The atomic hydrogen/atomiccarbon numbers were corrected to a dry ba sis using the Karl Fischer water re su lt s.

The mult iple l ine ar least-squares regressions, associated s t a t i s t ic a l param-

eters, and graphics were obtained on a PRO-350 ( D i g i t a l Equipment Corporation)computer using a s t a t i s t i c a l software package, RS/l (a trademark of BEN Research

Systems i n Cambridge, Mass.).

Results and Discussion

A correlatio n does not necessarily imp l y a cause/effect relat ionsh ip; rather ,i t only confirms an observed mathematical rel ati ons hip f or a given data s e t . If a

correlat ion is found t o be i n agreement with measured values for a largepopulation, i t can be viewed as usef ul fo r gen eral p redi ctio ns of a givenproperty. In t h e case of coal-derived ma ter ial s, p rop ert ies may vary as afunction of th e sampling point, the un it sampled, the process, a n d the feed coalused. The pres ent i nv es tig at io n compares co rr el at io ns with the Watson charac-te ri za ti on fa ct or from coa l l iq ui ds der ived from the SRC-I1 and H-Coal proc esse s,both of which used bituminous feed coals. For reasons ci ted earl ier , data from

those samples significantly soluble i n hexane ar e presented f or comparison.Results from property measurements re leva nt to t h i s manuscript a r e presented w i t h

the associated data for the correlat ions (Tables 1 , 2, 3 , and 4 ) .

A correlatio n obtained using a mult iple l inear least-squares regression is

evaluated for "goodness- of-fit" using seve ral cr i t e r i a . The softwar e employed i n

t h i s work (RS/ l ) prompts the operator to se le ct the best f i t that can be obtained

from the input da ta . The best f i tis

cha ract eriz ed by having a coef fi ci en t oflinear multiple determination ( R z ) close to one, a la rge F-Value (Regres sion MeanSquare/Fiesidual Mean Sq ua re ), a low st an da rd de vi at io n, and a low significancelevel . Variables ar e selected or deleted from th e multiple determi nation based on

t h e par t ia l correla t ion and s ignificance lev el of that variable. This evaluat ion

of property co rr el at io ns with the Watson ch ara cte riz ati on fa ct or employed com-parable data from H-Coal di s ti l l a te s and SRC-I1 d i s t i l l a t e s . With notedexceptions, only the best f i t , as described above, is reported.

Part I . Correlat ions of K, w i t h H-Coal Data

A plot of K w ver sus mid-boiling po int ( K ) i s given i n Figure la, and a plotof weight percent polars (bases, acids, and neutral nitrogen compounds fromTable 1 ) versus mid-boiling p oint is given i n Figure l b . The range of Kw values

exhibited by these H-Coal d i s t i l l a t e s is small, 9.84 t o 10.37. A comparison ofthese p l o t s (Figure 1 ) reveals a negative correlation between total polars and K,.

A linea r least -squ ares regressi on of weight percent pola rs versus Kw reveals acorre la t ion coeff ic ien t ( R ) of -0.941, sig nif ic an t a t the 99% confidence lev el f orN = 7 . The equation r e s u l t i n g from t h e regression is the following:

K, = -0.0239 ( w t X polars ) + 10.63 2 )

A correlation based on a multiple linear regression including the H /C data w i t h

the weight percent polars versus K d i d not yield a good f i t f or predict ing K w ;the resul t of the regression is the following:

K, = -0.0239 (u t% pola rs) - 0.0109 ( H / C ) + 10.642 3 )

T h e coef ficie nt of l in ear mult iple determinat ion ( R z ) = 0.885 for the regressionrepresented by Equation ( 3 ) . I f , however, th e mid-boiling poin t ( K ) is intro-duced, a multiple l ine ar least-squares f i t t o the same data corr ela tes percentpola rs, mid-boiling poin t (K ), and atomic H/C versus K w i t h R Z = 0.980. Themult iple regressi on equation is the following:

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I

Kw = -0.0199 ( wt $ pol ar s) + 0. 00265 ( m d- boi l i ng poi nt , K)+ 1. 52 ( H/ C) + 7. 12

4)

These dat a, i ncl udi ng t he observed, predi ct ed, r esi dual val ues, per cent di f f er ence(%A), and associ at ed st at i st i cal par amet er s, ar e gi ven i n Tabl e 2.

Par t 11. Cor r el at i ons w t h Kw f or Dat a f r omDi st i l l at es of SRC- I 1

I n 1983, Gr ay and cowor ker s publ i shed a paper [ 5J and an ext ended r eport [ 13]t hat i ncl uded t he r esul t s of anal yses of a ser i es of 19 narr ow- boi l i ng di s t i l l atef r act i ons of a pr oduct gener at ed f r om SRC- I 1 pr ocessi ng of Powhat an No. 5 M necoal on Pr ocess Devel opment Uni t P- 99 ( l ocat ed at Gul f ' s Research Cent er ,Har mar vi l l e, Pa.). Chem cal cl ass f r act i ons wer e obt ai ned f or each di st i l l at e

f r acti on. Fl uor escence I ndi cat or Anal ysi s (FI A) was appl i ed t o di st i l l at ef r acti ons boi l i ng bel ow 589 K, yi el di ng sat ur at e, o l ef i n, and t ot al ar omat i c cl assf r acti ons. "The pol ar f r act i on f r om FI A was cal cul at ed f r om t hr ee component s:t he phenol i cs cont ent of t he aromat i cs f r om a mass spect r omet er anal ysi s, ni t r ogencont ent , and sul f ur cont ent [5]." Pr eparat i ve HPLC was used t o separ at e t hehexane- sol ubl e por t i on of cut s boi l i ng above 493 K i nt o sat ur at es and ol ef i ns,neut r al aromat i cs, and pol ar aromat i cs. Hexane i nsol ubl es wer e grouped t oget heras "asphal t enes 'I Resul t s f r om pr oper t y measurement s r el evant t o t hi s manuscr i ptar e present ed w t h t he associ at ed data f or t he cor r el at i ons ( Tabl es 3 and 4 ) .

A pl ot of Kw ver sus m d- boi l i ng poi nt ( K) of t he 14 di st i l l at e f r act i ons con-si der ed i s gi ven i n Fi gur e l a, and a pl ot of wei ght per cent pol ar s i s gi ven i nFi gur e l b . The range of val ues f or Kw i s l ar ger t han t hat f or t he H- Coal di st i l -l at es , 9. 76 t o 11. 74. The shape of t he Kw pl ot appear s t o be sl i ght l y bi modal .As i n t he case of t he H- Coal r esul t s ( al so Fi gur e l ), compar i son of t he pl ot sappears to reveal a negat i ve cor r el at i on of t ot al pol ar s ver sus Kw. Note t hat t heSRC- I 1 case i ncl udes data f r oma much w der boi l i ng r ange t han was i ncl uded i n theH- Coal case. A l i near l east - squar es t r eat ment of t he dat a der i ved f r om t he SRC- I 1sampl es 1- 7 i n Tabl e 3 ( N . 7 , as i n t he H- Coal case) yi el ds a cor r el at i oncoef f i ci ent of -0. 969, s i gni f i cant at the 99. 9% conf i dence l evel , f or wei ghtper cent pol ar s ver sus Kw. However , i f al l 14 SRC- I 1 di st i l l at es ar e i ncl uded i n al east - squar es t r eat ment of Kw w t h per cent pol ar s, t he cor r el at i on coef f i ci ent i sr educed to - 0. 5773, stati sti cal l y si gni f i cant at t he 95% conf i dence l evel butusel ess f or accurate proper t y predi ct i on. However , as shown bel ow, Kw i s notsi mpl y a f unct i on of pol ar s pr esent , and t he dependence of Kw on ot her propert i esi s mor e i mpor t ant as t he boi l i ng range cover ed by t he pseudocomponent s i si ncreased. The r esul t i ng l i near l east - squar es cor r el at i on f or t he 14 SRC- I 1

di st i l l at es i s gi ven i n Equat i on (5).K = -0.0262 ( wt % pol ar s) + 10.87 5)

Equat i on (5), r esul t i ng f r om a l i near l east - squar es t r eat ment of t he SRC- I 1 dat a,i s st r i ki ngl y s i m l ar t o Equat i on (2) r esul t i ng f r om t he same t r eat ment of t heH- Coal dat a. A mul t i pl e l i near l east - squar es r egr essi on of t he dat a f or t he 14

SRC- I 1 di st i l l at es cor r el ates wei ght per cent pol ar s and at om c H/ C versus Kw w t hR2 I 0. 9943. The mul t i pl e r egr essi on equati on t hat f i t s t he Kw dat a i s t hef ol l ow ng:

Kw = -0.0118 ( wt %pol ar s) + 1.84 ( H/ C) + 8. 03 6 )

These dat a, i ncl udi ng the obser ved, pr edi ct ed, r esi dual val ues, per cent devi at i on,

and associ at ed st at i st i cal par amet er s, ar e gi ven i n Tabl e 3. The r esul t i ngEquat i on ( 61, whi ch r epr esent s a best f i t of t he SRC- I 1 dat a, shoul d be compar edw t h Equat i on (3), whi ch was a poor f i t f or t he H- Coal dat a. Bot h dat a set s yi el da negat i ve cor r el at i on w t h tot al pol ar s, but t he dependence on H/ C i n thi sr egr essi on of t he dat a i s di f f erent .

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Although Equation ( 6 ) represents the best f i t of the SRC-I1 data, a good f i tfor the correlat ion of Kw with percent polars, H / C , and mid-boiling point ( K ) i sgiven i n Equation ( 7 ) .

K w = -0.0106 (wt$ po la rs ) + 0.000651 (mid-boiling-point, K ) +

2.05 ( H / C ) + 7.38 7 )

The value of R Z was 0.995, and the F-Value was 605.8. A comparison ofEquation ( 7 ) fo r SRC-I1 di s t i l l a t e s and Equation ( 4 ) for the H-Coal di st il la te s

reveals the relat ive signif icance of each var iable to the correlat ion w i t h K w .

Part 111. Correlations with K,., fo r Combined H-Coal and SRC-I1 Data~ ~~~

The plots o f K w (Figu re l a ) and weight percent po la rs ( F i g u r e lb) versus mid-bo il ing po int of the d i s t i l l a t es revea l severa l s im i la r i t ies i n these data sets .

The K w values are similar. In the range of mid-boiling points between 490 K and550 K , the trend s for weight percent pola rs a r e si mi la r. The divergence of thetrends fo r weight percent polars i n the two data sets i s suspect based on thes imi lar i ty o f Kw i n the da ta se t s . One pl au si ble explanation can be found i n thedifferences i n the procedures used to is ol at e the polar fra ct io ns . Gray [13]reported 17.4% asphaltenes i n the d i s t i l l a t e cu t a t mid-bo il ing poin t 671.3 K . I nth e SRC-I1 cas e, the se as pha lte nes (hexane in sol ub le s ) were removed from thesample before the p ol ar s were iso la te d by prepa rativ e H P L C . Surely, theasphaltenes included pol ars as co nstit uents th at were not recovered. On the otherhand, asp halt enes were not removed from the H-Coal d i s t i l l a t e s ; ins tea d, theen ti re sample was subje cte d to the complete sep ara tio n scheme. The high est-

boiling H-Coal d i s t i l l a t e (mid-boiling point = 650.8 K ) included i n the combineddata se ts contained 6.9% hexane ins olu ble s t ha t would not have been analyzed forpolars i n the procedure used by Gray.

A multiple linear least-squares treatment of the combined data (combining 7

H-Coal d i s t i l l a t e s a n d 14 SRC-I1 di s ti l la te s ) co rre la tes weight percent polars,mid-boiling point ( K ) , and H /C versus Kw w i t h R 2 = 0.987. The mul tip le regre ssio nequation th at best f i t s the combined dat a is the following:

K w I -0.00685 (wt$ po la rs ) + 0.00278 (mid-boiling point, K )

+ 2.73 (H /C ) + 5.28

These da ta , including t he observed and predicted value s, ar e given i n Table 4; theobserved versus t h e predicted K, are plot ted in Figure 2 .

Conclusions

A negat ive cor re la t ion ex is ts for the weight percent polar constituentsversus K w for d i s t i l l a t e s derived from these coal li qui ds . Undoubtedly, Kw is

als o a function of the aromatics present; but the contributio ns of the aromaticfunctionality should be contained in the H /C measurement. A t l e a s t for these datasets, the weight percent of neutral aromatics does not change significantly i nadjacent dist i l la tes, whereas signif icant concentrat ions of polars a re confined t otwo di st in ct regions within the boiling range of t he d i s t i l l a t e s ( s ee Table 1 ) .

The rela ti ve contributions of aci ds and bases to t hi s corr ela tio n aredi ff ic ul t to ass es s. Gray and coworkers [5,131 did not separate these polar sub-

fra cti ons . However, a high cor rel ati on w i t h polars, although not the same cor-relation, was found fo r the SRC-I1 data and f o r the H-Coal da ta . There is noreason t o assume that the same correlation exists for acidic or basic componentsof the polar fra ct io n. There is a lso no reason t o assume tha t th ei r rel at ive con-

tr ibutions to Kw would not change from sample to sample. Changes i n K w a t t r ib u tedto the weight percent po la rs present may al so r e fl e ct the degree of assoc iatio n

i

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,

between the aci di c and basi c component s. The r ol e of bot h f unct i onal gr oupsshoul d be assessed.

I t i s unl i kel y t hat cor r el at i ons t hat woul d be gener al l y appl i cabl e to coall i qui ds can be extr act ed f r om onl y two dat a set s. However, t he dat a set spresent ed were obt ai ned on coal l i qui ds pr oduced f r om t wo di f f er ent bi t um nousf eed coal s f r om di f f er ent processes. Yet , an excel l ent cor r el at i on i s f ound t hatf i t s the dat a fo r t he char act er i zat i on f act or , Kw Subbi t um nous f eed Coal s mayyi el d di f f er ent f i t s f or t he Wat son char acter i zat i on f actor.

Acknow edgment s

We woul d l i ke to acknowl edge sever al coworker s f or t hei r cont r i but i ons to

t hi s wor k, i ncl udi ng Fr ank McCown who per f ormed t he separ at i on of bases by non-aqueous i on exchange, M ke Ferr er who assi st ed i n per f orm ng t he al um naseparat i ons, and J oseph Hacket t f or per f or m ng the m d- boi l i ng poi ntdet er m nat i ons on t he H- Coal di st i l l at es. We woul d al so l i ke t o acknowl edgeDenni s Fi nset h and J ames Gray f or i l l um nat i ng di scussi ons and advi ce.

A por t i on of t he resear ch on t he H- Coal was per f ormed whi l e M l dr ed Perr y wasunder appoi ntment t o t he U.S. Depar t ment of Energy Post - Gr aduat e Research Trai ni ngPr ogr amadm ni st er ed by Oak Ri dge Associ at ed Uni ver si t i es.

Di scl ai mer

Ref er ence i n t hi s r epor t t o any speci f i c pr oduct , pr ocess, or serv i ce i s t o

f aci l i t ate underst andi ng and does not necessari l y i mpl y i t s endor sement or

f avor i ng by t he Uni t ed St at es Depart ment of Energy.

- 0 K w SRC- I-- - K w H-Coal211.0

lo.ok , I * ..-.-.--=-

801 I , , , , , , ,- % Polars, SRC-E

40

vi

MID-BOILING TEMPERATURE. KFigure I Prof i le of K w and Weight % Polors o s a

Function of Mid-Boiling Temperature (K)f o r Combined H-Cool an d S R C - I D ot o.

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References

Watson, K . M . , and Nelson , E.F. Ind. Eng. Chem., 1933, 25, 880.

Watson, K . H . , Nelson, E.F., and Murphy, G.B . In d. EnR..Chem., 1935, 27,

1460.

Smith, R . L . , and Watson, K . M . Ind. Eng. Chem., 1937, 29, 1408.

Wilson, G . M . , Johnston, R . H . , Hwang, S.-C. , and Tsonopouslos, C . Ind. Eng.a,rocess Des. Dev., 1981, 20, 94.

Gray, J.A. , Brady, C.J., Cunningham, J .R. , Freeman, J . R . , and Wilson, G.M.Ind . Eng. Chem., P ro ce ss Des. Dev. , 1983, 22, 410.

Perry, M.B . , White, C.M., Finseth, D . H . , Sprecher, R.F., and Retcofsky, H . L .

Proc. NATO AS1 App li ca tion of New Spec tros copi c Techniques t o Coal Science.B .M . Lynch, ed., Martinus Nijhoff Publishers, BV, Dordrecht, The Netherlands,

t o be published i n 1985.

Green, J . B . , Hoff, R . J . , Woodward, P.W., and Stevens, L.L . Fuel, 1984, 63,

1290.

1 .

2.

3.

4.

5.

6 .

7 .

8.

9.

10.

11 .

12.

13.

Later, D . W . , Lee, M.L., Bartle , K . D . , Kong, R.C. , and Vassilaros, D . L . Anal .m, 981, 53, 1612.

Sch i l le r , J . E . , and Mathiason, D .R . Anal . %., 1977, 49, 1225.

Annual Book of ASTM Stand ard s, 1980, Part 24, 788-796.

Mitchell, J . , J r . , and Smith, D.M. Aquametry, 2nd Ed., Pa r t 111, 1980, 5 ,107-136.

Houde, M . , Champy, J . , and Furminieux, R . J . Micro Chem., 1979, 24, 300-309.

Gra y , J.A. DOE Report DOE/ET/10104-7 (DE810259291, 1981.

Table 1 .

Weight Percent of Various Compound Classes in H-Coal Distillates,

Normalized to 100 Percent Recovery

Mid-Boiling Neutr al Neutra lPoint, K Sat ur at es Aromatics Bases Acids Nitrogen

493.6513.6

538.0566.9595.8623.0650.8

30.0 51.O 8.7 6 10.0 0.24

31 .O 55.0 5.50 6.5 2.00

29.5 60.5 3.15 6.5 0.3525.5 61 .O 7.90 4.5 1.1022.5 61.5 7.29 8.5 0.21

13.9 63.9 11.50 6.3 4.4013.0 56.0 22.06 8.0 0.94

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I

Tabl e 2.

Resul t s of Mul t i pl e Li near Least - Squares Regr essi on of K Usi ng Wei ght PercentPol ars, M d- Boi l i ng Poi nt , and At om c H /C f or H- Coal Di st i l l at es

KW -0. 019876( wt % pol ar s +O 00265(mid-boil ng+1.521086(H/ C) +7. 118681a

poi nt , K)

Wei ght

M d- Boi l i ng Per cent HI C KW KWPoi nt , K Pol ars ( dr y) ( obser ved) ( pr edi cted) Resi dual b %Ab

493.6 19. 0 1.375 10.15 10. 140 0.009 0. 092513.6 14.0 1.351 10.26 10. 256 0. 003 0. 033538.0 10.0 1.360 10. 37 10. 414 - 0. 044 0. 429566.9 13.5 1.235 10.25 10. 231 0. 018 0.182595. 8 16.0 1.277 10.34 10. 322 0. 017 0. 173623. 0 22. 2 1. 198 10. 17 10.150 0.019 0. 189

650.8 31. 0 1.076 9.84 9. 864 -0. 024 0. 244

Var i abl eName

Coef f i ci ent St andar d Si g.Val ue Devi at i on l evel

I

I

Wei ght Per cent Pol ars - 0.019876 0.003605 0. 011745M d- Boi l i ng Poi nt , K 0. 002650 0.000696 0.03 1869HI C ( dr y) 1.521086 0.459905 0. 045481

Anal ysi s of Var i ance Tabl e

I

t

YI

sum of Mean Si g. Mul t i St d Devi ati onSquar es OF Squar e F Val ue Level R of Regr essi on

Regr essi on 0. 183857 3 0.061286 49. 88 0.0016 0. 9803 0.0351Resi dual 0. 003686 3 0. 001229

%A I IResi dual I K, observed) x 100

acoef f i ci ent s and const ant t er m gener ated by RSI l bef or e adj ust i ng to appr opr i atesi gni f i cant f i gures.

bcal cul ated bef ore roundi ng of f K ( pr edi cted) .

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Table 3.

Results of M ulti ple Linear Least-Squares Regression of K, Using

Percent Polars and Atomic H / C for SRC-I1 Dis t i l la tes

K = -0.01 1807(wt% polars) +1.840546(H/C) +8.028509a

Weight

Mid-Boiling Percent H /C K, KPoint, K Pola r s (d ry) (observed) (pre dic ted ) Residualb % A b

339.7 0.00 2.040 11.74 11.783 -0.045 0.387372.4 1.60 1.846 11.36 11.408 -0.046 0.406393.6 2.50 1.898 11.59 11.493 0.095 0.824410.2 5.70 1.699 11.12 11.088 0.035 0.319439.7 29.50 1.487 10.33 10.417 -0.085 0.824468.6 52.00 1.353 9.92 9.905 0.012 0.129

493.0 39.55 1.316 9.99 9.985 0.002 0.028524.7 32.40 1.279 10.05 10.001 0.053 0.527547.4 20.95 1.315 10.16 10.201 -0.044 0.442571.9 13.80 1.131 9.92 9.948 -0.032 0.328573.0 14.45 1.208 10.13 10.082 0.050 0.497615.2 12.10 1.090 9.96 9.892 0.062 0.630650.2 12.85 1.027 9.76 9.767 -0.003 0.038671.3 7.30 1.015 9.76 9.810 -0.055 0.564

VariableName

Coefficie nt Standard Sig.Value Dev iatio n Level

Weight Percent PolarsH /C (dry)

-0.01 18071.840546

0.0011 150.05 1536

0.00010.0001

Analysis of Variance Table

sum Of Mean Si g. Multi Std Dev iatio n

Squares DF Square F Value Level R ' of Regression

Regression 6.521707 2 3.260854 959.38 0.0001 0.9943 0.0583Residual 0.037388 1 1 0.003399

%A ( IResidual I /K,observed) x 100

acoefficients and constant term generated by RS/1 before adjus t ing to appropr ia te

bCalculated before rounding off K, (predic ted) .

s igni f i cant f igures .

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Tabl e 4.

Resul t s of Mul t i pl e Li near Least - Squar es Regr essi on of For Combi ned Dat a:SRC- I 1 (Rows 1 t o 14) and H- Coal ( Rows 15 t o 21)

Kw i 0.006847(wt% pol ars) +0. 002776( m d- boi l i ng poi nt , K)+2. 734032(H/ C) +5. 27978aa

Wei ght Hi d-

Sampl e Per cent H/C Boi l i ng K KWNo. pol ar s (dry) Poi nt , K ( observed) ( pr edi ct ed) Resi dual b %Ab

123456

789

101 112131415161718192021

\

0.00 2. 040 339. 71. 60 1.846 372.42. 50 1.898 393. 65. 70 1.699 410. 2

29. 50 1. 480 439.752. 00 1.353 468. 6

39. 55 1. 318 493. 032. 40 1.279 524. 720. 95 1.315 547. 413. 80 1.131 571.914.45 1. 208 573. 012. 10 1. 090 615. 212.85 1.027 650.27.30 1. 015 671.3

19.00 1. 375 493. 614. 00 1.351 513. 610.00 1. 360 538. 013. 50 1.235 566.916. 00 1.277 595.822. 20 1. 198 623. 031. 00 1. 076 650. 8

11. 7411. 3611. 5911. 1210. 339. 92

9. 9910. 0510.169. 92

10. 139. 969.769. 76

10. 1510. 2610.3710. 2510.3410.179. 84

1 1 . a0011.35111. 54611. 02410. 3639. 924

9.97710. 01310.2519.067

10. 0169. 8869.8059. 869

10.27910. 30310. 42310. 13710. 31510.1329.816

-0. 0620. 0100.0420.099-0. 03- 0. 006

0.0100. 040- 0. 0940.0480.056

- 0. 069-0. 041- 0. 113- 0. 129- 0. 043- 0. 0530.1120. 0240.0370. 023

0.5330.0960.3690.8910.3100.066

0. 1020.4070.9320.4920. 5590. 7010. 4271.1611.2740. 4230. 5131.0960. 2360. 3670. 243

Vari abl eName

Coef f i ci ent St andard Si g.Val ue Devi at i on Level

Wei ght Per cent Pol ars - 0. 006847 0.001725 0.0010H/ C (dry) 2. 734032 0. 237914 0. 0001M d- Boi l i ng Poi nt , K 0. 002776 0. 000667 0. 0010

~ ~~~ -$A i I Resi dual / K, observed) x 100

acoef f i ci ent s and const ant t er m gener at ed by RS/l bef or e adj ust i ng to appropr i ates i gni f i cant f i gures.

bcal cul at ed bef ore r oundi ng of f K ( predi cted) .

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Table 4. (Continued)

~~~

Analysis of Variance Table

sum of Mean Sig. Multi Std DeviationSquares DF Square F Value Level R 2 of Regression

Regression 6.875659 3 2.291886 437.59 0.0001 0.9872 0.0724Residual 0.089038 17 0.005238

12.0

0

E 11.0.uKI

10.0

10.0 11.0 12.0

Kw , bserved

Figure 2- Plot o f K w (observed) fo r Combined SRC-IIon d H-Coal Dolo versus Kw (p red ic ted) by

Mult ip le Regression) .

'Equat ion fo r l inear leos t -aquores l ine of best f i t .

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