1958_Montgomery and Boyd_A New Method of Hydrocarbon Structural Group Analysis

8/13/2019 1958_Montgomery and Boyd_A New Method of Hydrocarbon Structural Group Analysis

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-1-

CANADADEPARTMENT OF MINES AND TECHNICAL SURVEYSMINES BRANCH

OTTAWA

Fuels DivisionTechnical Memorandum - 83/ 58-RBS

A NEW METHOD O F HYDROCARBON STRU CT URAL GROUP ANALYSIS

by

D. S. Montgomery and M. L. Boyd

This pape r is published with the pe rm iss ion of the Direc tor ,Mines Branch, Depart ment of Mines and Technical Surveys,

Ottawa, Canada.

Pap e r Prep a red for Presenta t ion Before the Div is ion of Gasand Fuel Chemistry. American Chemical Society

Chicago, Illinois Meeting, Sep tem be r 7 - 12, 1558.hI

(Copy No. -1 June 1, 1958.

R


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-2-

A NEW METH OD O F HYDROCARBONSTRUCTUR AL GROUP ANALYSIS

byD.S. Montgomery and M. L. BoydFu els Division, Mines Branch,

De part me nt of Mines and Technical Surveys.

A B S T R A C T

A m e t J d o hydrocarbon s t ru ctur a l groupanalysis has been developed for application to pure com-pounds in which th ree chem ical and two physical proper -t ies have been ex pre sse d in te rm s of f ive s t r uc tur a l groupsin a f orm which m ay b e s imul taneously so lved by mod ernhigh speed computing equipment. Th e chemical propert ie si n c l t ~ r l - hn rarho-nand hydrogen content as well as the num-be r of a rom at i c c a rbon a toms p resen t pe r molecule.physica l pro pe r t i es requi red for the analysis are the molarvolume and m ol ar refract ion. This method has been testedon a selecte d gro up of 114 hydrocarbons whose propert ieshave been determined by A.P. I. P r o j e c t 42. The resul t sof ; the appl ica t ion of th is s t r uc tur a l analysis sys tem a r e des-cr ibed in detai l an d the accuracie s at tained have been tab-ulated.

The


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-3 -PRESENTED BEFORE THE DIVISION O F GAS 4ND FU EL CHEMISTRY

AMERICAN CHEMICAL SOCIETY'Chicago, Illinois, Meeting, Septe mbe r 7-12, 1958.

I

>

iid

I.,

D. S. Montgomery and M. L. BoydDepa rtment of Mines and Technical Surveys , Ottawa, Ontar io.

INTRODUCTION

The synthesis and systematic study of the physica l prope r t ies of pu rehydrocarbons has been in p r o g r e s s f o r a number of , y e a r s to fac i l i ta te thedetermination o f the molecu lar str uct ure of hydrocarbons direct ly o r byanalogy, that is by compar ing cer ta in proper t ie s of compounds of unknownst ru ct ur e with those of compounds whose stru ctu res a r e kaown.

The value of studying physical p ro pe rti es of a se r ies of Compounds, asa me an s of pred icting the pr op er ti es of unknown compounds a nd affording amea ns of checking the ac cur ac y of the physic al co nstants of compou nds, hasal so been repeatedly demonstrated. In genera l , the study of the physical prop-er t i es of hydrocarbons has been undertaken by a num ber of independent invest-igat ors and usually has been confined to hydro carbon s containing a l imited num-b e r of types of s tru ctu ral groups, o r , al ternat ively, only on e physical propertyof a l a rge va r ie ty of compounds has been examined.

Th i s paper des c r ibes a method of sim ultaneously analyzing c er t ain phys-ica l and chemical proper t ies of l iquid hydrocarbons to se cu re s t ruc tur a l informa-tion. Although the sys tem des cribe d is confined to specif ic cl as se s of hydrocar -bons, i t is mo re genera l than any system s o far proposed and involves the sim ul-taneous considerat ion of thr ee chem ical and two physical pro pe rt ie s to yield quan-t i tat ive information concerning f ive s tru ctu ral groups.promoted by a d e s i r e to improve exis ting s t ruc tura l analysis systems for purehydrocarbons and to faci l itate the study of natu ral ly o cc urr ing hydrocarbons.new possib ilities offered by mod ern high speed computing equipm ent provided a nadditional incentive to re-examine and extend the ea r l i er w ork in the f ield of s tru c-tura l analysis .

The invest igat ion wasThe

1 The most ex tensively used s t ru ctura l analysis s yst em applied to hydro-carbon mixtures has been developed by Waterman and his school (13) beginningwith the cl ass ica l Waterm an Ring Analysis of 1932 (19, 2 0 ) and extending to then-d-M method of 1947 (14). van Krevelen employed som e of the concepts of theWaterman Ring Analysis to develop a system that w a s pa rt ic ula r ly sui ted to thestudy of highly condensed aro ma tic str uc tur es which were ass ume d to be the majo rconstituents of coal (7 , 8). The chief c r i t i cis m of the var io us methods of s t ruc-

J


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- b -t u r d group ana lys is (15) of oil and coal is that when applied to pur e compoundspoor r esu l t s a r e ob ta ined .t o f o r m u l a t e a s t ru c tu ra l ana lys i s sys tem based on he physical pro pe rtie s ofknown compounds, but of such a form that i t could be used w i t h reasonable con-f idence to ana-lyze the s t ru ct ur e of high molecu lar weight mater ia l .

These cons iderat ions made i t de s i ra ble to a t tempt

The method p resen ted here w a s evolved from a method of carbon typeIn this method, van Krevelennal ys is publ ished by van Krevelen (4) in 1 9 5 2 .divided the carbon atom s in a s tru ct ure into four main types:-

CH . CH - CHarornatic; c4 = C, aromatic ;Cw h er e C n the denominator of each fract ion rep resented the to ta l number ofcarbo n a toms p er molecu le .relatio ns hips:

He then se t up the following fo ur quan titative

(a) C1 t C2 + C3 t C4 = 1 (carbo n balance)(b) 2 C 1 t C2 t C3 = H / C(c) c2 t c* = 2R/C(d) C3 t C4 = fa

(hyd roge n balance)( r ing balance)(aro ma tic carbon balance)

, The se equations w e r e not independent, and hence could not be solvedsimultaneously. van Kr ev el en solved these equations by giving an equation forC1 as a func tion of H/ C which rep res ent ed the sta tis tic al probability of the oc:cu rr en ce of a CHZ group in the molecule . The use of this e quation w a s open oconsi derab le question and consequently the method was never widely applied.Equat ions (a) , (b) and (d) , above, a r e t ru e by definition; however, equation (c),th e r i ng balance equation, is only valid f o r high mole cular weight hydrocarbonswhere the factor 2/ C can b e neglected and where two junct ions a r e associatedwith the format ion of eve ry r ing . The re a r e s t ruc tu re s where th is r e la t ion i snot valid, such as in sp ir o compounds, and in three-dimensiona l s tr uc tu res wheret h r e e r i n gs p o s s e s s a com mon side. van Krevelen's system was devised to eluci-da te the s tr uc tu re of coal and coal-l ike products w here the proportion of saturatedca rbo n atoms was sm al l o r negligible. While this choice of carbon types was suit-ab l e fo r the s tudy of coal, i t was undesirable fo r the study of petroleum since i tfailed to differe ntiate between chain and cyclic CH2 groups. Hence, a five-typecarbon c las si f i ca tion w a s chosen which differed from that of van Krevelen bydivid ing his C1 into two t ypes . The carbo n linkages have theref ore been dividedinto the following five types.

c1 = num ber pe r molecule of CH3, CH2, CH, and C groups in l inearand branched chains.


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- 5C2 = number per molecule 0.f CHZ groups in sa tura ted r ings ,including the ca se wh ere the hydrogen atom s ma y be

replaced by branched o r l inea r chains.number per molecule of CH groups which are junctionsin fused sa turat ed r ings, as wel l as s im i lar ly s i tua tedgroups whe re the hydrogen is replaced by l ine ar o r branchedchains.

c 3 = -

c4 = num er pe r molecule of CH groups in arom atic r ings , includ-ing the c as e where the hydrogen m ay be repla ced by branchedo r l inea r chains .

c5 = number per molecule C groups which a r e junctions in fusedarom atic r ings, a s well as junctions between satu rate d andaromatic r ings.

It is possib le to rew ri te the carbon balance, the hydrogen balance and thear om at ic carbon balance equations in te rm s of this new classification o f s t ruc -tu ra l groups. It should be especially noted that in the van Krevelen sy stem themol ecu lar weight was unknown and hence the s t ruc tur e was descr ibed in term s offrac t ions of the total number of carbon atoms. However , the pre se nt s yste m wasdesigned for the cas e where the molecular weight (as wel l a s 70 carbon, 70hydro -gen, densi ty, refra ct iv e index, and arom atic carbon content) was ei ther 'known o rcould be determined. The carbon classif icat ion w a s t he re fo re expressed in t e rmsof the actua l nu mb ers of the different carbon types C1 - Cg pre se nt in the molecule.Th e Ring Balance Equation could not be used when analyzing an unknown hydrocarboa,a s there was no ac cu ra te method of estimating the number of ring s in the molecule.The fundamental ba sis of this str uc tur al ana lysis sy stem , ther efore , consis te: infinding two addit ional physical prop ert ie s which could be a ccur atel y expressed inte rm s of the above s tru ct ur al groups to give five independent equations which couldthen be solved simultaneously.

Theoretically, any two physical pro per t ie s would be sui table, provide& i tThe two physical prope rt ies chosen we re the mo lar

we re possible to ex pre ss therm as independent equations in te rms of the s t ruc-tural types already defined.volume and the mo lar refract ion ( the Lo rentz -Lo renz expression) .physical properties of liquids can be approximately descr ib ed in te rm s of a l inearcombination of the ato mi c contributions, and both quantities have been extensivelyused fo r the purposes of elucidating struc tur e 7 , 18, 5 , 10). It w a s assumed thatthe s am e functional form of the equation would apply to both physical pr op ert ies ,and that both prope rt ies could be ex pres sed in te rm s of the sam e groups of chemlcaltypes. Owing to the intimate relation between the se two quantities, it was felt that thloss in accuracy associated with grouping together so many different ch emica l linkagsmight easily yield two expressions which we re me rely l inea r combinations of eachother. It remaine d for this investigation to dem on str ate that the difference s betweenthe expression derived f or the mol ar volume and tha't for the mo lar refract ion we reof such a magnitude that rel ia ble s tru ctu ral information could be sec ured by thesimultaneous solution of these expressions.

Both of th es e


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- 6 -DEVELOPMENT OF THE FIVE EQUATIONS

I t should be em phasize d a t the outset that this method as presen tly con-s t i tu ted is applicable only to certa in spe cif ic cla ss es of compounds.division of the carbon groups into thevarious types, c a r e w a s taken that thehydrogen balance equation should always be sat isf ied. It w a s recognized thatthis equation was not st r ic t ly t r ue a s defined for the no rm al and branchedparaf f ins . This c a s e wil l subsequently be d iscussed . The pre se nt syst em w i l lde al with monocyclic compounds and fused ring compounds, both satura tedaromat ic , but w i l l not include polycyclic non-fused stru cture s.and three-dimensional ring systems are a t o excluded . I t can be shown thatthe contributions to the m ol ar volume and mo lar refract ion of junction atomsin pi lycyclic non-fused compounds a r e not identical with any of the five typesdea lt with here , but i n fact , r e p r e s e n t a 6th (saturated) and a 7th (aromatic)type of linkage. Anoth er c la s s of compounds excluded a r e those containingolefin ic o r acety lenic bonds. Xx% this w ork only double bonds existing in aro-m a t i c rings have been considered.

In the

Spiro compounds

The method de pends upon the ability to measure the densi ty and refract-ive index of hydro carbon s in t he li quid s t a t e a t 20C. at one a tmosphere pres-s u r e , o r on the capaci ty to c or re ct to th is s tandard s ta te mea sure men ts nadeunder other conditions. Excep t where otherwise specified, the coefficients ofthe molar volume and molar refract ion equations have been determined fromthe propert ies of the hydrocarbons prepared by A. P.I. P r o j e c t 42 (16).

The Carbon, Hydrogen and Aromatic Carbon Balance Equations The carbonbalance, hydrogen balance , and ar om at ic carbon balance can b e wri t ten as fol-lows, by definition:

c1 t c2 t c t c 4 + c = C (1)3 5

Th e total numbe r of carbon atoms pe r molecule EC was calculated fromthe- carb on ana lysis and the mol ecu lar weight. The total numb er of hydrogena tom s pe r molecule GH, was si mi la r ly calculated from the hydrogen analysisand the mo lecu lar weight. The total numb er of aro ma tic carbon atoms in themolecu le, 6Ca, w a s not qui te so read ily available, although it could be dete r-mined by spectro scopic mea ns (1) .tion (testing the method on known compounds), direc t meas ure me nt of thisquantitiy was not req uire d.

F o r the purpos es of the pre se nt investiga-


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Th e Molar Volume Equation Th e following mo lar volume equation wasdeveloped for the purpose of this s t ruct ura l analysis system:

M . V . = C1(16. 38 + 30.61) + C2(13 .20 + 28.48) +a t .GC (4)20 c.

1 atm. C3(10. 981 + 20.679) + C4(12. 406 + 14. 042 - 1. 96 5 t 10.13C2p r e s s . ZC TC


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- 0 -

found to be: It

It w i l l subsequently be shown that the K's in each b racke t a r e no t iden tica l ,these have hence been designated kl o k5 respectively. The quantity K inthe above equat ion ex pr es se s the inc rea se in the molar volume that takes p laceon reducing the molec ula r weight of a p ar t i cula r species .

eDete rmina tion of v1 and klThe mola r volume for the 13 nor mal paraff ins on the l i s t of A. P. I.

P r o j e c t 4 2 16) was plotted a gainst the number of carbon at oms in the molecule.Th e equation of the re sulting str ai gh t l ine was determ ined by the method ofle as t squa res and found to be as follows:

M.V. = 16. 38C1 t 30.61 (9)Dete rmina tion of v and kThese quant i ties w er e calculated in a manner s imilar to that used for the

calcu lation of v1 and kl, using the phys ical pr op er ti es given by Ward and Kurtz(21) for cyclopentane, cyclohexane, cycloheptane and cyclooctane. Th e mola rvolume of these compounds could b e exp res sed by the following equation:

2 2

M.V. = 13.,20C2 t 28.48 (10)Determination of v4 and k4Some diff icul t ies w er e encountered in obtaining suitabl e dat a for compounds

containing only C4's . Th e following compounds we re used: benzene (pro pertiestaken from Egloff (3) , cyclo octate traene (pr op er tie s by Ecclesto n ( 2 ) et al) , andcyclopentadiene (W ard and Kurtz (21).cyclopentadiene is required.

A word of explanation about the use of theSince it contained one C, group i ts u se he re is ,

I4slightly differe nt method had to be used to determ ine v3 and kj, since

2o compounds existed containing C gro up s only. Compounds containing Cand c 3 g roups bad to be used, and fo r this reaso n the following proce dure was I-


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- 9 -adopted. [(M. V. observed - C (13.20 t 2 8 .4 8 y / c was plotted a g a i n s t1&C. Th e re su lt of this plot was- a strai ghfy ine whose slope was k3 andintercept.v3 . Using the following compounds fro m the A . P. I. List (16):bicyclooctane 543, decahy dronaph thalene 569 and 570, perh ydro fluo rene 561,perhydropyrene 578 and'perh ydro chry sene 575, v3 w a s det erm ine d to be10.981 and k3 to be 20.679. Th e coefficient of C was undoubtedly a functionof the r ing size, but the values found.for f ive- an% six-m emb ered r ings we realm os t identical.

2 3

5ete rm ina tio n of v5 and kThe se quanti ties we re determined in exactly the s am e manner a s tha t

used f or the determ ination of v3 and k3.in obtaining sui table l iquid s tate m ol ar volume d ata a t 20C for fused r ing aro-ma tic compounds that contained only C4 nd C5.have bee n determ ined by Ubbelohde (11, 12) for se ver a l fused r ing aromat i c com-pounds.By plotting (M. V.age in volume as a function of the d eg re e of condensation.tionship, the solid st at e mo la r volume data of van Krev elen .( l7) for fused r i n gar om at ic compounds was "conv erted" to the liquid st at e a t 20C. Using the dataobtained in th is mann er for anthracen e, ch rys en e, phenanthrene (Ubbelohde), andfor dibenzanthracene, chry sen e, py rene and coronene (van Krevelen 's data con-ve rt ed to the liquid sta te ) v5 w a s dete rmin ed to be 5.124 and k5 o be -5. 238.

Some diff icul t ies w er e experiencedLiquid mo la r volume dat a a t 20C.

This author a ls o determined the mola r volume for the sol id st at e at 20C.- M. V. s ) v e r s u s C5/ Cg, t w a s possib le to expres s th is shr ink-By means of this rela-

Th e molar volume equation thus obtained w a s used to calculate the mo la rvolume for the appropriate c la ss es of compounds on the A . P . I. L i s t ( 1 6 ) and tocom pare the resu l ts with the experimental values. The res ul ts of this compari-son showed that a study of the interactions between various types of st ru ct ur algroups had to be made.C4 oc cur red in the sam e molecule and when C2 and c4 occurred together . In thefor me r case , da ta f rom Ward and Kur tz (21) were used to evaluate the ma-mitudeof the inte ract ion, and in t he l a t t e r case A . P. I. data (16) w e r e employed. In br ief ,the method of determining the functional for m and magnitude of the interaction t er m sconsisted o f obtaining the difference between ob ser ved and calculated mo la r volumep e r C4 group and plot ting this d iffere nce against C / LC n t he f i r s t case and C /&Cin the second. Two strai ght lines wer e obtained, f?om which we re derived the twot e r m s in Cl /&C and C2 /c C which were added to the C t e r m in Equation 4.The a ccu rac y with which this I ' corre cted " equation predicted the mo lar volumeof the A. P. I. (1 6 ) hydrocarbons is given in Table I.

Th e mos t significant interactions w er e found when C1 and

29


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-10Table I - Accu racy of the Authors' Mo lar VolumeEquation Applied to A. P. I. 42-Hydrocarbons . ~-

N o . in Average Value ofClass of:rCompound

n-paraffinsbr. -paraffinsMonocyclic

s a t u r a t e sFused r ings a t u r a t e sMonocyclica r o m a t i c sFused r inga r om a t i c s

Class

133827182113

-MVcalc - MVobs x 100

MVobs.-0 .02to. 31t o . 10to.66to. 03- . 4 6

StandardDeviation

' 0.070.80 I0.330.800 .190 .89

The M olar Refrac t ion Equationequation was developed for the pur po se of th is analys is:

The followine mo lar refraction

20'C.1 atm.pres s . C3(3. 693 t 0.3395) t

Ec,

C5(5 . 73 4'- 14. 333) . . . .' . . -. . . . . . . . . . . . . (12)CCIn this equation, M . R. re f err ed to the Lorentz-L orenz expression

f o r t he m o l a r r e f r a c t ion e ,-'., here n w a s the re frac tive index for thesodium D l ine at 20C.exact ly the sa me man ner , and us ing the sa me compounds as in the mol ar volumeequation.the mo lar refra ctio n dat a for the fused ring arom ati c compounds of van Krevelen( 1 7 ) r e f e r to me as ur em en ts m ade of the compounds in benzene solution and havebeen referred t o by van Krevelen (6) a s I hypothetical l iquid sta te data". 1accu racy with which th is equation pred icts the mola r refra ctio n of the A . P. I. 42 '( 1 6 ) hydrocarbons is indicated in Table 11.

+ 2 dTge coefficients in this equation were determined inAttention i s drawn to the fact that, in the determination of the C5 e rm,

The


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- 11-METHODS O F SOLUTION O F THE SET O F F I V E E,2UATIGNSEquations 1, 2, 3, 4 and i?? const i tute the three chemica l and two

phy sica l prop erty equations that, when solved simu ltane oas ly f o r C1, 2, C 3 ,C4 and C5, form the proposed system of analysis.equat ions a r e l inear b u t equations 4 and 12 a r e quadrat ic in C l and.Cs e t of l inea r and quadrat ic equations w a s initially solved ia the followmg manner.Th e solution was obtained by redu cing the sy ste m to a l ine ar form by subst i tut-ing an ini t ial value C1 = Cz = 0 in the non- linear t erm s.:mear equations was then solved by the stan dard methods of m at ri x alge bra.

The f i rs t three of theseThis2

The resul tant se t of_ .Table I1 - Accurac y of the Authors Molar Refract ion

Equation, Applied to A. P. I. 42 Hydroc arbonsStandardo . & Average Value ofc lass of Compound C la ss MPLc,lc - MRObS x 100 Deviat ion

MRobs.n-paraffins 9 t 0 .012ST. -paraffins 3 7 [email protected] 9blonocyelic

satur ates 26 -0.01Fused ringsatu rates 19 -0.008Mono cyclicaromat ics 19 $0 .16Fused r ingaromat ics 8 to. 17

0,0560 . 2 60.200 .260 . 510. 64

Th e new values o f Cl in ea r te rm s and ano ther sofurion was obtained. Th is iterativ e proc edu re wasrepe ated until two consecutive solutions we re equal.solution was whether or not the i terat ive proc edur e would converge.pra cti ca l point of view the ra te of co nvergenc e was im portant.i te ra tions va r ied f r o m three for the paraffins to thirty for s o m e of the fusedring aromatic compounds.

and C fro m this solution w er e theii substirated in the n o n -IThe cr i t ica l aspect of the

F r o m t h eThe numbe r of

Since the- m el ar volume and the mo la r refract ion equations w e r equadrat ic in C1 and Cz, in general th er e would be four root s. S ince i t w a sc l e a r that the i terat ive proc edu re yielded only one root , i t was des irable toobtain a method of solution which would give a l l the roots . F or th is reason thes e t of five equations w as solv ed by a secondmethod. I t w a s possible, by simplealgebraic re-arra ngem ent of the three l inear equations, to expres s C g , C4 andC in te rm s of C1 and C These values fo r C C and c5we re then subst i tuted5 2 3 4


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-12 -- in the mola r volume an d mo lar refra ct ion equations and the fol lowing two

quadrat ic equations i n C1 and C 2 resulted:c1 + (13). 96 C;' t (0.077 EC - 1. 9 6 C a - 8. 17C2 - 1.962H - 9.3493-&z ( f C )

3.699EC + 1.42 5


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TABLE III.M C E P l . Y o r

-13-

orovs I - -rornmsQ 8 u 12.07 4.07Q9 13 13.U 4-04S3l 14 13.99 4.Olm 15 15.W 4-04534 16 15.99 4.01n5 17 i7.m 0.02 7 18 11.91 4.09542 20 19.59 4 - 0 1106 26 25.90 4 - 1 0

Gx-cup II - b r a n c b d p m m n .1

107109u3163164la191

222232527

345

gco51

5 l ONN5)

. 9 59 654955

554556557

6636)In

2634263623342832262626252626262819262020142616131026211418302826jzY

25.68 4.3233.91 4 - 0 325.40 -0.6036.22 4.2222.90 -0.1034.19 4.1928.30 Q.3432.10 rO.1325.18 -0.222 5 . 2 ~ -0.7324.62 -1.3824.85 -0.1525.62 +.la25.60 4.2025.46 -0.5427-72 -00.2818.68 -0.322522 4 - 1 819.34 4 .6619.75 40.25u.97 4-0324.91 -1.0915.68 -0.3212.66 4.349.66 4 . 3 4

25-17 4-8320.ffi 4.1410.79 -3311 1 3 9 4 - T l29-70 4 - 3 027.19 9 - 2 125.94 6-06p.14 9 .2 630.S 9.00

000000000

0000000000000000000000000000000000

4.094 4.0944 . 4 0 4.070-0.016 4.0164.030 4.0300.m4 9.024

d.m& -Q.CO0.10 4.100,031 4.0310.U 4.12

0.22 4.220.039 Q.0390.69 4.69

4.13 4.13a.n 9.n-0.12 4.124.41 4 - 4 74.0M -0.0440.16 4.160.63 Q.631.33 11-330 . 42 4 . 420-097 4.0910.U 9.U0.44 e.440.21 4.210.31 40.310.w 4.0970.62 ~ . 6 20.27 4.21O .O U 9.0121.02 .1m0.30 4 .3 00.34 40.340.29 4.290.75 4.750.15 4.15).LO r).W0.14 4.140.25 4.250.12 0.12

4.055 4.0550.18 4.180.09 .Lo32

a00000000

0000000000000000000000000000000000

0.425 4.4250 . 4 0 9.0300.026 4.426

4.45 4 . o l 54.016 4.0160.m9 4 . m 9

4.012 4.0124 . m 1 4.021-0.020 4,mo

0.099 4.0994.0098 4.W8-0.088 -0.0684.092 4-w4.0030 -0.0030-0.40 -0.400.14 Q.14

-0.061 -0.0610.067 9.0610.10 9.130.053 4.0530 . 4 5 4 - 4 50.080 4.0800.073 4 . 4 30.098 Q.0580.077 4 . 4 70.W14 4.00160.080 4.m0.040 4.M

4.027 4.Wo.o1e 4.0180.068 9.0680.018 4.018QmoP m 3 00.052 4 . 0 90.079 4 . 4 94.011 -om14.20 4.204.m3 4.0230.042 4.w0.096 4.0960.Y 4.120.41 *on0.051 4.0s

000000000

00000000000000000000000

0000000000

0.025 9.W0.40 9.0300.026 9 . 0 2 6

4.015 4.0154.016 +.E16c . m 9 4.ccl94.012 4.OU4 . m 1 4.0214.020 4.020

0.099 4.099-0.m98 -0.00984. 19 4 .0894.w -0.0924.0030 4.00304 . 4 0 4 . 4 001L .O.ll

-0.361 -0.0610.067 r0.0670.10 4.100.053 4.15)0 . 4 5 9.4so.*o 4.090a . m 4 . 4 30.098 *.a980.077 4.1170.~016 4.00160.080 4.0800.240 4.m

4.027 4.0210.013 4.0150.068 4.040.018 e . o i a

QDmP 4 1 w O 3 0O.OQ 4.090.079 4.49

4 . 0 l . l 9.0119.20 4.204 . 0 2 3 4.0230w 4.0.20.096 4.0960.u 4.120.m -.on0.09 *.on

000010000

0000000000000000000000000000000000

4.0254 . 0 3 0 S.0304.026 -0.026

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- 16-'At the outset , the effec t of t 'nis c omp arativ ely sm al l change was not knownand the origi nal hy drogen balance equation was used.n -para ff ins a r e shown in Table I V ,that, al though in e rr o r, they followed a ve ry recognizable patte rn. Sincer e s u l t s f o r all the nor ma l and branched paraff ins on t h s A. P. I. 42 (16) l is tgave th is s a me pa t te rn , i t w a s foLqd possible to have the pr o gr a m for the Type650 computer writ ten in such a way that when this pattern o ccu rred the revisedhydrogen bala nce equation 15, would be su bsti tuted in place of the original.

The resul ts on theAn examina tion of these re sul ts indicated

Ta ble IV - Analys is of n-paraffins to I l lus t ra te the U seof Unco r r e c ed Hydrogen Baianc e Equation

A. P. I. 42Compd. #

528529531532534535537540106

C1obs. calc. c2obs. calc. c 3obs. calc. c4obs. calc.12 10.1413 11 .1314 12.091 5 1 3 . 1 51 7 15 .1518 16.0520 18 .1726 24.12

16 11. 12

0 3.750 3.750 3.780 3.730 3.770 3.720 3.710 3.74o 3-82

0 -1..890 -1.880 -1.870 -1.890 -1.890 -1 .870 -1.880 -1.880 -1.86

0 0.110 0.120 0.120 0 . l i0 0 . i l0 0.130 0 . i Z0 0.120 0 . i 3

obs.,5 calc. ~,

0 -0.110 -0.120 -0.120 -0.110 -0.110 -0 .130 - 0 . i 20 -0.120 . -0.13

F o r s impl ic i ty and also to i l lus t ra te that the use of the revised hydro-gen balance equation ied to ac cu rate r esu lts , tl-e revi sed hydrogen balance (equa-tion 15) w a s used in analyzing groups I and 11 (Pa raff ins ) and the origin al hydro-gen balance (equation 2) for the rema inde r.analys is i s given in Table V.

A summayy of the acc ura cy of th is

The gra phica l method of solution which has been descri bed was appliedThe re la t ivelyo 17 r epresen ta t ive compounds taken i r o n the f ive major c las ses .

sm a l l num ber of compounds examined by this metho d was due to the fact that thismethod w a s much m or e t ime-consuming than the i t e ra t ive p rocedure .of the roots was esse nt ia l ly the sam e in a l l ca ses , they al l possessed only oner e a l root l e s s t h an zC . Th er e was one exception to th is ru le , A. P. I. compound#133 po sse ssed two real roots but one of th ese lay in the second quadrant, whichhas no phys ical meaning.solution showing the i nte rse ctio n between the mo lar volume andcurve s which yields the s ingle root le ss thanxG i s g iven in Figure 1.

The na tu re

One repre sen tat ive exa mple of the graphic al method ofmolar ref ract ion


17/150

-17-

I I I I I I0 M.V. QUADRATIC -8 M.R. QUADRATIC -

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18/150

- 1 8 -D I S C U S S I O N

Some addit ional information about the structure can b e obtainedby a detailed examination of the "pat tern" of the resul t s in Tab le 111, withinea ch of the sev en groups of compounds into which this table is divided. Thisinformat ion can beLuse da s a valuable ai d when applying the method to unknowncompounds. Bef ore d iscussing the s ignif icance of t he e r ro r s , i t should b epointed out that for a given composition in te rm s of the f i & charac te r i s t i cg roups , t h e r e is a f ixed relat ionship between the er r o r s . If the e r ro r in C1i s taken as x and the e r r o r in C 3 as y , t hen the e r ro r in C2 will be -(x t y) ,that in C4 w i l l be y and t ha t in C5 w i l l be -y.

Considering, f i rs t of all, the branched paraff ins, Group II, i t willTh ere a h e a r e d to be a d i re c t re la tionship between the number

be noted that whereas Cas high as t3.of branch es and the magnitude of the err or .and C5 we re les s than 0.1, the compound could be predicte d to be a normal paraf-fin with a high de gr ee of certainty .then the compound would probably have one branch? On the other hand, i f Cw e r e g r e a t e r -t h a n to. , the compound would probably have m o re than one branch.

should be zero, i t is in fact posi t ive and sometimesOn the ave rage , the e r r o r in C2

pe r branch was t-0.42Cz group. If, in the an aly sis of an unknown, c2, C 3 ' c4However, i f C were between to.1 and 4-0.4,

2

T h e a c c u r a c y of the analysis of Group III, monocyclic naphthenes.Li ttl e difficulty should be e xperien ced injdentifying this group in theA few s t ruc tu ra l e f fec ts wer e noted in the e r r o r s in C1 and Cz.

was unusually high, due, no doubt, to the uniformity of the st ru ct ur es withinthe group.analysis of -unknown s t ruc ture s , s ince Cr ing s ize) .si ze of the ring and the nu mb er of branche s on the ring would app ea r to be theeff ec ts having the m os t inf luence, whereas branching on a single s ide chain didnot appreciably inf luence the resu l ts.

he re mus t be g rea te r t han 3 (minimumThe

T h e a c c u r a c y of the resu l t s for Group IV. the monocyclic aromatics,was p rac t i ca l ly the sa me as for Group 111, and for ess enti al ly the sam e reasons.The acc urac y for compounds with a no rm al si de chain was ver y high, a s wouldbe expected, sin ce this was the type of compound upon which the interaction ef-f e c t of C1 and:C4 w a s based.r ing , t he e r ro r m C was about 0 . 3 and in C about to. 3 . T h e l a r g e s t e r r o r f o rthe en t i r e g roup occur r ed fo r cas es where the re wer e mo re than one s ide cha inattached to the ring. As with Group 111, th er e sho uld be no difficulty in recogniz-ing this c la ss of compound when analy zing unknown comp ound s, si nc e C4 shouldalways be s i x in this class.no doubt should ex ist as to the st ruc tur e.

Where one branched side chain was attached to the1 2

At th is lev el the e r r o r s w ere suff ic ient ly sm al l that

Group V, the fused r ing naphthenes, pres ente d a much mo re diff icul tca se to in t e rp re t .could inf luence the analys is, and the examples ava i lab le we re ve ry l imited, noregu lar pat tern between s t ruc tur e and the e r r o rs in the analysis could be deter -mined. However, se ver a l important aspe cts of the er ro rs asso cia ted wi th th is

Since there appeared to be many mo re str uct ura l factors which


19/150

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- 20-I

group should be mentioned.s m a l l f o r C3, s o that t he re should be no difficul ty in detect ing the presence ofa rela t ively s m al l num ber of C3 groups in a saturated compound.tion of the ana lys is of com poun ds 543, 561, 577 and 578 indicated that in caseswhere Cwhen th is occur red , i f the value of C1 was added to the value obtained for C 2 ,the t rue value of C2 was obtained. Th is s ugge sted that in the an aly ses of unknown tcompounds, i f a negati ve value of C occu rred, I t should be replaced by zero and ,1the negative value of C1 should be adde d to C2 to giv e the c o rr ec t amount o f Cpre se nt (#575 was an exception to this rule) . ;mon to thr ee r ing s app eared to have so me inf luence on the accura cy of the analysis.

Th e mean e r r o r and s t andard deviat ion were ve ryAn examina-

,I

1 ;as ac tual ly zero the analysis y ie lded sm al l negat ive values for C1

2Side chains and carbon atoms corn-

Group VI consisted of the A. P. I. fused r ing a rom at i cs . The e r r o rhe re was, of co ur se , higher than fo r the preceding groups, but st i l l sma ll enoughto enable the s t ru ctu ra l ana lysis sys tem to be used.lar ge st number of s t ru ctu ra l groups was presen t in a s ingle compound, the la rg es t number of interaction effects could be expected.available in this group was s o sm al l t ha t it was not possibile to make any gene ral- 1iza t ions about the re la t ionship between the e r r o rs in the predicted analysis andthe s t ruc tu re . .h ib it ed the h ighest e r r o r in C1 and C2.the evaluation of the in te ra ct io n effect of Cnot f i t the s t ra ig ht l in e re la t ion on which this interact ion factor was based.

In this class, where theThe total nu mbe r of compounds

Attention is dr aw n to the analy sis of compound #179, which ex-on C2 4

This re su l t was not unexpected, as duringit was obse rved that # 1 7 9 did

Group VI1 consis ted of fused r ing arom atic compounds whose propert ieshad been determ ined by van Kre velen (17). The e rr o rs in the predicted values ofthe s t ruc tu ra l g roups in this c la ss a r e considerably gr ea ter than in the other c lasseI t should be noted that the r es ul ts fo r corone ne and dodecahydrotriphenylene we renot unexpected.for coronene we re not consis tent wi th the o the r compounds and were the refo re om-i t ted. Consequently, it was expected that the acc ura cy of the analy sis of this com-pound would not be very high.s t r uc tur e which the pres en t s yste m was not designed to t rea t .te r i st ic of this st ru ct ur e was the prese nce of Cw i l l be recal led that fused r ing aro ma t ics contaming C2 groups we re not success -ful ly deal t with my dete rminin g the interac t ion effect of C2 on C4.method of s t r uc tur a l analysis was not appl icable to the ca se where Cand C5 = 0.c 1 usually indicated a t ru e value for C1 of zer o, and that i f this negative value of C1 were added to the value obtained for C the resul t ing revised c2would b e con-s iderably c lo ser to the t r ue value . The &her h igh er ro r for th is group as a wholewa s considered to be du e to the gen eral unrel iabi l i ty of the physical property data,which has alrea dy been discusse d. Th e accura cy of the molar volume and the molaref ra c t io n equat ions fo r th is group was not a s gre at as for al l o ther c lasses . How-ever , i t was cons idered necessa ry t o include this group, be cause of t he sca rc i ty ,of data for fused r ing aromatic compounds.

When the original coefficients for C5 w er e calculated, the data

Dodecahydrotr iphenylene represented a type ofThe unusual cha rac-

and C 5 in the absence of C4. ItClearly, t h i s= 0 and C2

As in Group V, u s e could be ma de of the fact that negative values of

2

3


21/150

- 21 -The average accuracy for a l l A. P. I. hydrocarbons analyzed was

considerably le ss than one carbon group for each type.adequate for determining the av era ge number of the var ious s tru ct ur al groups.

This was considered

It was realized, initially, that the mol ar volume and t he mol a rrefract ion w ere ver y intimately related prope rt ies and that the equations dev-eloped in te rm s of the five st ru ct ur al groups might not be independent. However,this investigat ion revealed that these two equations were in fact independent, andthat the differences between them w er e of such a magnitude that the ?elutions ob-ta ined were in substantial agre emen t with the known values of the groups present.Consequently, it was esta blished that i t was pos sib le to deduce a considerableamount of st ruc tur al information fro m these two closely related propert ies.

The r esu l t s OF the application of this method indicated the me ri t s andso me of the deficiencies of this type of s t ruc tura l analysis .er t ies become avai lable on fnew" types of s t ru cture s , the scope of this methodm ay be extended. Th is approach could be applied to types of st ru ct ur es not al -ready covered, by developing analogous equations for other physical pro per t ie sand also by considering additional interaction effects. One of the m er i t s of thiss y s t e m l a y in the manner in which the coefficients in the molar volume and molarrefra ctio n equations we re determ ined. This gave confidence in extrapolat ing be-yord the molec ular weight range of th e known compounds that we re used to e s -tabl ish the system.

As physical prop-


22/150

1- 2 2 - ,

Burdett , R. A . , Tay lo r , L. W . , Jones, L. C. J r . , "Molecular Spect ros-copy".of the Hydrocarbon R es ea rc h Group of the Inst i tute of Pet role um , London,

Repor t o f a Conference Organized by the Spectroscopic PanelOct. 28-29, 1954, p.3 6-

Eccleston, B.H., Coleman, H.J., Adams, N. G. , J. Am. Che m. SOC.72. 3866-70 (1950).-

Egloff, C., Phy sica l Constants of Hydrocarbons, Vol. 111, 25, A, C.S.Monog raph, R einhold, New York , 1946.

Krevelen, D. W. van, Brenn stoff-C hemie , 33, 260-8 (1952).-Ibid., 34, 167-82 (1953).Krevelen, D. W. van, Blom, L. and Cherrnin, H. A. G. , Nature 171.075-6 (1953).Krevelen, D. W. van, and Chermin, H.A.G. , Fuel , 33. 79-87 (1954).Krevelen, D. W. van, and Schuyer, J. , I Coal Science, Aspe cts of C o a lConstitution'' , C h a p t e r s VI and VIIS Elsevier , Amsterdam, 1957.Kurtz, S.S. J r . , andSankin, A., Ind. Eng. Chem. 46, 2186-91 (1954).- ILorentz, H.A., Ann Ph ys ik. 9. 641 (1880).Mahdi, A.A.K. Al. and Ubbelohde, A . R . , P ro c. Roy. SOC. (London),

-220A . 143-56 (1953).

Mahdi, A. A. K. Al., nd Ubbelohde, A. R. Changements de Ph ase s ,Com ptes-ren dus de la deuxieme Reunion Annuelle, SOC. Chim. Phys.,Pa ris , Ju ne 1952, pp. 360-65.

Nes, K. van, and Westen, H. A. van, " As pe cts of the Constitution ofMineral Oi ls ' f , pp. 299-314, Els evie r , Am ster dam , 1951.

Ibid., pp. 318 -49 and pp. 445-53.Ibid. , Cha pter IV.Schiessler , R.W. , and Whitmore, F. C., Ind. Eng. Chem. 47, 1660-5(1956); Am. Doc. Inst., Doc. 4597.Schuyer, J . , Blom, L., an d Krevelen, D.W. van. Trans. Far, SOC.49s 13 91-1401 (1953) .


23/150

(18)(19) Vlugter, J. C., Waterman, H. I., and. Wes ten. H.A. van , J. Inst.

Schuyer, J. , and Krevelen, D . W. van, Fuel, 33, 76-83 (1954).Pe tro le um Technol. 18. 735-50 (1932).-

(20) Vlugter , J .C ., Waterman, H . I . , and Westen, H.A. van, J. Inst.Pe tr ol eu m Techn ol. 21. 661-76 (1935).-(21) Ward, A . L . , andKur t8 , S.S. J r . , Ind. Eng. Chern. Ana l . Ed.

10. 559-76 (1938).

h


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,I

PRODUCTION OF PIPELINE GAS BY BATCHHYDROGE3IOLYSIS OF OIL SEIAIEbYE. B. Shultz , Jr. and H. R. LLndenIns t i tu te of G a s TechnologyChicago, Illinois

The conversion of oil s h a l e t o high heating valuegases by d ir ec t hydrogenation was i nves tiga t ed t o de te r -mine i f the production of pipeline gas by th i s methodwas feasible and i f i t offered potential advantages overa l te rna te methods fo r u t i l i z a t io n of the la rge rese rveso f this f o s s i l f ue l.of a 22.9 gal. per ton Fischer assay Coloracio oi l shalewere obtained a t a maxi mumreactor temperature of 1300F.,maxi mum pressures of 1200 t o 5700 p.s.i.g., hydrogen-shalera t ios equiva lent to 50 t o 200 per cent of stoichiom etricrequirements f o r complete conversion of the organic carbonplus hydrogen content t o methane, and f o r th ree p a r t i c lesi ze ranges. Nearly complete conversion of .o rg aa ic carbonand hydrogen t o a fu e l gas wi th a heating value of over800 8. t . u . per s tandard cubic foo t w a s obtained i n re-l a t i v e l g shor t r es idence times a t temperatures of U0Oot o 1300 F., with o n l y l i t t l e formation of carbon oxidesf rom mineral carbonate decomposition. In view of ther e l a t i v e l y low mater i al cos t s , t he se re s u l t s i nd ica t eth at seriou s consideration can be given t o supplementingthe future supply of natura l gas with synthet ic highheating value gas f r omo i l s ha le , p a r t i c u l a r l y i n areasserved by long-distance transmission l i n e s passing i nt h e v i c i n i t y of the Colorado deposits.

Data on the batch hydrogenolysis

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-26-NOT FOR PUBLICATION

Presented Before the Division of Gas and Fuel ChemistryChicago, Illinois,Meeting, September 7-12, 1958American Chemical Society

PRODUCTION OF PIPELINE GAS BY EATCE HYDRDGEMISSIS OF O L SHALEE. B. Shultz , J r . and H. R. LindenI n s t i t u t e o f Gas TechnologyChicago, I l l i n o i s

A n explora tory inves t iga t ion has been made of the dry, high-pres-su re hydrogenolysis (hyd roga sifica tion) of o i l s ha le as part of a con-t inu ing program concerned w i t h the production of natural gas supple-ments and s u b s t i t u te s from l i q u i d and s o l i d f o s s i l f u e l s .Previous publications in t h i s s e r i e s have d e a l t w i t h the high-pres sure h ydro gasif icatio n of petroleum o i l , bituminous coal andl i g n i t e s , a n d p u r e compounds r e l a t e d t o petroleum Thepurpose of the pr es en t work w a s t o determine if the recovery of theorganic const i tuen ts o f o i l shale i n the , form o f high heating valuegas would provide an a t t r a c t i v e a l te r n at i v e t o the conventional ap-proach of maxi mzi ng l i q u i d products recovery. Resul ts indi cated t ha tra pi d, and ne ar ly complete conversion of the organic carbon plu s hydro-gen content of o i l shale t o a high methane and ethane content gas o fover 800 B.t.u./SCF (standard cubic foot a t 600F. , 30 inches of mercurypressure , saturated w i t h water vapor) heating value can be obtained atr e l a t i v e l y moderate temperatures and pressures .throughout the study, si nc e th is material appeared representative ofthe Green River formation deposit of Northwestern Colorado estimatedt o con ta in about 1260 b i l l i o n ba r re l s of o i l . eA n i nd i ca t ion of the need f o r development of economical methodsfor the produc t ion of pipeline gas from the large reserves of so l idf o s s i l f u e l s can be ob tained from a recent s tudy of f ac to rs influencingUnit ed S t a t e s crude o i l and n at ur al gas p r o d ~ c t i o n . ~ he r e s u l t s o ft h i s st ud y show t h a t on the basis of an estimate of average d r i l l i n gr e tu r n ( r a t i o o f es t ab l i shed re serves t o foo tage d r i l l ed ) , domesticcrude o i l prices would have t o reach $6 per b ar re l t o achieve an u l t i -mate recovery o f 160 b i l l i o n b a rr el s, and that a t a maximum pr ice o f$4 pe r ba r re l on l y 140 b i l l i o n ba r re l s would be u l t h a t e l y recovered .These crude o i l prices were computed after allowing f o r natura l gasrevenues ranging from 50 cents pe r bar re l a t present, t o over $1perb a r r e l a t the time u l t i m a t e crude o i l recovery reaches 160 b i l l i o nba rr e l s . S ince 88 b i l l i o n ba rr e l s of domestic c rude o i l had a l readybeen discovered a t the end of 1957, t h i s would correspond t o addit ionald iscover ies of only 52 b i l l i o n b a rr e ls a t a maxi mum r ice of $4 perbarre l, o r 72 b i l l i o n barrels a t a maximum pr i ce of $6 per barre l ,assuming average d r i l l in g re tu rn. A t an expected average future recov-e r y of 6000 cubic fee t of nat ur al gas per b a rr el of crudethe t o t a l addit ional gas supply, including pres ent reserves of 247t r i l l i o n cubic fee t , would then be about 560 and 680 t r i l l i o n cubicf e e t , r e s p e c t i v e l y . This i s subs t an t i a l l y less than a recent es t imateof 1 2 0 0 t r i l l i o n cu bic f e e t (corresponding t o an ultimate crude o i lrecovery of 250 b i l l i o n bar re l s) , based on geological fa c to rs withoutconsidera t ion o f economic limitations on exploration andcrude i s per mi tted , la ck of economic in ce nt iv es may r e t a r d developmentof a major portion o f po ten t ia l domestic crude o i l reserves .shale would correspondingly gain i n importance as an a l te rna te source

A Colorado o i l shale of 22.9 gal . per ton Fischer assay was used

Thus, i f increased importation o f re la t iv e l y low-cost fore ignO i l


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-27-of pi pel i ne gas i n vi ew of t he l ar ge and wel l - known pr oved r eserves,appr oachi ng i n mapi t ude t he t her mal val ue- of econom cal l y r ecover abl ecoal r eserves. l l 2 APPARATUS AND PROCEDKRE

The one- l i t er Aut ocl ave Engi neer s hi gh- t emper at ur e, hi gh- pr essur er eactor used i n pr evi ous bat ch hydr ogenol ysi s st udi es was used in t hi st he pure compound st udy. 14 The r eact or was charged at r oom t emperat ur esand pl aced i n t he r ocki ng f ur nace, whi ch was al so at r oom t emper at ur e.Heat i ng at full i nput ( 4. 5 w . ) was mai nt ai ned t hr oughout t he r i si ngt emperat ur e port i on of t he run, wi t h t emper at ur e r i si ng at about gF.per mnut e. Si mul t aneous t emperatur e and pressure measurement s weret aken, and gas sampl es were obt ai ned at i nt erval s t hr oughout tnecourse of each run whi ch consi st ed of a 128 t o 152 m nut e per i od ?e-qui r ed t o reach t he nomnal t emper at ur e of 1300F., and an addi t i onal30 &Ute per i od at 1300OF. I n al l cases r eact i on was i ni t i at ed wel lbel ow 1300OF.; t he i ni t i at i on of r api d gasi f i cat i on appear ed to cor r e-l ate wi t h t he appear ance of a wel l - devel oped t emper at ur e di p at 1025OF.I n accor dance wi t h pr evi ous pr act i ce, t hi s was desi gnat ed the i nLt i algasi f i cat i on t emper at ur e f or oi l shal e and was ar bi t r ar i l y used as zzer o t i me base f o r t he space- t i rne yi el d cal cul at i ons. Feed and r esi dueshal e sampl es wer e subj ect ed t o si eve anal ysi s, and t o ul t i mat eanal ysi s f o r t ot al carbon and hydrogen. . M ner al car bon ties deter m nedgr avi net r i cal l y f r omt he car bon di oxi de evoLved wi t h eci d, i n at echni que empl oyed by t he Bureau of M nes Exper i ment St at i on, L a d e ,Wyoming; organi c carbon was obt ai ned by di f f er ence. 17 Carbon di oxi del i ber at i on val ues det er mhed f r omr esi due shal e anal yses wer e f ound tobe uni f ormg gr eat er t han val ues obt ai ned f r omgas anal ysi s dat i , be-cause of cont i nued evol ut i on of car bon di oxi de af t er runs wer e t er -m nat ed; concl usi ons concerni ng carbon oxi des f ormat i on were drawn f rcopr oduct gas yi el ds and composi t i ons.Product gas sampl es were anal yzed wi t h a Consol i dat ed EngLneer j ngCo. Model 21-103 mass spect r omet er ; heat i ng val ues and speci f i c gr avi -t i es wer e cal cul ated f r omt he anal yses. Product gas vol umes and heat -ing val ues were cal cul at ed at 60F., 30 i nches of mer cur y absol ut spr essur e, and sat ur at i on ui t h wat er vapor , assum ng the i deal gas l aw.Speci f i c gr avi t i es wer e cal cul at ed on a dry basi s f r omt he aver agemol ecul ar wei ght of t he gas r ef er r ed t o ai r of mol ecul ar wei ght 28.972.I ni t i al hydr ogen vol umes were obt ai ned by di r ect measurement ; t he r e-act or was char ged wi t h shal e and hydr ogen t o t he desi r ed pr essure,and t he hydrogen was sl ow y vent ed t hr ough a wet t est met er . Use ofcompr essi bi l i t y dat a at r oom t emper at ur e per m t t ed the cal cul at i onof r eact or f r ee space when char ged wi t h shal e. Pr oduct gas vol umesdur i ng t he cour se of t he r un at t emperatures of 950F. and above werecal cul at ed f r omobser ved t emper at ur es and pr essur es and the i ni t i alr eact or f ree space, assum ng i deal gas behavi or . Pr evi ous wor k w t hcoal has shown t hat gas vol umes cal cul ated by t hi s met hod agr ee wi t hval ues measur ed by wet t est met er , wi t h a devi at i on of about 3 percent . 13 Fur t her , t he r easonabl y cl ose agr eement of r eport ed organi ccar bon and hydr ogen conver si ons based on comput ed product gas vol umes,and or gani c carbon conver si ons based on r esi due ul t i mat e anal yses,suppor t s t he use of pr essur e- t emperatur e- r eact or vol ume measurement swi t h assumpt i on of i deal gas behavi or . The f eed shal e anal ysi s i sgi ven i n Tabl e 1, and t he ef f ect s of pr ocess var i abl es ar e shown i nTabl es 2 , 3 , and 4, and Fi gur es 1and 2.

The pr ocedur e was essent i al l y t he same as descr i bed in


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Table l.-ASSAY AND ANAL;ysIS OF U . S . BTJREAUOF MINES O I L SHALE SBR58-40XaFi sc he r AssayO i l , w t . $ 8.8water, w t . $ 1 . 2Spent shale, w t . $ 88.0G a s + l os s , w t . d0b1, gal./tonWater, gal . / ton

Tota l

r a v i t y of o i l6 O7 0 O ~ . ', 0 .2.0l T5322.93 . 0

917-0. 918Sieve Analysis'40-100 Mesh SampleRuns 3, 4, 5 , 10, 11U . S . S . Sieve W t . %

A040-5050-6060-7070-80- 10080-100

0.825.320.019. 116 - 713.64 - 5Tota l 1583

Sieve Analysise140-325 Mesh Sample. -Run 9U.S.S. Sieve W t . B+140 3.2140-170 24.5170-200 0 .4200-230 32.8230-270 11 . 2270-325 0.2-325 27.7Total 1oOo

bCarbon-Eydrogen Analysis /Carbon, w t . %Mineral 4 .a8Organic 10.52Total r nHydrogen, w t . $ 1.59Ash, w t . .% 68.98YEneral GO* , w t . $ 17.88 f

sie;Je h a l y s i s d5-20 Mesh Sample,Run 8 -U.S.S. Sieve W t . p+55-88-10

4.641.34.71 0-12 8.41 2- 1 4 %*11 4-16 13.416-18 0.618-20 13.2-20 5.7Total 100.0a) Average of U. S. Bureauof Mines R u n s 53456 and53457.b, Average of U. S. Bureau

of M nes Runs l o291 and10292. l7I . G . T . Lab. No. 3910.

d, I . G . T . Lab. No. 4012.e) I . G . T . Lab. No. 4013


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-34- IEFFECTS OF PRESSUREAt al l t hr ee pr essur e l evel s st udl ed, 340, 735 and 1710 p. 3. i . g., i ni t i al pressure (1215, 2430 and 5540 p. s. i . g. , r espect i vel y, uponat t ai nment of 13OOOF. ) , t he resul t s showed t hat hi gh heat i ng val ue pro-duct gases wer e obt ai ned at hi gh or gani c carbon- pl us- hydr ogen Conver -si ons as t he nom nal run t emper ature of 1300OF. was approached; pro-duct gas di l ut i on wi t h carbon oxi des was not excessi ve and pract i cal l yno l i qui d pr oduct s were f ormed ( Tabl e 2 ) .f l owi ng and had vi r t ual l y t he same si eve anal ysi s as the charge.

( pr l mar i l y met hane, ethane and propane) at t emperatures of only 1200Ot o i 3OO0F, was pr i mar i l y r esponsi bl e f or t he low evol ut i on of m ner alcar bon oxi dese; t hi s dFf f er s si gni f i cant l y f r om the r esul t s obt ai nedi n hi gh- t emer at ur e ret or t i ng at low pr essures and in t he absence ofcar bon di oxi de evol ut i on, t he apparent yi el d and mol e per cent of car-bon dioxide was not af f ect ed si gni f ' i cantl y by pr essur e l evel ( Fi gure 1).However , t ot al gl el ds of carbon oxi des were decreased at t he hi gherpressures, r ef l ect i ng t he decrease i n carbon di oxi de conversi on t o car -bon monoxi de by t he r eact i on COa + H2+ CO + G O , as t he hydr ogen con-tent of t he product gas decreased.t ot al car bon oxi des cont ent was o n l y 22.4 mol e $. ( The repor t ed /

The hydr ocar bon hydr ogenol ysi s r eact i ons, an& t he sequence ofappear ance of t he st abl e i nt er medi at es Fn met hane product i on f romhigh-er mol ecul ar wei ght car bon- cont ai ni ng mat er i al s ( such as oi l shal eker ogen) , corr esponded cl osel y to t hose obser ved i n hydr ogenol yzi s ofpet r ol eum oilsla and pur e compounds r el at ed to pet r ol eum o i l s .Pr opane and hi gher par af f i n hydr ocar bons f ormed i n ear l i er port i ons ofeach run were soon hydr ogenol yzed wi t h i ncr easi ng appear ance of ethaneand met hane. Ethane yi el ds and concent r at i ons i n t urn passed throughmaxima w t h i ncreases In t i me and t emperat ur e, as methane, t he st abl ef inal pr oduct , cont i nued t o i ncrease. Maximum et hane yi el ds were ob-ser ved at at t ai nment of l.200F. at al l pr essur es ( Fi gur e 1).effect of pr essure i ncr ease was t o i ncr ease the r at e of ethane produc-t i on bel ow 1200F. and t he r at e of et hane di sappearance t o methaneabove 120O0F.wi t h i ncreases i n pr essure, accompani ed by i ncreases i n conversi onsand space- t i me yields.sur es, t oget her wi t h l ower carbon oxi de yi el ds and hi gher met hane yi el dsr esul t ed i n consi der abl e i ncr eases i n pr oduct gas heat i ng val ues.exampl e, heat i ng val ues of 792, 871 and 908 B. t . u. / SCF were observedat at t ai nment of 1300OF. as pressure w a s i ncreased f r om 1215 t o 2430t o 5540 p. s. i . g. , r espect i vel y ( Tabl e 2).At t he t wo hi gher pr essur es st udi ed, as wel l as i n ot her runscar r i ed out at 1005 of stoi chi omet r i c f eed r at i o, t he gasi f i cat i on oforgani c carbon- pl us- hydr ogen decr eased sl i ght l y at t emperat ur es of1200O tu 1300F., accompani ed by a decl i ne i n gas heat i ng val ue 14excess of t hat corr espondi ng to i ncr eased carbon oxi de f ormat i on. Thi si ndi cat es that i nsuf f i ci ent hydr ogen may have been pr esent i n thel at er por t i ons of t hese runs to pr event a smal l amount of carbon format i on f r ompr oduct hydr ocar bons.at hi gher pr essur es, due t o decreased hydr ogen concent r at i ons broughtabout by t he hi gher hydr ogen consumpt i ons char act er i st i c of hi gherpr essur e oper at i on.

The spent shal e was f r eeRapi d at t ai nment of high conversi ons of t he organi c mat t er t o gas ,,

hydrogen. "' I: Al t hough hi gher pr essure woul d be expected - to suppress

Even at t he l owest pressure l evel , ,-N2 + CO cont ent s wer e pr i mari l y car bon monoxi de. ) . -

TheMethane yi el ds were consi derabl y i ncr eased above 1200OF.

I ncr eased hydr ogen consumpt i ons at hi gher pres-For

Thi s ef f ect appear ed to be great er


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-35-FZWECTS O F iM3RCGDT-SiWL;E FIE3 FATI0F i g w e 2 presents gas y ie ld data a t hydrogen-shale feed r a t io s of50% (Run 11) 1005 (RUT 1 0 ) and 200% (Run 5) of s toi chi on etr i c reqdire-ments for coriversion to methane; .complete resul ts for 3uns 11 ~cclare given i n Table 3 and for the key t e s t , 2x1 l o , i n Table 2 . i ttemperatures below 1200F., the ex te nt of g as if ic at io n a t 505 of'stoichiometric hydrogen-shale feed r a t i o was agproxiaate ly the sramas a t the higher feed ra t i os so t h a t , i n the absence of excess hy&o-gen dLlution, ear l i e r formation of high heating value Froduct gasoccurred. Eawever , a t m e higher temperatures, conversions were re-duced su bs ta nt ia lly by decreases i n hydrogen supply, but not oropor-t i o na l ly t o reduct ions In feed ra t i o . For ins tance , a t l 3 O O 0 $ . ,gas i f i c a t ion of organic carbon and hydrogen vas 77 ve ight 5 a t 505 ofstoichiometric , 90 w e i g h t 5 a t 1005 of stoichiometric , and compl et sa t 200% of sto ich ion etr ic fee d r a t i o . Considerable vapor-Fnase et?-bon formation was indicated during the l a te r port io n of tine run a t 335of stoich iome tric, and none a t 200s of stoichiometric . This c c q a r e sw i t h evidence of onl y li mi te d vapor-phase carbon f m a t i o n , Indiceteaby a gradual decline in conversion and product gas heat- value, l a t ein the course of the run a t . l 0 0 $ of stoichiometric feed r e t i o .Pressure leve ls for Xuns 1 0 and 5 a t l oo$ and 2005 of s t o i c h i m e t r i cfeed r a t i o , res pec tive ly, were qu it e comparable, p erm itti ng a di restevaluat ion of the e f f e c t . o f hydrogen concentration on carbon oxi desformation.. Total carbon oxide yi el ds were about the sarxe f o r these

fe ed r a t i o caused much gre ate r conversion of evolved carbon dioxi& t scarbon monoxide.Ethane yields were increased by increases in f ee d r a t i o f r c a 5t o 200$ of stoich iomet ric; however, ethane conten ts were gre et es t e t100%of stoichiometric feed r a t io . Di lut ion of the proauct g t s :, it:?excess hydrogen reduced the ethane content a t 20075 of stoichLomet?ic,and pyrolysis reactions favoring methane over ethane formation E ~ L X & .the ethane content a t 505 of stoichiometric .EFFECTS OF PARTI CLE S I Z W G E

t w o m s , but increased hydrogen concentration a t 2005 o f s t o i c h i m e t r i c . I

In view of the subs t an t i a l cos t of o i l sha le s i z e r sduc t ion , loit would be d es ir ab le t o u t i l i z e r e l a t i v e l y l ar g e p a r t i c l e s i z e s t f ap ra c ti ca l hydrogenolysis process can be developed for movi ng- lor 3 . ~ ~ 2 -bed operation. In Table 4 , it can be seen t h a t i n s i p d ' i c a n t e E e c t son gas yields and composition resulted f r oma va r i a t i on in p a r t i c i es iz e range f r o m 5-20 m e s h t o 140-325mesh.

COPEERCIAL POSSIBILITIESl i q u i d fuel production because of higher conversion of o r m i c m a tt er( 90- 100weight $ f o r hy dro gas ific atio n, compared t o about 80 weight 5conversion t o l i q u i d and gaseous products in convent ional re tort ing2)and elimination of c o s t l y l i q u i d p r c 3 x t r e f i n i n g o p er at io ns . Xydr o-gasif ica t ion, i n addi t ion t o -producing a free-flowing residue con-t a in ing l i t t l e o rgan ic ma tt er , al so Y Z e l d s only negl ig ib le quant i t i e sof l i qu id products . T h i s d i f f e r s from o i l h y d r o g a ~ i f i c a t i o n ~ ~ , ~ ~and pgr ol ysi s of crude shale where sub stan tial qu an ti t ies ofliquid by-products &re formed. Absence of a@omeration probl emsshould permit the &.?velopinent of continuous moving- o r flu id -b ed 09shale hyd rog asif ica tion processes. Fixed-bed oper ation woul d 'nave theadvantr.ge of redwed f zed pre par atio n co st s. Hydrogen requirementscould be met with convantiond ca ta ig ti c steam reforming and carbon

Production of pipelin e' gas from o i l sh ale may be pre fe rab ie t o


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-36-oxide removal processes, u t i l iz ing a por t ion of the p w if ie d productgas f o r feed and fue l .t o 100%of s to ich iometr ic feed ra t ios , about 4900 t o 6600 SCF/ton of'1000 B.t.u./SCF eq ui va le nt gas can be produced w i t h 3800 t o 7600SCF/ton of hydrogen feed . T o t a l product gas requirements f o r hydrogenproduction, including a l l fuel requirements, w i l l be about 1900 t o3800 SCF/ton, leav ing a ne t 1000 B.t.u./SCF equiv alent gas yi el d of2800 t o 3000 SCF/ton. Heat requirements for the shale processing stepestimated from gas combustion retort data3, w i l l be about 500,000B.t.u./ton, so that i f product gas i s used as a source of heat, a net .g as y i e l d of 2300 t o 2500 SCF/ton would f ina l1 be obtained. A t 50 cenit o n mining cos t and 25 cent/ton crushing cost Jg0 t h i s would result i na r a w mater ial cost of 30 t o 33 cents/1000 SCF o f 1000 B.t.u./SCF gasequivalent for 22.9 gal . per ton shale. Large deposits of shaleaverage 30 gal. per ton or more,' so tha t raw material cost could bereduced t o l e s s th an 30 cents/MCF w ith t he ri ch er shale.Existing pipeline systems and requested extensions could supplythe major West Coast and Middle West marketing areas w i t h pipeline gasproduced Fn Colorado. With adequate sto rag e, alr ead y under considera-t i o n by Congress, the flow of the Colorado river i s adequate t o pro- ~vide water for a 2 mil l ion bar re l per day o i l shal e industry, which i s ,equivalent t o about 8 b i l l i o n cubic f e e t per day of net pipel in e gasproduction. lo

'On the basis of the results with 22.9 gal. per ton shale a t 50

CONCLUSIONSNearly complete conv ersion of th e org anic matter of a typ ica lColorado o i l shale t o high methane and ethane content, high heat-value f 'uel gases has been achieved i n batch hydrogenolysis a t 12001300'F. in the presence of su ff ic ie nt hydrogen t o convert the organiccarbon and hydrogen t o methane. Lib era tio n of mineral carbon dioxidew a s kept a t a l o w le ve l by opera t ion a t these r e l a t i v e l y low tempera-tur es. P ar t i c l e s i z e range var i at ion s from 5-20 mesh t o 140-325 meshhad no s ig n i f i ca n t e f f ec t on gas i f i ca t ion r a te s and y ie lds .i n pressure t o 5500 p.s . i .g . res ul t ed i n more rapid formation o f highhest ing value gas, h igher gas yields and lower total yields of carbonoxide s. However, pr es su re inc rea ses above 2000 t o 2500 p. s.i .g. di dno t appear t o a f f o r d advantages commensurate with th e c os t i ncrea sesthat would be invo lved i n a commercial application. Hydrogen feed of

twice the stoic hiom etric requirements f o r methane formation resul tedi n complete conversion of orga nic carbon con ten t, but excess hydrogend il ut ed th e product gas. Hydrogen fe ed of one-half of th e sto ich io-met ric requirements re su lt ed i n lower conversions and some vapor-phasecarbon depo sitio n, b ut pyrol ysis react ions brought about high yieldsof high heating va lu e gase s a t 120O0F.po si ti on appeared t o begin. Low hydrogen con cen tra tio ns i n the pro-duct gas slowed conversion of carbon di ox ide t o carbon monoxide,an undesirable reaction which consumes feed hydrogen. Although fuelgases of pip eli ne qu al it y were produced i n t h i s stud y without f 'urthertreatment, i t would probably be economic t o remove carbon dioxidebef ore high -pres sure transmission. On the basis of these res ul t s ,high heating value gas production by hydrogasification of o i l shalew i t h hydrogen produced from a portion of the product gas appears bothtech nica l ly and econonically fea sib le . In view of the large reservesof o i l Shale, v a s t l y exceeding estimated ul t imate crude o i l reservesand approaching i n magnitude the thermal value of economically re-coverab le coa l r ese rves , se r ious cons ide rat ion to t h i s a l t e rna te s o w ~of pipe line gas should be given i n stu die s of f'uture gas supply.

to -

Increases'

before appreciable carbon de--


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\ ACKNOWI;EM3MElIT, This study was conducted as p a r t o f the basic research programIj of t h e I n s t i t u t e o f G a s Technology w i t h f'unds provided by i t s Members, and Co ntributors. 14. A. E l l i o t t , d t e e c t o r of the I n s t i t u t e and? H. M. H x ~ r y ,president of the N.E.G.E.A. Service Corporation were) very- lielpf kl i n form ulating the progrm-. H M Thorne, Cuef of1\ required f or the study.i by R . F. Johnson. D. M. Mason and J . E. Neuzil provid2d the ana ly t i c a i

Oil-Shale Research, Region 111, Bureau of Mines, made the o i l shaleSupply and anal yses avai la ble and contr ibuted valuable infornat iondata,.

The batch hydrogenation tests weTe performed,j

?

I


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h e r . Gag Assoc. , h e r . Petroleum Inst. and Canadian PetrolemASSOC. , Proved Reserves of Crude Oi l , Natural Gas Liquids andNatural Gas i n the Uni t ed S t a t e s and Canada, December 31, 1957,"No. l2 The S o c i e t i e s , New Y:rk and Calgary, Alberta, 1927.Brantley, F. E. and others , High Temperature Shale O i l ,Eng. Chem. 44, 2641-50 (1952).Camron, R. J . and Guthrie, B., O i l fromShale," Chen. Eng.Channabasappa, K. C . and Linden, H. R. , "Fluid-Bed Pretreatmentof Bituminous Coals an$ Lig ni te -D ir ec t Hydro en at io n of th eChars t o P i ffe l ine Gas, Ind . Eng. Chem. 3, 37-44 (1958) .Davis, hJ. , A Study o f the p t u r e Produc tive Cap aci ty and Prob-able Reserves of t h e U S.,1 9 5 8 ) .Donne11, J . R. , "Preliminary Report on Oil-ahale Resources o fPiceance Creek Basin Northwestern Colorado, U S. GeologicalSurvey Bul le t in 1042-H, Govt. Print. Office,Washington, D. C.,Ri l l , K. G and others, "Future Growth o f the World PetroleumIn dus try, The Chase Manhatzan Bank, N e w York, 1957.Jukkola, E. E. and otf;lers, Thermal Decomposition Ra tes of Car-b on ate s i n O i l Shale , Ind. Eng. Chem. 45, 2711-14 (1953).Linden, H. R. and o t i e r s , "High Tem peraEre Va or-Phase Crack-i n g of Hydrocarbons, Ind. EM. Chem. ?, 2467-82 (1955).Pr iec , C. H. and Savage, J . I f . , "A Sha e - O i l Indust ry i s on i t sWay, Ch e m. En- . Pro . 52, 16-5-26-5 (1956).Rubel, A. C . , " S h a l e T i l - a s a Fu ture Energy Resource, IMines ma^ az i n es,2-76 (1955) October;"Shale, k a l Gas t o Supplement Natural,ahul tz , E. B. , J r . , Channabasappa, K. C. and Linden, H. R . ,Hydrogasification of Pepoleum O i l s and Bituminous Coal t oNatural Gas Subs t i tu tes , Ind . Erg. Chem 48, 894-905 (1956).Shultz, 3. B. , Jr. and Linden, H. R. , "Bat& HydrogenoAysisReactions of Pure Com ounds Rela ted t o Petroleum O i l s ,En- Chem. &, 2011-18 (1'357).W and others, 'Entraineg-Solids Retorting of ColoradoO i l Shale-Equipment and Opration,(1955)Terry, L. F. End h'inger, J. F. , "Future Growth of t h e Natura lGas Industry, The Chase Manhattan Bank, New York, 1957.Thorne, H. M. , Bureau of Mines Experiment Station, Laramie,Wyoming, Private Communic$tion, February, 1958.Tihen, S. S. and others,O i l Shale-Product Yields and P ro pe rt ie s,

Progr. 50, 336-41 ( 1 9 5 4 ) .

O i l Gas J . 56, 105-19 (February 24,

1957.

O i l Gas J . 56, 110-11( Apr i l 7 , 1958).

Ind. Eng. Chem. 3 461-64

Entrained-Soli$ Retorting o f ColoradoInd. E ~ R . hem. Q,464-68(1955).


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PERFORMANCE OF SUPPORTED NICKEL CATUSTS I N CYCLICi STEAM FEPORMING O F N.A RAL GASb YJ . M. Reid and D. M MasonI n s t i t u t e of Gas TechnologyChicago, I l l inois\

ii4 AESTRACT

Comparatively l i t t l e data are availz ble regarding the perform-{ ance of ca ta lys t s i n the cyclic steam-hydrocarbon reforming process1 used by the u t i l i t y gas ind us tr y on the East ern Seaboard, and more1 extensively in Europe and A s i a . In this study , se ve ra l commercialtypes of supported n ickel ca ta lys ts having e i t i e r alumina ormagnesia as the base ma teri al were subje cted t o cy cl ic process con-d i t i m s i n a lab ora tor y refomzing apparatus. Ca tal yst perfommi-ceand ca ta lys t l i f e were signif ' icantly affected by the oxygen which' was present during the hea t ing port ion of the cycle.' continuous s team-hydrocarbon reforming process used extensiveiy bythe chemical indus try f o r production of hydrogen and amnonia syn-1 thesis gas, performance of the cycl ic process w a s not found t o be4 singular ly dependent on the act ivi ty of the c a ta l y st f o r the steau-hydrocarbon reaction, but rather under ce rt ai n conditi ons t o be con-

t r o l l e d by t h e r a t e s of oxidation and reduction of the nickel .these tes ts , l i . fe of alumina-supported catalyst w a s r e l a t e d t o t heformation of an unreactive compound between nickel oxide and thesupport. W e of the magnesia-supported catalyst w a s r e l a t e d t os o l i d so lu tio n formation between nick el oxide and the support. Theinadequacy of present manufacturing specifications and testing pro-? cedures f o r nickel ca ta l ys t for cyc lic reforming i s i l l u s t r a t e d by, hese r e su l t s .

1)

U n l i k e the

I n

ii


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-LO-.NOT FOR TUBLIGATIONPresented Before the Division of Gas and Fuel ChemistryAmerican Chemical SocietyChicago, I l l i n o i s Meeting, September 7-12, 1958 /

PEFPOWCE O F SUPPORTED N I C K E L CATALYSTS I p? CYCLICJ . M. Reid and D. M. MasonI n s t i t u t e of G a s TechnologyChicago, I l l inois

STEAM REFORMING OF NATURAL GUS i

I NTRODUCTI ONw e i g h t hydrocarbons i s a w e l l estab l ished process.6~29132~39y40y41It has been applied extensively i n the chemical industry where largequantities of hydrogen are required, as i n the case of ammonia syn-thesis . A f e w I n s t a l l a t i o n s have a l so a ppea re d i n t h e u t i l i t y g asindu stry f o r the production of low heat ing value f u e lThe process i s carried o u t i n a tube furnace i n which preheatedsteam and hydrocarbon are passed through ex te rn al ly heated cata lyst-f i l l e d tubes.carbon monoxide and some carbon dioxide. Thi s reac t ion i s high lendothermic. Reac tion temperatures range f romabout 120O0F. o d O O F .and press ures from atmospheric t o s ev er al atmospheres. The mos tcommonly employed catalyst i s reduced nickel oxide supported by a highsurface area re fr ac to ry mater ial ; n icke l concentrations range fromseve ral weight percent t o more than 30.Performance of these catalysts has been extensively invest igated.-53031 In addi t ion t o process condit ions, the major f ac to rs in f lu-encing the c a t a l y s t behavior have been shown t o be poisons such ass u l w compounds conta ined i n the f eed streams, and physical proper-t i e s of the c at al ys t such as surface area, porosi ty and c r y s t a l l i t esi ze . With proper co nt ro l of process var iab les , the ca ta ly s t appearst o have e ss en t i a l ly un limi ted l i f e i n commercial operation.

Cata ly t ic steam reforming of natural gas and other low molecular

The hydrocarbon and steam re a c t t o produce hydrogen,

Cyclic ReformingPr io r t o World W a r 11, t he u t i l i t y gas i nd u st ry i n the U n i t e dS t a t e s was based almost en t i re ly on carburet ted w a t e r aas moduced .from coke, steam and o i l in cyc lic apparatus. The a v a i r a b i h t y of low-c o s t n a t ur a l gas t o major population c ente rs through long distancepipe lines constructed in the post-war era made processes based ons o l i d f ue l economically unfavorable. Where conditions warranted thecon tinued d i s t r ibu t io n of low heating value gas, i t was necessary tof l n d some means for conver t ing natural gas. The c a t a l y t i c s t e m r e-forming process was i d e a l l y s u i t ed f o r this purpose.process as developed by the chemical Industry i s car r ied ou t i n con-tinuous tube fbrnaces.would requ ire the ca pi ta li za ti on of e n t i r e new manufacturing plants t or ep lace the ex i s t ing ca rbu re t ted water gas plants. A more at t ract ivescheme f o r t he u t i l i t i e s w a s made possible by t he United Gas Improve-._.ent Company,which pioneered the development of th e cy cl ic reformlngprocess in the United States.20~26~34~35r42944he c yc li c process Icould be ca rr ie d out by a re la t i ve ly low-cost modif icat ion o f theexis t ing carbure t ted water gas equipment. A s a r e su l t , 17 cyclic pro-c e ss I n s t a l l a t i o n s a r e i n us e in the ees tern pa r t o f the UnitedS t a t e s . 3925 -

However, theT o adapt t h i s process t o the gas industry


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-4l-The Cyclic Catalytic Reforming ( C C R ) process di f fe r s from theconventional continuous process, bas ical ly, only i n the manner i nwhich the heat requirements are suppl ied . F i r s t , the ca t a ly s t bedlocated i n one of the refrac tory -lin ed sh el ls from the carburet tedWater gas apparatus i s heated to reaction temperature by the passageof hot products of combustion supplied by e i t h e r o i l or gas burners.This Ls followed by a reforming step i n w'nich steam m-d hydrocarbonar e passed through the ca ta ly st bed.r y shapes used f o r process steam preheat a d in t he ca t a lys t bedduring t ' le heating step i s used during t i e reforming step. SteamPurges are normally used t o separa te the h e a t k g and re foming s teps .The entire cycle sequence is generally completed i n less t hm f i v eminutes.The catalyst employed i n the cyclic reforzing process i s similarto continuous reforming catalyst in that it i s met all ic nicke l support-ed by a refracto ry materia l . Propert ies o f t'ne re f rec to ry supccrtar e necessari ly more s t r in gen t fo r the cyclic process because ei' thethermal shock associated w i t h cycl ic heat ing and cooling o f t'ze catailyst bed and because of a tendency for the bed t o l i f t o r move .s l i g h t l y with cy cl ic flow changes. The asteria1 used almost ur2:ier-s a l l y i n commercial operation con sist s of fused spherss 1/2 t o 1 inchin diameter, of impure alumina (90%) having medium poros i ty ( W - ' + O $ ) .The catalyst i s prepared by impregnating the spher ica l s i a q o r t w i t h 2.nicke l s a l t solution and then decomposing the nickel s a l t t o nicke loxide by heating i n ai r t o about 6 O O O C .Performance o f the catalyst has been commerciall'y ecceptable f o ru t i l i t y operat ion, but the cata lyst has decidedly short l i f e coqxred.

t o ca t a lys t s used in the continuous reforming process.25 O rd i c z r i l ymore than 50% of t he o r i g i n al c a t a l ys t a c t i v i t y i s l o s t a f t e r 2000 t o4000 hours of operation w i t h one inch diameter ca t a lys t . For 1/2-inch diameter c ata ly st ,where r el at iv e l i gh t ca t a lys t loading i s used,somewhat longer l i f e i s obtained. Plant capacity i s obviously affect-ed by l o s s in catalyst activity,and replacement of a t l e a s t p a r t o fthe ca ta lys t i s required annually.Efforts t,o improve catalyst performance in the cyclic processhave re ce n tl y become of conside rable in teres t t o u t i l i t y compaziesusing the CCR process.z5 In addi t ion, extension of tine CC?, p=.ocesst o l i q u i d hydrocarbon o per atio n and the development of severel newgas manufacturing processes which incorporate i ~ . s o a eorn theprin cipl es of cycl ic c at al y ti c steam reforming of hydrocarbons 'navefocused attention on the performance of ca ta ly st under c yc lic condi-t i o n ~ . ~ ' ~ ~ ~ ~ ~ , ~ ~ ' ~ ~n a recent study a t t he ' I n s t i t u t e of G a sTechnology, the cy cl ic performance of se ve ra l suppor ted ni ck elca t a lys t s was invest igated under c losely control led condi t ions i n thelaboratory. It w a s the object o f th i s s tudy to determiie the fac torsunique t o the cy cl ic process which governed c at al ys t performance andwere respons ib le fo r re la t iv e ly shor t ca ta lys t l i f e . S ignif icant re -su l t s of th is study are presented here.

The heat sto red in-t ine refr acto -

il

EXPERIMENTALThis study was l imi ted t o commercial catalysts containing approx-imately 5 w e i g h t Support materials were either fusedalumina ( a AL203p or fused peric lase ( Q O ) Al l of the ca ta lys t

p e l l e t s were i n the form of nominal 1-inch diameter spheres except forone sample w i t h high-purity alumina support which consisted of i r reg-ularly shaped, 1-inch lumps. Onl y the lower purity aluminabase catalyst contained magnes ium oxide promoter. Pr op er tie s of the

e r cent nickel.


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-42- ~ 1

unused catalysts are shown below.Catalyst Designation AAcid Soluble Nickel, w t . 5 5.14Magnesium Oxide Promoter, w t . $ 1.81Support Composition, w t . $ 86.852 0 3MgO ;si02 12.90C a O --Fe 0.25P e l le t Shape Sphere--

C J4.48 4.99 5-16 jI

BNone None None

0 . 3-- 5.5-3.0-1. 0-0 .2--9c---- _-- --- -Ir re gu la r Sphere Sphere(Catalyst nickel concentra tion data appearing throughout thispaper re f er t o t ha t nic kel port ion of the ca ta ly st which w a s solublein n i t r i c a ci d. The nic ke l content was determined by boiling a pound ,(minus-100 mesh) sample w i t h concent ra ted n i t r i c a c id un t i l the disap-pearance of brown rUmes, fol lowed by f i l t r a t i o n and gravimetric determination by a standard dimethylglyoxime method.X-ray di f f rac t ion pa t te rns of the ca ta ly st s were obtained by theDebye-Scherrer powder camera method.Reforming t e s t s were conducted i n the apparatus shown i n Figure 1.The reactor consisted of a 3.125-inch I . D x 102-inch long, Type 310stainless s t ee l t ube with a cent ra l l y loca ted 0.675-i nch O.D. thermo-wel l of the same alloy inserted through the bottom. The re ac to r tubewas suspended i n a Smith al lo y wound el e c tr i c m rnace w ith f ou r inde-pendently co nt ro lle d he ati ng zones. The temperature in each zone wasregulate d by potentio metric temperature ind icat or- con trol lers i n com-

bina t ion w i t h chromel-alumel thermocouples. The co ntr ol thermocouplewas welded t o the outsid e ski n of the reactor tube a t the center ofeach heati ng zone. Add iti onal chromel-alumel chermocouples locat ed i nt h e internal thermowell were used t o measure t h e catalyst temperaturea t three poin ts w i t h i n the bed and the feed gas stream temperatureimmediately before entering the bed.Provision was made t o weigh d i s t i l l e d water,which was fed by achemical propo rtionin g pump through an el e c t r i c a l l y heated steam gen-erator t o the top of the reactor tube . Natura l gas w a s f ed from high-pressure cylinders through a pressure regulator and gas meter t o the topof th e re ac to r tube,where i t w a s mixed with the steam feed. Product gas was withdrawn from the bottom of the reactor tube through a water- ,cooled tube and s h e l l condenser,where e

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