I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1516
with the amount of steam reduction for a particular source (Table 111). Table IV compares the magnitude of molecular weights reported in the literature tTith viscosity molecular weights. The viscosity method gives result6 indicating t h a t the mean molecular weightq of asphaltenes are relatively low. The values correspond with the lower limit of the range of molecular weights rcpotted in the literature. T h e viscosity molecular weights at finite, concentrations are lower than the cryoscopic molrcdar \wight at the same concentrations : Asphaltene Concentration, Keight % 4.7 6.6 8.1
lIolecular Weight Cryoscopic Viscobity (caniphor) !benzene) 1802
2118 ?i13
1433 15.49 I64Y
Thus, on the basis of all comparisons niatlt,, I l i t , vi.cw.it gives Ion. molecular xeight values.
>. tni~thod
Vol. 39, No. 11
SURIkl A R l
The v i s o s i t y method of nieasuring riiolccular weights appears t o be satisfactory for the oil and resin fractions from asphalts. The values for v s p / cand log v 7 / c for oils and resins do not change appreciably with increase in conccnt ration, b u t values for asphaltvncs show a gradual inereax in vhpr'cand log q,!c with increase in concent rat ion. For concentrations of asphaltenes in benzene ltbss thaii 1.0 grain per 100 ml. benzene, differences between [log vi,'cIc and [log v r 'clC = 0 are less than 5yGof [log v,/cIc = 0. Both equations proposed by Staudinger apparently can be applied t o oil and resins from asphalts since [ v a N / c l and c [log vr.!clC for these constituents are linear functions of the cryoscopic niolecular !\.eights. The mean molecular \wights of asphaltcncs viere determined by the viscosity method, using constants based on the molecular w i g h t s of the oil and rcsin fractions. The molecular in time of air blowing \vcxiglits of asphaltenes increasv witli incre (BS indicattd by melting point fiir asphalts from oiic source') of t hi. oiipinal asphalts.
Method 5000-6000 4300-3600 2210-5160 2400 IO60 80,000-140,000 1800 700-1800
Cryoscopic (benzener Cryoiropic (benzene) Crvoiconic (cnnlnhori ~. . , Cryoscopic (benzene) Cryoicopic (naphthalene) Aionornulecular filni Viscosiry of dilute s o h . Viscosity of dilute solti.
Because of the posibility of agglomerated asphaltellea iii l ~ e i i zene solution and the viscosity-iiiolecula~~ w i g h t constant usctl, the validitj- of t h e I o n molecular w i g h t s obtained reniains t o 1x: confirmed. The development of a solvent in xvliich it is ciJi,t:+iii that the asplialtcnes are complc~telyciiswlved ~ o u l deliniitiat~~ oiie disadvantage that can bo clainitd for benzcne solutioii.. lopmenis in elrctron microscope techniquo may ~ I Y J vide required information on t lie actual sizes and iiiol(~ul;w weights of asphaltcw-.
Chemical Characteristics of Banded Ingredients of Coal I
1-THE ~ o r oii k Illinois coak i i i this 1:ihcJratory, c c I t i 4 i ! i w l i h , attentioil has been given t o stutlirs of t lie, physicd :tiid chem-
ical charact,cristirs of the banded ingredients vitraiii, cl:train, durain, and fusain. T h e Stopes clajsificatioii (15) of bniitled ingredients is based on macrovisual appe:trance. It i; of intcrest, therefore, t o coniparc t h t ~ evi.sually selected irigrcdients t o learn .r\-hether each elion-s niorci or less specific cheniical ch:tr.;icteristics. It is also of interest t o learn nlicthcr each ingredient. secured from coals of different ranks, varies ii; c~licmicalcliararteristics as do the source Tvhole coals. Published analyses for the b a ~ i d c ~ itigtdictits l stio\v tr-ielc dit'ferences in chemical composition for ench ingi,etlic~iit. 1'rok)aIil~~ the composition of each ingrctlient, at loasst of Titrain, clarnin, anti durain, is influenced by the t l c g r c ~of tiic't:tiiior~)li~~is undcrgone:
INDUSTRIAL AND ENGINEERING CHEMISTRY
November 1947
ranks of co:zl-high volatile bituminous -1:B, and C-i~c~presented in Illinois. The ~ v o r kreprewits an effort t o olitain information 011 variations of chemical characteristics of ingredients as related t o rank of source coals, and in addition to secure information on differences due t o variability in visual selection, particularly of the fusains. TESTS ON COAL SAAIPLES
Four sets of samples, including n-hole coals and bandcd ingredients from Gallatin, Franklin, AIacoupin, arid Henry Counties xwrr studied. These represent coals of high volatilc bituminous ranks .1,B.C, and D, respc~etively. T h e hole coals were channel samples, cut don-n, landed-iiigrcdien and sealed in sample cans in the miri ction being made samples viere hand-picked in the macroscopically. These samples t o pass a 4-nirsh sieve and xere sealed in sample cans: in t h e mines.. I n the laboratory, samples xere air-dried, crushed t o -20 mesh sizr, in a H r a u n - t q x 6 CP pulverizer, arid furt hclr pulverized to smallei~ sizes in a tiall mill. Several tests n-cre used t o compare clirmical characteristics oi
t o a tentative I.S.T.II. method (2). IIoisture chararteristiw wcre det ermined by the cquilihation method tlwerihed by Stanfield aiid Gilbart ( 1 4 ) and latw used in this labor at or^ (10). Further studies n-ert' made on the hand-pickcd rusanis. Fu>aiii n-cre made on these nanip1e.q by t h e Hsiao nic~rliotl t portions (Hsiao fusaiiisj rrniaining at'tcr nitric of the hand-picked fusains n-c're studied activities b y the C.R.1,. mclthod, and moisture charact y the equilibration mi,thod. Proximate ai w-rre niadt, according to .\,S.T.lL. standard met hods. AX.&LYS E S
I'roxiniate analyses, total sulfur, ailti calorific values for whole coals arid hand-picked ingredients arc' summarized in Tablcl I. In general, analytical valucs for the vitrains, clarains, and tlurains vary in the same n-ay as do t h o w fur the ro coals. Iloisture arid calorific d u e s ai'? of pa con~ideringvariations due to rank. .\s-rcwivetl moisture values for vitriiin. (,larain, and durain increase with do t1io.e for tlic \\-hole coals. JIoisture values for the, fusairis s h r ~ \ vRII cxccptiori in regular increazr with dc!
D a t a are presented OII certain fundamental c-hcniical characteristics for four sets of banded ingredient* a n d \+ hole coals from Illinois representing three rank.-high \olatile bituminous 4, I), and C. Eiidence is shown of \ariation h! rank of the banded ingredients Titrain. clarain, and durain. Ebidence of \ariation6 b? ranh of fusains is more erratic. Comparison of characteristic- of €1-iao fusains with those of hand-piched fusains indicates that the hand-picked samples contain rather large p r o portions of more reacti\e materials. Variations i n reported anal)ses of banded ingredients appear to be due partially to the influence of vaqinp rank, b u t alco to \ariatioils in the selection of iamples.
corwspondirig s o u i w coals; that for the Fi,:inliliri ('ouiity lusaiii is hig1it.r than t h a t of t h e fusain Irom tlie lower rank LIacoupiri County coal. Fus:tin inoisturo valuvs itrtfi distinctly Iiighvr I ha11 those for othvr ingredieiits. ('alorific values 011 the moist miiieral-matter-free basis, fur all in rank of the source whole iiigredienw, decrease with dccre coals. I n general, calorific values 011 the dry mineral-mattc,r-fre~ hasis for vitrain, clarairi, arid durain shotv this same trend, although values for vitrain arid c h a i n from Henry County are higher than those for the same ingredients from Macoupin County. This is also true for the corrcsporidiiig whole coals. Fusairi from the Franklin County rank B coal shon-ed the highcst calorific valuc, or1 t h e dry mineral-matter-free basis. \Tit11 t h e exception 01' the fusain from t,he Gallatin County rank h coal, calorific values (dry mineral-matter-free) for fusains are higher than for othctr banded ingredients and whole coals. This is in accord with t h e findings of Parr, Hopkins. and llitchell (8) in a study of Illinois fusains. Honever, the work reported by these authors covered fusains from high volatile bituminous B and C' coali; h u t not for fusain from high volatile bituminous ;i. REACTIVITY AND FREE SWELLIR-G INDICES
Tal~ltbI givrs reactivity indices for t h e samples studir.d. The T:5 arid 7'-j values f o r thc \,-hole cwals decrease n-ith tlc~crc~ast~ it1
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F Q A N K L I N COUNTY
.. . . .
H E N R Y COUNTY
~
~
-
G A L L A T h CCUhTY
...'
FQ4hKL N COdhTY MACOUPIN C O U U T Y
14-
1517
G A L L A T ' N COUNTY MACOUPIN COUNTY
.
c
Y
12
a a I 10 W
3 r
L" 8 .
i
1
I0
Figure 1.
20
30 43 5: EO 3 ' RELATIVE ~ U M I D l T Y - - O E R C E h T
80
93
IIoisture Characteristics of T h o l e Coals
100
I
I
10
20
Figure 2.
30 40 50 60 RELATIVE h J M 3ITY-PER
70
@3
90
CENT
IIoisture Characteristics of \-itrains
100
INDUSTRIAL AND ENGINEERING CHEMISTRY
1518
...
18-
__ 16-
G A L L A T I N COUNTY
.__ F R A_ N K L I_ N COUNTY
-. .
MACOUPIN C C U N T Y HENRY C O U N T Y
Id-
.
#-
z
J I2U
w Q
I 10U
a
3 F
t?
8-
0
I
6-
4-
2-
I
MOISTURE CHARACTEKISTICS
k'igurc's 1 t o 5 she\\. graphically the results oht a i i i d . Smiples, groutid t o ptss a 14-inesh sievc, n-ere brought t o cquilit~riumai diffcrviit huiiiiditiim, and moisture coiitcrits w r e theii clctcrniined 11)- l i c ~ ~ t i nin g a n c u u i i i o w n at 105' C:. for 3 hours. These r:tl~wsiri:r(' plutted against the comzpoiidiny reliLtive huiiiidities. tudied, the iiiterrelatioiis of nioisturcI n general, vitrairi curvcw ai'^^ higha1 are nest, duraiii is soiiiiin.hat lo\ver, :ind fuxiiii is decidedly lair-er u p t o high humidities \\-here the cui'ves rise steeply. Comparisons of the moisture-huniiditv eiirves Cur tlie four ivholc coals studied, as w l l as rmpoiidirig baridctl iiigrediciits, show n-ide differeri for vitt.aiiis., clarains, arid duraiii.5 have the same g iititl oci~upytile saixe rc1:ttive positions as do curves fur the difC I ~ I , ( Y ~ i,niik ~ \\-hole coals. Tlic, fusairi cui s (Figurcx 5 1 do not oc*i~u~)y the saiiie relntirc positior,.. 1 t l w coinparisoris appear t t r ahow that iiioi;turcl c i i a r a c t r i iit iw iiit1ic:ite vwiatioiis by raiili iii vitrain, clsrain, a i d duraiii as iii i l l ( , \\-liolt. coals. Indications of variation by rank of fusains M Y ' l l ( J T CleLIl'.
20
10
Figure 3.
30 40 50 60 70 RELATIVE ~ J M I C I T Y DER C E N T
90
80
IO0
RIoisture Characteristics of C h a i n s
rank. This same trend is exhibitecl :tko by thc b:xicled irigredielite. Rewtivity indices for iiigiwlieiits and n-hole c:osls from t h e sanie soiiiw are aiiniliw. I l c ~ s u l totit:iiiicld ~ 1)). thi: C.II.1.. test are probnbly niore n w r l y :i 1iie:tsur~of tiit' reac.ti\-it>- of 1 ile most reactive portion of mixed sarn1)lch. Shernlan c f ( I / , (I.? I gave evidence of t,his. JIacro topically picked iiigrcdi!,iir * i i i i ~ j - be jiiixturcw coiitaiiiiiig port ons of various other iii:yt,ilitwis as impurities. This may account fur t,hc siniilarity of t i i t ' r : ~ l u c ~for s m e sourc('. T h e f x t tliut iiigrctlieiir rcwtivwith tleci~easein raiik of c~orres~ioiiding ~liole cu:1,1s is furtliei. eviderice of variatioii of ingredients wit t i r31ik. Table I alao gives free svivelling indices for ~vliolecoals axtl banded iiigredients. These values do not, shon- Iirogrc4vi: decrease n-it11 rank as do the reactivity indices. S:tiiiplc~from the highest rank coal from Gallatin County slion. the liigliest free swelling indice?. Saniples from t Iic nest highest rank coal fro111 Franklin County show the lowest. I-alues for the t w o C rank coals appear t o be similar for both hole coals anti banded ingredients. Fusaiii is nonsn-elliiig, and values grei1tc.r than 1 shown in Table I indicate the prcserire of small aniouiits of swelling ingredients in t h e hand-picked fusairis.
FRANKLIN
I----
........,...
.
COUNTY
HENRY COUNTY
.
$1 IO
Fixed C ( d r y , :ish-free), '.; (::illatin I'ranklin Alacoupin Henry
Tot:i! S ( d r y ) . ' (:a:!arin Franklin Macoupin Henry
>
Caloriiic value, f3.t.u. Aloist mineral-matter-free G a l l a t in Fr:inklin
0
y
Vol. 39, No. 11
lIR(.I)npII1
Ileriry Thy mineral-niatter-free Gallntin I'ranklii! lIacoupln
1Iriiry Free s x e i l i n e index (::illatin l.rarikliii llacriiipin Henry
,. Pt. 111; 111). 1-28, Method D271-43. ( 2 ) Ihfd., Pt. 111. IIU. .. 154-7, Tentative Method 4720-43T. (3) I'idier, C . FI..,Spruiik, G . P , , Cizner. 1..O'Doiiiiell, H. J., Clarke, L.,anti Storch, H. I I . . U. S. Bur. SIiner, Tech. P a y r 642 (1942). (4) I~'uc~11~. IT., Gaugei..-1.K., H h o , ( ' , C . , axid Wright, C. C., Pa. S t n t c ('olleae. Mineral Induh. 1,:xut. Sta.. B7111. 23 (1938). ( 5 ) Len. 1'. AI.. a~ydXuise. H. IT.. J . S&. C'hem.Ind.. 58, 277 (19393. (6) L o w y . If. H . . .I. Geol.. 50, 357 (1942). ( 7 ) l I a i ~ I i d 1(,' . I,;., Fuel. 22, Y o . 8. 1.10 (1943). (SI Pn1.r. 8 . IT-.. Hopkiiir. H. C., and 1Iitchell. D. It., IiJid.. 10, .\in. Yoc.
t o be higliw. It \vns suggested that, sincae the C'.R.I,, ~ i i i ~ f l i ~ d probably iix'murc's 11101'e iicarlh- the rcxactivity of the niwt active conutitumt of :t mist ure, the values fuuritl ir-ere represcliitat ive IJE the most reactive constituent in niised sampl(5s and riot of t h c x particular baiidcd ingredient supposedly bcing twtrti. If this 33, 410 (1941). (10) Itee-. 0 . IT.. Ileeti. 1;. H., and L a n d G . IT-.,Ill. State G c d . were true in the c:tse of the fusains, removal of the niorc wactivc. Survey. Rept. I n ~ e s t 58 . (1939). material should h a r e given residues n-hose react irity iiidicos w r e (11) Sehrt?tiun, J . J . S.,atid brayers, SI. A , , I s u . 1;s~:.C k m f . , 2 9 , definitely higher. This is esactly what happi~nctli n t li(x H A ) 1118 11937). fusains. (19: $Iiet.tnan. 11. .\., Pilrtirr. .J. Xi., and Ostborg. 11. S . . A.S.T..II. Hltil. 112, 23 (1941). Some differences in reactivity indice,5 for the four ~:tmplrs:m' (13) $ ~ I , L I I I ~G, . C',, J . G e o l . . 50, 411 (1942). apparent. Ylj and Ti; valuw are highest for the smiplt. (11) $tailsfield, Edgar. aiid Gilhai.t, K . ('., Traus. Am. I r t s t . .lliniriu from the highest rank coal. The TIj value is lowest for rhv .\let. I?/turs., 101, 125-43 (1932). sample from Macoupin Courity, and the Ti:value lowest for tliv (15) Stopen. 11.C . , I'rot.. KO!/.S n c . (Lolitloti!. B90, 470 (1919~. Franklin Count,? sample. S o definite corrcxlat ion with rank is RECEI\-LD October 18, 1946. Published b y permissiou of t h e Chief, Illinois apparent'. State C;eoir,gical Survey It \vas thought t h a t differences in ri:activity indices might he due t o differences in specific surface of t h e samples. Sheriii:tii et c d . (12) showed that increasing t,he spc,cific surface, riwi1t.i in Biriarv 3Iixture of rt-Butane, Isobutane, and 1lon-ering reactivity indes' Tv-hen studying the sanie coal. .\inButene with Furfural-Correction cordingly, specific surface dctc~rniinatiori,~ were made by tlic' T,cx;t a n d Surse method ( 5 ) . Table I1 s h o w t h a t the s:t~iipltx i'roni Thcx following cum~c~tioriu phould lie niade in this paper which Gallatin County n i t h the highest Tlj and T1! values had tlic liigtiappcwc~din .June 1947: Pagci 790, in Table I1 the second virial est specific surface; tlie sample from 11ac.oupiii Clounty n-it.11 t h ( a x -578 ml. 'gram mole. coc~fficicntlor 1-butene itt 123' F. should t loivest Tlj value showed thc lon-cst specific surface. .11thougli a Pagcs 796, eitntioii (25j hhould 1.c.at1: Scatchai,d, G., arid Rays t u d y of t h e relation of surface t o reactivity should he niadi, on nioiid, ('. I,., .I. Aim. Chrni. ,Sac., 60, 1278-87 (1938). the sanie coal, the authors wished to d(btcrmine \vhc1111c~rtherr T. S. lIi,:mk;z \SI).I,f'. COLRI.R.U t l i t s rc'lation might be such a correlation for these samples. here is the reverse of t h a t t o be expected, it seems assume that differences in reaetivit? indixs for these ,sa~iiplc~ :ut\ due t o more fundamental causes. Ternary S y s t e m s rt-Butane-1-Butene-Furfural ~IOISTL-RE CHARACTERISTICS. Results obtained b?- tho eqiiiliaiid Isobutane-1-Butene-Furfural-Correction hration m(~t1iodare slionn graphicall>- in Figure 6. Coniliat'iaori 1lrr:it :i havci t ) i * ( - i i fourit1 in this .Junc~1'347 papc1' as i'ollo~r-s: of Figures 5 and 6 indicates that iiioistule-humiditS. curv(+ f o r P a p c ~708, aii iiirorriTet values of si is showri in tlie .anipli~ calculathe IIsiao fusniiis arc ~iiorcsimilar than are the c u r v c ~i'o~,t h c s tion. Thc line Cor y i nc%r thrl niitltll(~of the serond column should hand-picked fusains. All samples (Fiyuw 6) sho\r- a gratdu:illy rc2tl: increasing moisturc content \r-ith increasing humidity, but thcxre is practically 110 indication of high moisture take-up at liigli humidities such as t h a t exhibited b< the hand-picked fusains. h t prcsvnt there is no definite explanation for this clifferiw~(~ l'agc. 800, :I full liiic. of E:yuttt i o i i 7 (scw)ntl column) was oniitbetn-een the Hsiao and hand-piclted fusitins. Previous data (9) ted. It should iwltl as f'ollo~s: indicate that the differerices in moisture characteristics c:tnnot t)(, due t o the presence or absence of n-ater-soluble salts. It scbvnis log y1 = 1-12['4-? T 2.r1(.4-1 - - A - ? ) I rcasonable to suppose that possible e h a r i g i ~in porosity 01' surfa'w .r3~[.-l1--.3 L 2Sl(.L? - A - ? Y chnractcristics, or both, resulting from nitric acid oxidation might account for the differences in moisturc charactc~ikticsh t m ~ e n 2.1.sn[.-12-1 .11LJ - -I.,-! $- 2 L i ( . 1 3 - l - A l A ) hand-picked and Ysiao fusains. In an attc~niptt o secure further information regarding b a n d d 22.3(;LJ-? - A - , )- C ( l - 221)l ingredients of Illinois coals, sonic ~ o r l chas been done with tht. Page 803, in Figure 10 tlic dottcd lines shoir-n for relat'ive volaelectron microscope. Through the coopc,ratiori of G. I,. Clark, of tilit,y of 20 molcl 5 purcb isobutane and 20 molc % pure n-butane tlic L-niveri;ity of Illiiiois, electron microscope pictures at varioub are given only as a guide to trends; they should be used 13-ith niagnificatioiis were niadr for one set of banded ingredients and caution, airice it is probahlr that sucah coiiceiitratitms exceed the This Tr-ork appears promising but , for the four H-iao fusaiiis. miscibility limits for these hydrociubons in furfural. has not progressed far enough to permit definitr conclusioiin t o CERYTER, T. S,~IEHTE';, .\XI) A. P. COLBCRN .J. be drawn.
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+
+
+
-+
