The Generalized Phase Behavior of Paraffin-Tetralin-Bitumen Systems Citation Billheimer, John S. (1949) The Generalized Phase Behavior of Paraffin-Tetralin-Bitumen Systems. Engineer's thesis, California Institute of Technology. doi:10.7907/7b1g-ka12. https://resolver.caltech.edu/CaltechTHESIS:06172025-221443684 Abstract The addition of paraffin hydrocarbons to a solution of bitumen in tetralin will cause partial separation of the bitumen. Increasing the paraffin concentration will increase the separation of bitumen providing a second liquid phase characterized by high solvency for bitumen does not form. A maximum in the bitumen separation is thus obtained at the paraffin concentration corresponding to the formation of this second liquid phase. An increase in temperature generally results in a decreased separation of bitumen. These complex phase behaviors have been investigated for the addition of methane, n-pentane, and decane to a restricted bitumen-tetralin system. Item Type: Thesis (Engineer's thesis) Subject Keywords: (Chemical Engineering) Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemical Engineering Thesis Availability: Public (worldwide access) Research Advisor(s): Sage, Bruce H. (advisor) Lacey, William Noble (advisor) Thesis Committee: Unknown, Unknown Defense Date: 1949 Record Number: CaltechTHESIS:06172025-221443684 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:06172025-221443684 DOI: 10.7907/7b1g-ka12 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 17468 Collection: CaltechTHESIS Deposited By: Ben Maggio Deposited On: 27 Jun 2025 21:14 Last Modified: 27 Jun 2025 21:26 Thesis Files PDF - Final Version See Usage Policy. 17MB Repository Staff Only: item control page

TI-IS GE1'TSHALIZED PHA8S BEHAVIOR OF Thesis by Johns. Billheimer In Partial Fulfillment of the Requirements For the Jegree of Chemical Engineer California Institute of Technology Pasadena, California ., A.BS TRACT The addition of paraffin hydroc a rbons to a solution of bitumen in tetralin will cause partial separation of the bitumen. Incr e asin g the paraffin concentration will incr e ase the separation of bi tu.men providing a second liquid phase characterized by hi gh solvency for bitumen does not form. A maximum in the bi tu.men sepa. ration is thus obtained at the paraffin concentration corresuond in r; to the f orr,1,;i.tion of this sAcond. J.i rmi-l nhase. An increase in temnerature generallv results in a de- creased separation of bi tu.men. These complex nhase behaviors have been inve8tigat9d for the a ddition of mAthane, n-p entane, and decane to a restricted bi tumen-t8tr a l in s;vstem. i .i PRSFACE Bi turnen will separate from a. solution of bitumen in tetralin upon addition of paraffin hydroca.rbons. The investiration cf the conditions causinr thjs separation is presented i n fjve parts divided accord:inB; to the experimental methods applicable to the various svstems and cond i t,j ons. Part I presents the prenaration and properties of a bj_tumer.-tetra1 in 8C' lution. Part TT c 0 ncerns addition of paraffin hydrocarbons at atmos-oheric pressure. :i.n P.: l ass centriftJge tubes, whereas Part TT J concerns similar operations performed in a pre s m:re bomb at 200 psi absolnte. Pa.rt I V introduces the fo:rmatfon of a second liquid phase and its effect upon the stud:' of t.he senar ation of bi tumAn from the 9ystem. Tn Part ,_r 8 vanor pJ:-,ase is obtaine4 5r. the j-n- vesti :ation of th s C!1 aternar:r 9,rst0m containinr_i; methane, dec"lne, 0 1 tetralin, and b:i.tnme:1. . In co,,..,cl 1si.o:1. jt, "is h:r-oothesized that 1 the djsco:1.tinuJties in th"' 1-,itu:rnen sepciration c,1rves are a conseauence of the mul tj_phase nat,,r".') of the overal 1 system and not specifically e. propertv of th"' hi+·,,-,,e,,. iii AO Kl'·C'WLEDGMSNT B. i.-!. Sai:,- e, W. T>-:. Lacey, an d P.. H. Reamer ?:ave en courap- ,:,ment and i,nterpretative counsel. T.ee T. Carmichael aSAisted in mo d ification of the apparatus. The first preparation of refined bitumen, the determination of its properties, and the determinations of phase separations of bitumen-hydrocarbon systems at atmospheric pressure were uerformed by S. Yanak. ~~. Erickson and J . D. ~ eal ry. 7,immerman assisted materially in the preparations, standardi7,ations, and the renderj_no- of the natl=l. Photoo-r8nhic, micro-a.YJ a1vtical, and technician aAsistance have be en provid ed bsr l\Jnericen Pr-.troleum Tnstitute ProiFlct 7?7. -;. vundt nerform0d the l a ter exper'ir1 ents pertain i n" to refin"d bitumen sample 2. iv TABLE C'F C011T'T'SNTS . . . .. .. .. .. .. . . .. ....... . i Preface. . . . . . . . . . . . . . . . . . . . . .ii /\cknowled crments. . . . . . . . . . . . . . . . . . . . . ii:i. page Abstract I. Simulation of !:atural Asphalt-Crude Ci.l Systems by a Refined Bi tumen-Tetralin Svstem. • • • • • • • • • • 9 • 1 I I. The Pentane-'T'etrali n - Bi tumen and the Decane-Tetral inBitumen Svstems at Amospheric Pressure • • . . • • • • • • 7 III. The Attainment of Equilibrium in the Pentane ... TetralinBitumen System at 200 psi ab solute. • • • • • • • • • • 12 IV. The Formation of a Second liquid Phase in the PentaneTetralin-Bitumen and 1Jecane-Tetralin-Bitumen Systems • • • 16 V. Mul ti phase Behavior of a Res tricted Methane-~ecaneTetralin-Bitumen Sy stem. • . . • • • . • • • • • • • • • . . . . .. .. .... ... .. .... . References. . . . . . . . . . . . . . . . . . . . . . . Conclusion. 22 27 29 Figures. • • • • • • • • • • • • • • • • • • • • • • 0 • 30 ..... . .. .. . . . . ..... ..... 32 Tables • PA?T I BY A TTSFIW@ BITUivfEIJ-'T'".:TR AJT' SYSTEM \ bi tumi.nons ms.teria1 may seuar9.te under certain conditions cr:~urrine; ic1 the prod.i.;ction. of petroleum. The ad.di tion of the light hydrocarbons, metl ane throur;h decane, favors the seps.ration 0 cf this ma.terial. .,,he separation of bituminov.s material from a Santa-Fe-Sprh::.gs crude oil has been investigated by addi ti.on of metl,ane, ethane, propane, i so-b _1tane, n-butane, a:r.d n-pentane. r 1 ~ 1 Is • I A similar investigation has been made with trap liquid from t:'le '.7ree1ey Field upon addition of the associated trap zas •( 2 ) Ir.. ~eneral, increas:inz the tempergtt1re reduces the separation of the bituminous materis.l. >-1'owever, tl-ie phase behavior of such natural bitumen-hydrocarbon systems is cliffic1J1 t to study quanti.tati 11ely as the bituminous material which separates is not a simple substance. r:.'rvde bituminous material obtabed fro::, t!,e Soutri Coles Leveie Field was subjected to aYl extensive nurifice.tio:, urocess a nur1fied "bit1)~en." t0 ~;iel:1 The crude m0terial was leached three times with :pe:ntane at 220 rle2: F at t,,e vap0r press1_1rc of penta"".e. m1-,,,, resid1rn was dissolved in tetrREn at 190 dep: F an-:1. the i'rso1uble foreisn me.tter was separated b:' 8 centrifva-e anrl discarded. Penta.ne was then added to the tetra1 in solution until t}~e uentar.e cone entration was 0.90-0.95 weic;ht fractfon of the mixture. culent bitumen separated. PJack, floe- It was centrif'uo:ed, wasred with penta.ne, and dried in an air bath at 1.20 dep.; F'. was re-peated three times. A 11 wax 11 separated when the first pen- ta>1e liquor was cooled to 32 ders F. penta'1e liquors nrod.uced a The purification process 11 resin. 11 ?.vaporation of the subsequent 'I'he 111 t:irna.te a.na.lyses of these 11 hi tumen 11 components are shown in Table I. The purified tained as shiny black particles. The specific gravi t:'l of the bi tu- was ob- men was 1 ell5 at 77 de;-i; F compared to water at its mqxi"'urn density. The particles were brittle, but apparently amorphous. Prolonged ar~i tat.ion cf this nurified bitumen w:i th tetra.Un at room temperature will produce a solution containing a max:i.rnum of 0.07 weight fraction bitumen. A tetralin solution containing 0.05 weio:ht fraction bitume!'. was therefore proposed as simulated crude oil to investigate the conditions causin[:; precipitation of the bi tumen. Materials The tetra1:i.n used in these investigations was obtai.ned from E. r. du Pont de Nemours and Company. The material was fractionated in a thfrty-plate glass column at a pressure of approximately 1 psi. The initial and final 10 percent portions were discarded. The pur- ified tetra.Un showed an index of refraction relative to the D line of sdd:i.um of 1.5401 at 77 deg F. Its specific volume was O.016699 cu ft per lb at 77 deg F. The n-pentane was obtained from the Phillips Petroleum Company with an analysis which indicated that it contained less than 1 mole percent of material other than n-pentane, which was mainly iso-pentane. The n-pentane was used without further treatment for all operations associated with the purification of bitun1en. !-:owever, s·tx;:iplies of n-pentane were fractionated at reduced pressure in a glass-ringpacked cohunn for use in the majority of the measurements involved in the study of the restricted ternary system. The primary objec;;. tive of the limited purification of the n-pentane was to remove the dissolved noncondeneible gases such as nitrogen. The pertinent physical characteristics of the n-pentane were obtained from data available in the literature.(;;,4) The Bitumen-Tetralin Solution Solutions of bitumen in tetralin prepared by saturation at temperatures exceeding 220 dB~ F contain greater than 0.10 weight fraction bitumen. Upon cooling they form a gel. A solution that is stable at room temperature can be obtained by dissolving 0.05 weight fraction bitumen in tetralin at 190 deg F and cooling to room temperature. The stability of a 0.05 wei~ht fraction solution was established by preparation of tetralin solutions containing a maximum of 0.07 weight fraction bitumen through prolonged agitation at room temperature. Three days were required to reach this con- centration by agitation of solid bitumen with tetralin at room temperature. To determine the rate of solut~on at various temperatures, samples of the liquid phase were taken after agitation of the solid bitumen with tetralin for definite intervals of time. Successive concentrations atta ined at the several temperatures are presented in Table II. 4 The solution rate constant (k) is assumed to be de scribed by the first order rate equation ~ = k(C 00-C). '!'he wei r:ht fraction of bitumen in the li.quid uhase is represented by (C) at any time (T) and the weight fraction of bitumen in solution when the Hauid phase i.s in eauilibrium with the solid phase is represented by (Coo). Sstimated values of the equilibrium solubi.Uty and the rate of solution constant are presented in Table III md Fignre 1. The advanta p;e of preparinp: solutions at elevated temperatures is evident. The low rate of approachinp: equilibrium in the binary tetralinbitumen system at room temperature will later be found a controlling influence in the investig:ation of the pentane-tetralin-bi tumen system at low concentrations of pentane. Since the soh1hili ty of bitumen in pentane has been determined to be of the order of 0.001 weight fraction bitumen, equilibrium difficulties will not be expected at hi r h concentrations of pentane. The Analytical Determination of Bi t1Jmen .vhen pentane is added to a solution of bitumen in tetralin at 1 room temperature, bitumen separates from the solution. ~xperiment shows that when the pentane amounts to 0.90 to 0.95 wei r;ht fractfon of the total mixture, substantially complete precipitation of the bitumen from the solution will be obtained. Noting that the solu- bUity of bitumen in pure pentane at room temperature is less than 0.001 weight fraction, the precipitation of bitumen from tetralin solution by 0.90 to 0.95 wei~ht fraction pentane is considered 99.9% complete. This process is therefore defined as the analytical 5 determination of bitumen. ( ) 5 In practice the sample is agitated with this concentration of pentane for two hours at room temperature and centrifuged at 1000 times the acceleration of gr avity for 30 minutes. The separated bitumen is washed three time s with pentane, t hen dried in an air bath at 120 d e P: F'. ':'IJpicRl r esu lts obtained in th e standardization of a tetralin solution containing 0.05 weight fraction bitumen are shown :i.n Table IV. The validity of this determination iA also contin.P:ent on the homorrnned. ty of the purified bitumen. It will be noted that the method of analytical dete;mination is substantially the same pentane separation process employed in the ori ginal purification of the bitumen. If the purification has been sufficient, there should be no change in the ultimate analysis when the material is subjected to a further process of solution in tetralin and separation pentane. b:r Th is i s confirmed by the followin ~ experiments: Solid refined bitumen was leached with tetralin at 34 deg F and at 220 deg F. The bitumen was recovered from the tetr alin extracts by the standard pentane precipitation. '!'able V compares the ultimate analysis of the bitumen from th~ extracts to the analysis of the mat erial undissolved by the tetralin. Only a sli ght shift in the C:H r at io is observed between the first cold tetra.lin extract and the residue from an incomplete hot tetrali.n leachinr:. The hydro gen content in all cas e s differs not more than 0.3% from the average for two samples of the orip; inal refined bitumen. The carbon contents in the wax and resin as shown in Table V 6 differ by .? and: 2 percent respectively from that of refiried bi tvmen. Refined bitumen can therefore be considered as essen- tially e. single component w:ith rer:ard to the nrocess of solntion in bitumen a_-ri_d separation by a hie:h concentration of pentane at room temperature. Conclusion A refined bitumen can be obtained from the bituminous material occurring in crude petroleum by successive cycles of dissolvin~ the material in t9tralin and reprecipitatin8 it by addition of pentane. ~he material obtained is essentially homop;eneous wj th reference to extractinn b7 tetral in and precipitation by pentane. A tetralin solution containinp; 0 .05 weight fraction bitumen can be readily nrepared by heating a mixture of bi tu.men and tetralin at 190 de_p; F. This solution will remain stable at room temperature. The rate of soluti.oYJ of solid bitumen in tetralin is exceedirn;ly slow at room temperature, but solution proceeds at a practical rate at temperatures excfledinp- 160 deg F'. A restricted system formed by this 0 .05 wei[ht fraction bi tumen-tetralin solution with varyinf': amou.nts of uentane will be investir:ated as a simulification of the natural bi tumen-crvde oil svstem. Tt is -expected from the behavior of the binary bi h1men-tetra1 in system that the ternary system with pentane wil 1 be very slow in attaininr: eotdlibrh1m when onlv smal 1 a"'!ounts of pentane are in the system. 7 PNn IT The sep 8.ration of an asuhal ti,:: phase from naturall y o ccurring h}rdrocarbon mixtures upon the addition of natt•ral <::aB or hydro- carbons of low molecular weight has been reported.(l 2 6 7 8) The ' ' ' ' addition of pentane or decane to a solution of bitumen in tetralin results in a similar seuarat:i.o'.1 of the bitumen. For those temper- atures and concentrations such that the vapor pressure of pentane or decane from the s y stem does not sir.71ifica.-.,,tly exceed one atmosphere, the operation may be perfo rmed in r;1ass centrifuge tubes. Experimental Methods Pentane or decane was added o; ravimetrically to a glass centrifuge tube containing the bitumen-tetralin solution. The investigation has been restricted to systems co n tainin i;,: bitumen and tetralin in the weight ratio of 1: 19. The centrifuise tube was sealed and the mixture was mechanically shaken in an air batr. at 70, 160 or 220 def F for two rwurs. It was then centrifu?;ed at approximately 1000 times the acce1eration of gravity. Temperature could not be maintained entirely constant during the centrifugation, but tests i nd icated that the error so incurred was inappreciable. decanted and discarded. The liquid phase was 'f'he residue was washed three times with pentane, dried and weip;hed. A correction for the extraneo u s bitumen resul tin~ from the occlusion of a portion of t'!-le liauid phase was calculated from the wet weio-ht of th~ r ~s idue. 8 Sxperjmental Results The addition of pentane to the bitumen-tetralin·solution caused separation of bitumen as a solid or plastic phase. At 70 deg F and one atmosphere of pressure, separation of bitumen resulted when the concentration of pentane exceeded 0.2 wei r-ht fraction pentane in the total system. Table VI and Fi gure 2 show that the wei .o:ht fraction of the total bitumen which separated increased when the pentane concentration was increased. Substantially 11 total 11 precipitation was accomplished when the pentan.e concentration exceeded o. 7 wei R;ht fraction of the entire system. The decanted liquid ph8.se was kept for a week and examined. !1o further precipitate was collected in the case that the pentane concentration exceeded 0.3 wei p,ht fraction of the total system. However, for lesser concentrations of pentane '!'able VII shows appreciable additional bitumen separated upon retainin~ the decanted liotiid phase for a week. Thus equilibrium between the solid and liquid phases in the pentane-tetralin-bitumen system is not completely attained wi t hin two hours of afl; itation at 70 de p; F. This slow attainment of equilibrium applies when the perr- tane concentratioYJ. is less tha"1 0 •? wei p;ht fraction of the total system. Furthermore, a correction must be made for the bitumen contained in the liquid phase occluded in the precipitate. 'I'his correction increases in relative maR"nitude as the quantity of precini tate decreases while the bitumen concentration of the liquid 9 phase is correspondingly increasinp;. Table VIII indicates that the correction fo:r bitumen in the occluded liquid phase becomes of the same order of mai:i;nitude as the true bitumen precipitate when the pentane concentration is decreased to 0.2 1 weiP:ht fraction of the total system. Thus the larfe relative errors when the fraction of the total bitumen separated is small prevent the direct experimental determi-· nation of the minimum concentration of pentane capable of causing separation of bitumen from this system. This region of the phase diagram is therefore studied indirectly by considering the ratio of bitumen to tetralin in the liquid phase of the ternary system in equilibrium with solid bitumen as a continuous function of the concentration of pentane. As the concentration of pentane :is re- duced, this rati.o must approach the value prevailing in the binary system in equilibrium with solid bitumen at that temperature. The ratio of bitumen to tetralin in the saturated binary system at any temperature can be calculated from Table VI. The ratio of bitumen to tetralin in the liquid phase is plotted in F1p-ure 5 for the experimentally satisfactory systems containing pentane in excess of 0.25 weight fraction of the"total system. Semi-logarithmic coor- dinates are used for convenience of scale. ~his curve is then ex-. tended to the ordinate intercept which corresponds to a saturated binary system at that temperature. Considerinr: the total system containing 0 .05 weio:ht fraction bit1men, the ratio of bitumen to tetralin is restrict0d to 0.0525 10 in the svPtem as e. who le. 'T'h11.R ff"'~r concentration of ne11+,8.ne for which the allowable ratio of hj_tumen to tetralin in th0 liouid phase js·less th an 0.0"52"5 wil1 necessitate seuaration of bi+.umen from that 1iouid u1--iase. '!'he intersection of thi s curve with 0.0525 then corresuonds to the threshold concentration for pentane; i. e., for any hip:her PAntane concentration, senaration of hi tum.en should occur. '!'his threshold concentration of nentane is transposed to form the abscissa intercept of "?'1a;ure 2. ':'his permits completion of t he bitumen separation curve for low conc entrations of pentane. It is noted that in this region of hi£;h average molecular weight, the experimente.l bitumen se!)arA.tion is consistently less than that i.mplied from eoyilihrium consideration s . This is arrnribed to a ,a:reat- er role of su rface enerE;j_ es in +,h:i s region than 01;c1.ff s in the s:rs tems effective t~s.r, per,tane in ca, _, sinp; sep a r e.t:ion of bi b ;T1en fro:n the liquid phase. Tab le IX and '."i ; ur0 11 show t J:2.t rlecane ca.,..'s0s sub- stantially total precip:i.tation of t he b itumen when the decane concentration exceeds o .50 wei p;ht fraction of t he to+.a J system at 70 deg F and one atmosphere pressure. ':/hen tJ,9 t.emDer at,.lre 1:ras j,,_c reas- ed to 160 de_r; F, preci n5t.g_+,jon wa s st1bstantial ly t"+,al a t O. 7 we~sht cent.rat.ion permits 0.0'-1- vreiNht fract:ion of t.h~ tnt.Rl hjti.1m.er1 to remain i n th e lio vid Dhase. ~re t 1i res1:old j_nterce'!"'ts f rr +,h"'?0 bit.,·mer 11 sepa:ration curves have heen obta:Jned fr o::1 :"i n-ure 5 :in t.h0 mR..nnor descrihed above for the case o f nentene at 70 der ~. 12 PJ\.RT TTJ r'.iques do y,ot D(')rmit stor:ino: of t,he decanted liqnid phase at tJ,,.,, onerat1nrr 00:~diti.o::'_"l +,o determine th0 attainment of eq11j_]Jbriuy,,. T'-'erefore special techni.ques were emp10:,red t0 determi::'.e th e time necessary t o attain equiHbrium. Experimental !foth cd The stain less steel wei rrh~n ~ b omb described in a previo u s paper 0f t:'15-s laboratory was employed •(l) T},is bomb h0__d been especia_ll:'/ designed to permit centrifu2:ation and displacement of tho phases while l'ln1r.tain:i.n_r•: cor.stant pressu res up tc 10,000 psi&-. 7i t•_1J'l1':':;'tetraUn solu tion was introduced i~tc the evacu ated bomb and t h e weic".'ht of s olutio~ takey, was obta1ned :".:' difference. Pentane was then introduced into the bomb at the desired temperatvre until a pressure of -200 ps:i.a was obtained. Pressures were measured - oy a pressure balance accurate to 't 1 us:l.a in the 200 psia r anse. The bomb was subsequently cooled to room ter.iperature and the wei ,.,.ht of 13 pentane obtained by difference. :!Jeterminatfon of t h e ra.te of heat transfer to the bomb from the a:ir t.hermostat indicated th"l t,;!:'le req1.: tired to restore th0 system to opera tin!', te!:1perature. The cool- inz of the bomb du ring subsequ ent man :l. nv lations was •e stimated from dooling curves of the bomb to not affect the temperature of the liquid system more than 2 def F. The bomb was mechanically agitated for 70, 160, and 220 deg F respectively. 25, 10, or 4 hours for The relative periods of a g ita- tion were estimated from the rate constants for the dissolvi n.~ of bitumen in tetralin g iven in Figure 1. After sufficient a f', i tat.ion, the bomb was centrtfuged at 10,000 RPM within the t h ermostat. After centrifugation, the liquid phase was displaced from the bomb by a source of mercury at a pressure co n trolled within '!: 3 psia'. Experimental Results Table X and Fi gure 2 give the wei p;ht fractio n of t}--ie total bi tumen separated for various concentrations of pentane at 160 and 220 deg F. The threshold intercept is obtained as described previously. The relation of the separation of bitumen by pentane at 160 and 220 deg F to the separation at 70 deg Fis approximately the same as that described above for decane. 0 To determine the weight of pentane introduced, it h ad been necessary to cool the borr.b from the addition conditions. t;_ few exper- iments were performed tra.nsferring the pentane from an auxiliary weighing bomb in an attempt to avoid the effect of cooling on the precipitation equilibrium. In these experiments, the tempeFature 14 was maintained constant throughout the addition, agitation, centrifugation, and displacement. To determine whether equilibrium was attained, the liouid phase was in this case displaced into another evacuated bomb. The agitation, centrifu";ation, and displacement process was then repeated. Finally, when it was believed that equilibrium had been reached after the fourth cycle, the displaced solution was allowed to cool to room temperature. It was then restored to operating temperature for two hours, centrifuged, and displaced. This is analogous to the cooling; necessary for weighinp; in the normal procedure. The weizht of bitumen retained in the bomb i.n this case is shown by Table XI to be of the same order of map;nitude as that obtained in each of the four one hour primary period. 11 equil ibrium 11 steps above, after the Furthermore this was approximately the amount of bitumen retained on the bomb walls when the process was repeated without centrifugation. It appears therefore that the 0 bitumen obtained in the equilibrium and reconditioning operations, excludin'T the primary, is simply that obtained from solution adhering to the bomb walls. It is therefore concluded that for temper- atures of 160 and 220 deg F and pentane concentrations exceeding 0.3 weight fraction, the separation of bitumen attai!1s a rapid aYJd reversible eauili.brium. At room temperature however, the laws of simple sohition are invalidated by apparently sj_o;nificant surface energies. indicates that reversible equilibrium cannot be attained. Table XII At 15 70 deg F and a. pressure of 8000 psia with o .555 weight fraction pentane, 0.534 weir;ht fraction of the total bitumen separated after 19.5 hours of agitation. An additional 0.311 weir:ht fraction of the total bitumen was obtained after 21 hours of further ar;i tation. However, under similar conditions a continuous agitation of 56.5 hours yielded a bitumen separati.on of 0 .210 weight fraction. It will be noted that this result is comparable to the first of the above agitation periods only, instead of the expected separation comparable to the sum of that obtained in the two 20 hour periods. It is t.hus concluded that simple solution laws reasonably describe the pentane-tetralin-bi tumen system for temperatures not less than 160 deg F, and concentrations not less than 0.5 weight fraction of pentane in the system. At low temperatures and high average molecular weights of the system, surface energies a...nd low equilibrium rates invalidate simple solution measurements. 16 PA"IT TV THS F'ORMATICYJ\T OF' A S~CQl'<f'l JI 0 nrn PFASE p:r 'l'HS PENTA.NETSTRALI:N-BITUMSi'r .I\Jl"'D DSC f\J!E-TETRAUW-EITU11.1S!! SYSTEMS As many as four phases have been caused to separate from a crude oil by the introduction of a natural gas or propane at 70 deg F and 1500 psia. r 1 ~ \ At least one phase was a liouid sub- O / stantial1y free of components of hi1,:h molecular weir,:ht.(l) The separation of an asphaltic phase from a Santa Fe Springs cr~de oil resulted from the introductian of methane and the separation reached a maximum between O.14 to O.19 weight fraction of methane in the system. Sthane gave similar resu1ts.(l) The decline in the separation of this asphaltic phase with further increase in concentration of the paraffin hydrocarbon was accompanied by the appearance of an additional condensed nhase consisting of a dense, viscous liquid. This liauid had a distinctly higher specific r-rav- i ty and average molecular weight than the normal liquid phase. ( 2 ) A similarity between the separation of bitumen in the field and the separation of asphalts from lubricating oil cuts has been reported. ( 9 ) Experimental Observations This second liauid phase has been obtained under certain conditions in the pentane-tetralin-bi tumen and decane-tetralin-bi tumen systems at 8000 psia. Towards thA end of the disnlacement for 1.ar7e hydrocarbon concentrations, the displaced flu:i.d may suddenly change 17 from a low viscosity fluid to a dense viscous mass extruiin~ from the bomb. This dense viscous nhRse waA obtained very conclusive1:r as shown in Fi8-:ures 6 and 7 at 160 de,i: F with either nentane or • decane in concentrations exceeding o .5 wei.P 'ht fraction hydrocarbon in the total system at 8000 psi a. '!'he second li quid phase was also obtained with pentane concentn1tion s e:xceedjnp; 0.5 wei ;"_;ht fraction at 200 psia for 160 deg F only. and In the case of decane at eooo nsia o.lJ.* weight fracti6n decane, t!'le shapeless viscous flow:inz mass shown in Fi gure 2: was obts.ined. I n the case of 0 .6 wei ,sht fraction hydroc a rbon, Figure 9 shows the s e cond liquid phase extruded from t!'le bomb in e. consistenc:.' reta:inin g its form when collected in a glass ce:ntrifuse h,be. ''!:it:", pentffro A.t 8000 ns:i.<>. at 'bot½ 0.lr and 0 .6 weir,;ht fraction hydrocarbon, secor.d liqu:id nhase of extrudablc consistency was o~t,a.ined. At 200 Niia, the sa"Tle ex+,rudable ms+,e:rial was 0bt•lined for 0.6 weight fraction pentaY1e, but at 0.4 wei :::h~ fraction pentane a secor.d liquid nhase did not anneR.:r. ~'o determinations were made with decane at 200 psia, but at atmospher:i.c pressure in glassware, the formation of only a slight amount of this second Hquid phase was observed. Hhen the temperature was increased to 220 deg F., only a small 1 quantity of a second liquid phase was obtained for o.4 and 0.6 weisht * Hydrocarbon concentrations in the range 0.55 to 0.45 are referred to as o.4 wei ght fraction, and the rang e 0.55 to 0.65 as 0.6 weight fraction for simplicity in the discu ssion of the system. 18 fraction decane at 8000 psia, and at atmospheric pressure the formation of a second liquid phase was questionable. For all penta:r.e C8ncentrations at 220 deg F and both 200 and 8000 psia, the supernatant fluid was followed immediately by the displacement mercury, no second liauid ohase beino: observed. At 70 dep: F, a second lia_uid nhase in the consistency of a viscot1s fluid similar to Fif'Ure 8 was obtained for both O.4 and 0 .6 weight fraction deca!'le at 8000 psia. The viscous phase appeared in small quantities a_t atmospheric pressure. Pentane at 8000 psia and 70 deg F produced a larv.e quantity of the viscous fluid at a co ncentration of o.6 wei9:ht fraction hydrocarbon. A lesser amour>.t of viscous fluid was obtained at o.4 wei~ht fraction nentane. A second liquid phase was not observed upon addition of pentane at 70 de_i,; H' and atmospheric pressure. It is generalized from Tables XIII and XIV that the ratio of second liauid phase to the total liquid phases increases with the concentration of hydrocarbon for a given temperature. For a o:iven concentration of hydrocarbon, decane appears more favorable to formation of a second liquid phase than pentane. In all cases the formation of a second liquid phase was accompanied b~r a decline in the fraction of the total bitumen separated in the bomb. ,,,his is shown by the ne,ratively sloped solid lines on the rio:ht side of Fir;ures 6 & 7 which represent the fraction of the total bitumen that separates in the bomb. The dashed lines in Figures, 6 & 7 rep- resent the sum of the bi tu.men retained in the bomb and the bi tur.ien 19 in solution in the second liquid phase. 0b-riously, the differ- ence of this sum from unity reuresents the weight fraction of the total. bitumen :remaining in the first liquid phase. It is apparent from the fj_gures tha.t the advent of a second liouid phase causes no discontinuity in the concentration of bitumen in the first liquid phase. These results are of the same type as those reported by Botkin and Reamer(l, 2 ) if it be recoo;nized that the plastic uhase they obtained with crude bitumen corresponds essentiall~r to the solid bi tumen which separ!il,tes in the bomb for the purified bit:.1men system, and their dense liquid corresponds in the uurified system to the com- plete rane:e from viscous fluid to ext:rudable mass. Powever, they obtained the second liquid phase only for methane and ethane at all temperatures including 220 der; F and at no temperature for propane, butane, or pentane. It appears probable that the behavior encountered in the less refined systems, using crude bitumen, is limited to syst'ems 11here substantially larre quantities of hydrocarbons of relatively· low molecular weight are present. The additional liquid phase is generally ebtained at high pressures and at temperatures below 220 deg F for a hydrocarbon concentration exceeding 0.4 weight fraction. The con- sistency of this additional phase varies from semi-plastic at 160 dep; F to viscous fluid at 70 deg F. The high bitumen content of thi.s dense liquid results in a maximum in the precipitation of solid bitumen at the incidence of its formation. 20 Quantitative Results The data for the measurements carried out at a pressure of 8000 psia are presented in Fir;ures 6 and 7 and Tables XIII and XIV for both the pentane-tetralin-bitumen and the decane-tetralin-bitumen systems. The same method was used to determine the threshold points for these measurements as was previously explained in connection wit~ "'" 1p;ures • The systems are compared at low pressures in Figure 10 at a temperature of 70 deg F and a pressure of 15 psia. The effec- tiveness of decane jn causinr: separation of bitvmen is substantially equal to that of pentane at low hydrocarbon concentrations. At high- er concentrations the decane appears somewhat more effective. At a temperature of 220 deg F, data on the penta.ne system is unavailable at 15 psia due to the vapor pressure of the pentane, so comparison is made between decane at 15 psia. and pentane at 200 nsia. Ta1dne; note of the pentane 8000 psia separatjon l:ine, it would appear that at a temperature of ij20 deg F decane is more effective tha.'1 pentane at comparable low pressures. In the decane-tetralin-bitumen system an inversion of the effect of temperature on the separation :i.s noted in Fir:ure 5 for a pressure of 8000 psj_a. The inverted effect of temperature on the senaration caused by decane is compared in "'igure 11 to the normal decrease tn seParation·upon i.ncrease :i.n temnerature obta:inecl with pentsne. A simiJ.9r inversion of the effect of t<>mperat11re on aspha.lt qenaration i9 renorted in a ~alifornia qesearch "orPoration pavina-asnhalt nrocess.r 101 \ ., ' Since the invers;on does not occvr :i.n the corresponding nentane system, the temneratur0 seouence of the decane i?othnrms 21 must reverse before interAectin~ the orrlini=tt") renr9se?1tinr:,: the binAry bitumen-tetralin svstem. '.:'11e to tnis temnerature inversion in the d.ecane s:·stem at PiOOO pAia, no ·'-lirect compe.riso11 of hydrocarbon effectiveness is made at hi~h pressures. T""ltrodvcti c:r. of m0t:t,,_an e iYJ.to a r es tricted d ec ane-te traliP.hi tume:1 sy stem si.mulates the nat11ral asphalt-cru de oil-tra p g as systems investi gated by Botkin, Reamer et, al.(1 At the 8000 . ' 21, psia operatinp- pressure used in the previ.ous jnvesti.p;ation, the s olubility of metra.ne in a methane-te trali.n-Mturnen system i.s not su f ficient to se pa r a te si r:;n ifican t qua.YJ.ti ties of bi tumen . Con- sequently in thj s i:1vesti o:a Uo n v a riou s amounts of meth <Jn c h ave been Bdd ed -1:,o a decane-tetralin-b:i.t.umen syst0m restricted to the proportions 2: 19: 1. 'T' 1~e proportion of decane was sel e cted as the maximum for which thede-c-ane-tetralin-b i tumen solution wo1,1 ld be stable at 70 de_q; F and one atmosphere pressur e . The proportion of methane h a s been v a ried from t h e dew point to the bubble point at a pressi.J.re of ll000 psia a.YJ.d a temperature of 220 deP.; F. A limited number of determinat:i.ons at the same pressure were also ma.de at 70 de r; F. A maximum in the ,i ep a rat:i.on of bitumen was obtained s:l.mHar to th a.t reported :i.n Part I V fo:r the decan e -tetral i n-bi tl1men system. I n addition a minimum in the bitumen separation was obtained for a methane concentr a ti on between that of the separation maximum and the dew point. !xperi.mental Method ':" he experimenta l method presented in Pe.rt III of t h i s paper was used fo:r this system. However, the p9rtial volumetric data 2:5 were not available for estimating the proportions of the re~ stricted decane-tetralin-bitumen solution and of methane to obtain a desired concentration of methane in the system. In the early determinations this was estimated from the following information: (a) The partial volume of methane in the methane-decane system at 8000 psia, 100 and 220 deg F(ll,l 2 ) applied as a function of the methane concentration, (b) The partial volume of decane in the above system applied as a function of the sum of the decane and tetralin concentrations, (c) The partial volume of benzene in the methane-benzene system at pressures up to 5000 psia and a temperature of 100 deg F(l:5,14). (d) The ratio of the specific volume of tetralin to that of benzene at 77 deg F and one atmosphere pressure. The actual methane concentrat:i.ons obtained by means of this estimation from partial volumetric data for the first three determinations at 70 deg F were 0.015 ~ 0.007 weight fraction of the system lower than expected. For the first two determinations at 220 de.a: F the actual methane concentrations obtained were 0 .05 + 0 .01 wei?ht fraction of the system lower than intended. Using these empirica.l corrections, subsequent bomb loadin,r:s were within T 0.01 weight fraction of the methane concentration desired. The composition of the vapor phase was determined by measurj_ng 24 the methane throu()'h a wet test p:as meter and collecting the less volat:i.le comnonents in a dry :i.ce-acetone trap. The conce:1trations of decane and tetraJ.in in this condensate were found by refractive index measurements. ~ro anpreciable amount of bi ti.,men was obtained from the vapor phase. It was assumed that only negligible amounts of volatile components were present in the separated bitumen phase. The composition of the liquid phase was therefore calculated by difference from the tot.al ccmnosition of the system. The calculation of the liquid phase composition by means of refractive index data on the condensate was later confirmed by c. Yundt usinq; p:ravimetric analysis based on the specific volume of the liauid phase and knowledge of the partial volumes of decane, tetralin, and bi tu.men at that state. Data on two samples analyzed by both methods are presented in Table xv. The materials are the same as reported in Part I of this paper except that a new bitumen preparation was used for the latter portion of the investigation. ly except that a The new bitumen was prepared as previous- three-day soxhlet extraction with pentane was add- ed as a final step in the preparation. Table XVI indicates that the carbon-hydrogen ratio was decreased slightly in the second preparation. Fig:ure 12 shows that the separation of bitumen from the decane-tetralin-bi ttunen solution upon the addition of methane is similar 1.n behavior for the two bitumen preparations, but that the latter bitumen preparation is slightly less soluble at a. given state 25 of the s:vstem. Experime~tal Res~Its The weip:ht fraction of the total bifomen present that separates as a. solid phase is presented in Fir:ure 12 as a function of the wei.o-ht fraction of methane in the total system. A maximum was obtained in the fraction of the total bitumen which separated as a solid phase when the methane coricentration was 0.:5 w~irrht fraction of the total system. This is ema.1ogous to the behavior previousl:r cited for the pentane-tetralin-bi tumen ancl the decane-tetralinbitumen systems. The compositions of the phases for various states of the system from the bubble point to the dew point are dven in Table XVII. The composition of the liquid phase is presented in Fir;ure 13 as a :function of the weirrht fraction methane in the total system. The maxi- mum in the separation of bitumen in FiP:ure 12 corresponds to the minimum in the solubility of bitumen in the linuid phase in F'ir-ure 1:5. It is evident that this minimum solu.bilit:':' of bitumen correl- ates with the maximum in the sum of the concentrations of decane and tetralin in the liquid phase. The AOlubility of bitumen in the liquid phase is thus related inversely to the concentration of methane in the liauid uhase, as shown in Figure 14. The solubility of bitumen i.n the liquid phase exnressed as o::rams of bitumen per .,:,;ram of volatile material is presented in Table XVIII as a function of the averar:e molecular weir-ht of the liauid 26 phase. For t,1---'.ifl nurpose the molecular weizht of the bitvmen was taken as 1000 althou~h its value has been variously reported ae 1000 to 4000.(l, 2 ) Squ:ilibrium 11 conRtant"l 11 for the rlistri.- bution of methane, c1 ec"l.ne, and t0.tral in between the gas and liquid statAs arA aJ.cio presente0 in 'I'able XVIII. 'T'he equilib- rium constants are o:i ven in Fir,:ure 15 as a function of' the weio-ht fraction of methane in the total Aystem. rrre apn8r"mt1y irrep;- ular senaration curves for bi +,umen in the metha.ne-decane-tetralinbi tumen system are thus reduced to continuous functions when the solub:ili ty of bitumen in the lioy:i.d phase is plotted with reference t.,o th8 C':'mposi tfon of the liquid phase rather than th8t cf the total s:/stem. 'T're --1.4 scontinni t:i.ss of the curves of bitumen separatfon ns a function of t:->0 composition cf the sytem thus appear to be c1-)j_ef1y a consequence of the pha,;o rohtions of the methane-decane-tet:ralin· system and not di:rect-ly a property of the hi tv:rnen. t'nder co11dj t:ions of 70 deg F and. AQ00 psi a, a s"'Jco:ir:1. linnirl phase was obta::.-:ed fro1YJ ti,,e rest:rictd. metr.arie-d.ecane-tetraPn- that nreviously reported from th?. ne2:+8.n?.-tetre.En-b~ fa:.men nnd decane-tet:ralin-bi tumen systems at certai:r st.ates & Tab le XIX ind:i cates t'.'19t th:i.'l seconc1 Uo·_dd n"hase was asi=ioc-i ated with the maximum in the separation of bitumen analor;ous to the maxil!:um previously :reported for the co:rrespondinz pent,ane ar:d decan-:; s~rstems. The data are of preliminary ·nature and insufficient to 27 warrant graph:i.cal presentation. In the more extensi,,e work at 220 dep; F already presented, the occurrence of a second lic:uid phase is suspected by analozy to be asso0-iated with the maximum observed in the separation of bitumen • However the flashing of methane from th() nhase displacement tube makes it imposs:ihle to detect a liqui.d phase change if it were to occur in t he methane system investigations at 220 dep; F. Conclusion \sphal tic bi t urnen is qvi te s olub le in tetralin bu t relatively insoluble ~--.,_ aliphatic hydrocarbons. Ad dition of methar1e, pentane, or rl.ecane , to a tetralin solution of bitum<::n will cause precipitation of the bi timen as a so 1 id phase. In ?;eneral the separat:i.on of bitumen increas es with the addition of al:i.phe.t:i.c hydrocarbon.. Powever, under certain conditions, especially at hirh pressures, the separation of solid bitumen reaches a maximum and decreases upon further add it ion of a.linhatic hydrocarbon. It appears that the maximum separation of solid bitumen is related to a charp;e :in the nature of the 1. ioui.d phase. .fhen the 1 solubility of bitumen in the liquid uhase is taken as a f\mction of t1:-:e compoei tio:i1 of the 1 iquid pha.se itself ratl:'ie r tl:an trat of the total s y stem, a continu ous f un ction is obta:ir..ed. '.Jue t o the exuerirn.en tal technique being i.nr:vieqvate to separate the two liquid phases under all conditions where they occ 1J.r, the overall composition of the liquid phases is used in these correlations. 28 'T'he continuity of the bi tu.men solubility when referred to the composition of the liaujd phase is shown in Figures 3, 5, and 14 for pentane, decane, and methane as the ali.phatic constituent respectively. Any study of the apparent solubility of bi tume11. in hydrocarbon systems must therefore take co,rnizance of the phase behavior of the other components. 29 1. lJ. F. Botkin, H. P-. Reame r, B. u. Sar:e, and '.:'! . N. Lacey, 11 Mul tiple Condensed Phases from Crvde ens-Santa Fe Spring s Furldamental Resea rch on C'ccnrrence and '1 ecovery of Petrol011m, l\merican P0trole')m Instjtute, New York, ~3JPield, 11 2. 'J. F. Potkin, P. Reamer, r:;. ''.• Sacre, a"!"d '·!. 11r. Lac e:", Condensed Phases from ~rt1 de Oils-1'1-reeley Field, 11 Ibid. American Petroleum Institute , :-Tew York , ( 1946). P. 11 ~.ful tiple E:. :-r. Sare, W. Lacey, and J. c:. Schaafsma, "Some ThermoDynamic Properties of }:or~al Penta..v:ie, 11 Ind. -~.:1 ?: . ~hem. 3_], M• 48-50, (1?35 ) . 4. B. H. Sar;e and W. F. Lace,,, 11 Thermodyna.111ic Properties of n-Pentane, 11 Thin. 34, 730-T57? (1942). ~: . -~.bra.ham, " Aspha lts and Allied Subst ance s ," 5th Ed., D. Van :!'T ostrand Co. , Yew York, (1945). r-.. S. von Pilat, "Fractionation of Petroleum Residues with Eati.iral Gas under Pressure," Oil Gas J., 35, 10, 54-59, (1 936). 7. n. L. Katz · and o. a. Sinr; leterry, 11 Sip;nificance Ori tical Phenomena in Oil and Gas Production, 11 Inst. :Mininr- }Jet. Sngrs. , 132, 103-119,(1939). P. . of the Trans. Am. "1 . L. Katz, n • .J . Vink, a.YJd R . A. T) avid, "Phase Diae; ram of a Mixture of Ifatural Gas and 1'Tatural Gasoline Hear the Critical Conditions," Ibid. 13~, l06-p6, (1940). 9. P. T. r1 raff and H. o. Forrest, "Propane Precipitation of Petroleum Resins, 11 Ind. Sny;. Or em. 32, 294-298 ( 1940) • L. Kastens, 11 Pavinr- Asphalt from California Crude Oil, 11 Ibid. 40, 553, (1948): 10. l•/. 11. B. !-! . Sa p;e, H. Y. Lavender, and '.! . ~r. Lacey, "Phase Squi libria in Hydrocarbon Systems," Ibid. 32, 743, (1 940). 12. :r-:. H. Reamer, R. f 13. ?. P . Sa:>:e, 'J . s . ·/ebster, a , d '•!. -r-r . Lac ey, "Solubility of Methane in Benzene," I.12.iS.• ~' 1045, (1936). 14. E. P. Schoch, A. S. Hoffman, A. S. Kasperik, ,J. H. ti ghtfoot, and F'. '1 . Mayf ield, 11 Solubili t y of Me thane in Renzene, 11 !bid. 5 ~ , 7 88 , ( 1940) • • Olds, B. F:. Saz e, and ':I. l'T. Lacey, "Phase Equilibria in Hyd rocarbon Systems," .!_bid. 34, 1526, ( 1942). 1 1 Figure 1. Figure 2. The solution of bitumen in tetralin at atmospheric pressure. Separation of bi t11men frnm restricted pemtane-tetralinl:ii tu~e~ s~rstem at low nressures. Somposition of liquid phase in restricted pentanetetraHn-bi tumen s'rstem at eouilibrium with solid bitumen 70 dep; F, atmospheric pressure. The separation of bitumen as a plastic pha s e from decane-tetral in-bi t1.1men system at atmospheric pressure at a weio-ht ratio of hitumen to tetralin of 0.0525. C:omposition of the liquid ph ase in restricted. decanetetrali.n-bi tumen system in eouilibrium with solid bitumen. Fip-v.re 6. Separation of the bitumen from the pentane-tetralinbi tumen s:,rstem at ,°-000 nsia. Fi .o :ure 7. Separation of bi b.1.men from the decane-tetralin-bi tvmen system at E:1,000 psia and a weir:ht ratio of bitumen to tetralin of o.0~25. li"irrure 8. 'T'he nature of the '1 econd l iriuirl nhase obtaj ned from the r-lecane-tetra1 in-bi tum<>n su tem cnntainino- 0 .4 wei ,o-ht frqc+:ion rl 9cane anrl O .0'566 weirrht fraction bi +."men R.t l~O r-leo- 17', 8000 nsia. 0 mh0 m1t11rp of thA Aecond lit1uirl nhRAe ohtained from the decanl'l-t0tra 7 :i n-hitumen system co1:taininrr O.6 w0io-ht fraction dcca.'1.e a nd O .0~49 weic:rht fraction bi tu.men at li<O d e-- P', 8000 nsia. "'irr11re 10. '"'ompara tive 8epa r>1.tion of b itumen :fom th"l nentane-te trali.nhi tul"leri "l.nd the decanP-tetralin-bi tumen ?V f-1 tems. ?:i o-11re 11 • ';ompara.tive infliJAn~e of t0mnerR.ture "Pon 8eparation of bitumen from the pentane-tetralin-bi t1Jmen and decanetetralin-bi tumen systems contain:i.n7 0 •J? we:i. ''.ht fraction paraffin a.Y1d 0.032 we i r-ht frg_ctfon bitumen. ':'.'he we:ia-h+. -'."r,qctio:: o+' t 1-o t0t"] 1::-i_h,cnen separated RS a soli1 nhqs0 at 2000 psia a::d 220 de~~ as a fn::c+jo,, of +h,=, w0jcr',,+ f.,.cictio:"' "1"''·' ci"'e :i:: +.1-0 +c.,.sl ~~.,.qte:>" (II '"h-s corrmosit5o": of t,1-,r, 1ia,,jrl n1--·c,_se ,.-ri.,_l, ?c}j_rl h:it'Jtno'~ at, PQ00 psiP 8.nc1 :iY', 0n,,jl-ibrium 220 deer ::11. sol'1h-i ]-it:.' nf 1---i +,,"'.'P'' i-r, t1·0 e ] i01dd nh_qse at PQ00 psi8. ard 220 derr 171 as 8 f''nct-io:' o-£' tte we:i.~1-,t frBction me+hgnc-. in +,h"' 1i011j,J n 1..,Pse. "' 1--:c, •c:avi1.:ihrj,rm C"':s+.ants for m0tnan8 1 rlecan0, aYJd tetra} 11~ in t},e re,1trictc:d auaternar;< rwstern. w:i.th bit11me:1 at P-000 n::iia anrl 220 r:ler: F. z w 1/J ::J 5 J: a: ~ I- iii 0.12 t - - - - - + - - - - + -- - + - - - - + - ------1,rl- z 0 j:: I) <( a: IL 1- 0.10 t - - - -J: -+--- - -+-- - ----4- ~ IJJ 3: 120 80 40 160 200 TEMPERATURE °F T;'I " o • z w 0,, " ~ r_r1,,,,. u tior ,..,f atmo p½ ri~ nre 0 0 re. e 1o•F '30 AT SM. PRESS. 0 l60• f 200 PS I /J22C/F ZOO PS I iii J:f 0, / 0.2 0,4 WE IGH T Fig . 2 FRACTION 0.5 0.6 PENTANE 9PDArati0n of bi~mn~ fr ~ rE'<>tri c-t9d y tP...., Rt l0w u~n+<me-tetr9lin- · t v PTPS"3 ' ref!. 0.14 i - - - - - - - - + - - -- - + - - - - - + - - - - - 1 - - - - -1---l-'------l z w VI a: ~ :::, :) 0 I I- iii 0.12 i--- - - - - t - - -z --+-- - - - - - 1 - -- --+- ---Jl--+-- 012 ~ ! 0 j:: VI <.) z <( 8 a: u. I- 0.10 .__ _ _ __,_ _ _ ____._ _ _ __J__ ----,,,,__,-----1--- - ------J o .oe w I ~ ,o~ a: . ::,"- UJ ~ & e;,O v ~ z Q I- ~"'"'" ' - - + - - - --1-----~Q04 :l ~ 80 40 120 160 200 TEMPERATURE °F e so ut · on ~f itumen in tetr91;~ at atmosp~eric reQ ure. ~ ~ 0.8 :,; :, ... • 1o•F AT SM. PRESS. 0 l60• F 200 PSI /JZNF 200 PSI iii J ~ ~ 0·sr - ---t----1----J-'...._+--74--:~:__-+-___j____ __J ...0 ;:t 0.1 0 .2 0.3 W E IGH T Fig. 2 FRACTI ON 0.4 0. 5 0. 6 PENT ANE ~Pnarat · o~ of bit ~r• fr0~ r~Qtri~ Pd p~n+1cme-tetr9l1n- b ' t,, en 1:1:•.,,+.0~ at uresi,l''.,. "'R ■ 0w '-,- ,- '' -' ' , - o.1ot:...:~ ~-=--,= - '-'~~...L~ _- __ -"--,- - l - - - - - l - - -- --l-- - --+-- - -+ - - -- --.. --- Cl04 z :; < <( ,_ ,_"" 0.02 g ~ ~ 0.011--- - _ j -- - - - +- -- .. iii Q008 1-- - - - - ' - " - - -- --+---'<-- ~ -~ ...,...->,c - + - -- -- t - ---'s-- -F-'"<-----' 0 0 Q006 ;: "Q 70• f , 15 PSI ,_ Q004 ,:1220" F, 15 PSI 12 "0 70° f, 6000 PSI < 0 160 • F, 15 PSI <( :,: "'3: 9 160° F, """° PSI CJ' 220• F. 6000 PSI Q002 0.1 0,3 0.2 WE IGHT ,.,omno" ri l"\f' 0. 4 FRACTION 0.5 OECANE + ~P,~an~- tPtr~ ~n .,, +1-, " ic'l b . t e,.., . n e u ' bri , 0 Q 7cf F 0 l 60° F z 0.8 "'::, J:f 22<:f F ::i; ,_ ai _J ~ ,_O 0.6 u. 0 z 0 ;:: j ~ 0 .4 ~ ,_ I :,: ,1 I "'3: 0.2 f I I I ~ 3 0 I 0 .2 WEIGHT i). I I I 0.1 I I I I ,. 9 t i o -n r- "'trA.] . r,- 0.3 FRACTION 0.4 0.5 0 .6 PENTANE J,-, e l--i "''ti",.., +'r0"'l +i,~ it !nP""' oirrotom at POOO nni 13!1 a-nP- } _..,.. _..,.. p / / --- O.B 70°F 160°F 220'F ~ o p COMBINED BITUMEN IN NEW LIQUID ~ • f ~ ~ _..,.. /o / i3 .,,...- AND PLASTIC PHASES / / BITUMEN ~ 0 . 6 > - - - - - - + - -- IN PLASTIC PHASE / / --- --- ---+----+--+---+------1-r----+-------< 0 I- "0 z ~Ml------+------+----++----+---+-'a.,L---'0......,,--j-----+----~ 0 ~ a: "- I 1- :,:: I ~ "' 3:0.21------+------+---+-+-+---~-+-------t-~....,....-+-------i I I I I 0.2 0.1 F• • 7 0.4 0.3 WEIGHT FRACTION DECANE 0.5 0.6 eparation of bi tnnie'!" fro,., t e ecanetetra in-bit en system at A000 pis nd a wei~ht rat · o of i men to etra of 0.0525. ip;. 8 -- '!'he na turP of the '3P~ond li~ ' d Ph4se ~btain d from he e0ane-tetra1in-b'tumen system co~tainin~ O.4 w i,..,.:bt fractfo"' derme and 0.0?~6 ve · ~ht fract·0ri bit•ime. at 100 e"' A000 p9. I'! • \ J ... z UJ ~ :) f- en o.8 DECANE AT 15 PS/A _J ~ ~ -- -- w 0.6 I fLL 4, -- 200 ':.g_tv.!:_Atvt / / --- 4; cl 0 -- --% z -- ~S/4 Q 0.4 f- u<( ?SIi'- a: LL f- I - i>-' 0£.CI'-~ _,.. - 0.2 Q w s 100 e,cf)O -- _,.. -- 130 160 TEMPERATURE Fig. 1 u. O 190 OF 0omparative inf enc o~ tempera~'re upon separation of bitu~e~ fro~ the pe tane-tetra inb • t11:me-n and decane-tetralin-bi t umen svstem" conta ·ninR" 0.35 weie-ht fract;on uaraffin a'1d 0.032 wei~ht fract;on bitume~. 0.B 1--- - + -- +-------+-----+------+-++r-----J z 0 .=u <( ct'. u.. j: z 0.6 l--- - + - --+f- - - - - - +- - + -- - - + - - - - - + t - - - t - 1 - ---1 - w:;: ~~ C) ~ en 0 ..J ~ ~ 0.4 1---"'+----+-+--- - - - - + -f-<l~ - - + - - --+----tt-- - t - ----J <( 0 er: >- rf.w en 0.2 Fip-. 2 0.6 0.4 WEIG H T FRACTION METH ANE IN SYSTEM O.B 'T'he weie:ht fr act· ,...n of the total b; t., men rPua atAd is a solid phasP at eooo psia ar,n ?20 deo- was a funct · on of the wein-1-it freeion methane in +,h"' total A"StAm. --- - 0.6 I - - - T ETR ALIN 0.4 UJ ~ I Q.2 Q. 0 0 METHAN?- b-.. ~ cu 3 0 J I..._---,- z 0.06 ~ -.,I.___ I l DECANE I 0 L.._L_ z Q.04 0 I ~ I t- u. I~ t- I ,2 0.0 1 L-~ I UJ :;:: I I 0.006 Fz..... - ~~ I' -<,/ ~ 0.02 W---6 / ( oo JJ, i ' - .----- --l---J t::::-t- ~ L , /V ~ 0 Q. BI TUMEN :;:: "':::, "' UJ 0 Q.004 0.002 W ro Q.2 M M WEIGHT FRACTION he composit · o.., r · 1un w· + gel "d M M W ~ METHANE IN SYSTEM f tne lia".i p asP in eau l ' '"1 i tnl!'e'" at POOO p A· a 'lnd 2?0 ecr :'. \ 0.12 z uJ ~ w 0.10 t::' .'.l tO I n. i5 g Cl08 Ei5::i \ \ I\ ~ <{ ~ w 0.06 I I- tI t\. ~ ~ ~ (104 w ~ ~ o <102 0~ 0.02 Fie . 4 0.12 0.10 0.08 0.06 0.04 WEIGHT FRACTION METHANE IN THE LI Q UID PHASE - 'l'he so ibi 1 4 t" o-P b • tumcn in -'-hf.) 1 i q i p'~ase 4t Q000 nsia and 220 de~ Fas a functio~ of the we;P-ht fraction mPtha.n"' in the l;at•in p:base. 1 4.00 f- z 1.00 <( f- z 0.60 (/) 0 l) 0.40 ~ ::) a: co 020 • _J ::) aw 0.10 0.06 0.04 0.02 0.2 WEIGHT F'iP'. 1"1 0.4 0.6 0.8 FRACTION METHANE IN SYSTEM Sauilibrium cons ant" for me+hanP, decarE", 8.Y'd tetralin in the restricted auaternar' svstem with bitumen at 8000 pa·a and 220 deP' w. '!1US ~;r.rr:r~-:·' \rri: ,i\.~ . . _AJ .~~~ss ('~ :11?.0, ir S?,..:~~ T-"'!rr'!J!- ':~~: ~ rr,r_r- ';f'!T~.'T'T~T'"'.'"f\TM"i~ 1JEP .\.:"?.A'!1Si) TT ..c.i.. "'F'~ S".'"TT Tl)T"G'."' "r!:•np ,,,,y ('?' "I"'T'l_'!'~' IN rii1crr,ri .~:: :r~· 6.CS'::9.1:T~''"'. ,r,r, ~ :"Tn "''" C':'.-r::~n n A,,,S ~"'r_r !\.TT0Y. 00~:-0.1\?I~r~r 0:" ';S'l'~q1IJ!T~.'!'I0 11TS CF 'JC!·:PO:iITIC: OF m'.~TT\AT.H:- T)rmr__~-~y ~CT_T_T'T'TC'~rJ. '!.'f-1'?, SSPA~ ~ .m:rc,:: ('1i' nTmr_,~·'S"' !"'~("' rrrrs P'!:!~TAI'TE-'!.'~TR.A!, T"'T0 ::'!":r~llT S'TS'T'':?-' ~,T 70 :::sa :c,' A~TJ •\T··!C~PESlIC: PR-S<:;St'?E'. I~!FLT_!?!TC,S c~ ':'!'-~~ P-P('~~ s:P_~q \'!1TO!T OF BI~r:-.rE:~ PS"'T Ar~E 1/1:2:IGHT -~ .l\!J'J'IOl'TS. -~rn LC'':! vs~ 1 ~SSU!.."'P'::'. ?tir~., 'l't:';: CC??:C::C'::'TC" :"C".) ~"'T'~ "!~0~~<:!, nrmr_1 11 CC:'.JIU'3IC''T ('F A Po1m1r.:r-r 0? 'flTY~ T 1'°' 11) PHA'3S. '"!~"': S"!:!' •\PATIC'"' 0:1' 0 ITt:!-·:S:" A<:; PP.STIC PEA~E !<'R01~ 'l'FE 9.~~,,,'-l.JC'!'S!) ')SC ~J''S-'1:'~T~Al ,IY-BITlTI1EN SY~TSH AT ATMOSPHS:\IC P~SSSURS, TABTE X '!'PS q~PA'-H.TT(W C'F' Bim". 1i .".E~• AS PU.Q"'T-; pr.TAS? F'-lO~: ri:'ES '1~~,,,'1T0TS1J P~"''T'A~~-TS,,,?.AT,IY-BITCT.fS~T SYSTEM AT 200 P'3JA. TAP-LE XI T.-:E :\PP -~RT--;1':T PJ'T1~ry.Jf~:r ~T~P .~..R \T'~1J ~on C'F A~TT \,,,TC•fT. TA!' LS XII TPS P'VALIT;I,,,Y 0:<' S! MPL": srtr'mir?r LA't!S FC -q mp:;: QSPA!U'ITC''!'-r C'F PT'"T_r><r;:~r Am 70 ';!'.:(} F' ~'"'; 8000 PSI A. qT._ 7 :? "'::~r.'S;'~~ PSRJC,:JS '!'t1~'. q~PARAmioH 0:<' 0 I'T'T!:·J1S~· AS PJ.\S'0f'; pµAS~ F'f.{Olf TT?. r~SS'T'PJC:T?") P~?-T'T'~'·'S-'1'?,'T'!"> ~_T ;lT-PJ'"'T}_H,~1\T SYSTEM AT 8000 PSIA., riiAPLS XIV ,r,p;;:: ~sPA:1 ATICYr,r rF RI'::'t.1:--m:T As PL -\ 0 mrc PP Ass FROM Ti.:s 'TSSri:'1JC'f'S1J T)ECAWE-TST.RAT -IH-BJ'T"_T;'~:T SVQ'Rif A.T 8000 PSIA. TABLS XV A CC'MPA'UC\etr OF 'l'H1~ GJ:{_AJTIJvfS'l'RIC AYD ?SF'RACTOMSTRIC !.1STEOJS FOR DETSR'UFIWG 'l't.rS CC'l'f.POST rrirc,]'lr OF 'flirp: LnfID PHASE. T ABLE XVI ULTIMATE A1\:ALYSSS OF "'Hr.: T':iO BTTUt-'!S:: FR'"'.PAHATIO~rs. 'l'ABLS X'!TI CPA,-qACTERISTICS 0F 'T'f-1..,, Rr.:c-.rn1ncTS1J MST!Hl''""'-'"'t?GANETSIBATTT-BI".'Fil~~r 9YST'?J1 A.'11 8000 PSIA AND 220 DEG F. TABI.S XVIII '!'HS EQPILIB.RITTI 1 CO~rS"'A:r-TT:J AN!) '111:S SC'I.PBUITY OF PI TUMEY FC'R A Rr:sT'UCTSD r~STHA}TS-DEC A1'TE-TSTRALINBI'T'lJ!,f:E?T SYSTJ~~'. A<'.1 A Fu:rcTIO]'IT ('F' 'l'f-JE y/,E~T\T !v(OLECT:LAR ·:!EIGHT CF 'i'HS LI').'l'ID P)'.US~. TABLS XIX ""f-lE SEPAR'ATIOl'r OF PITD~-!Sl': FRC'M THS RSSTRICTS"!:l !·-TSTHAJ'-'E DEOAJTE-T7 TRA.I nr-3I'!'UHr.:!T SYS'T'EM AT 8000 PSIA A.l'ID 70 DSG F. Constituent J ax (a) Resin (b) Pitumen (c) \ ( a) I :feiP-ht fraction of constituent 1 Sarbon ~{ydro pen ~Ti tro s en Sulfur Ash 1•/t. Ratio of Carbon to Hydroe;en 0.8481 0.8373 0.8208 0.128? O.0997 0.0742 0.0090 0.0185 0.0119 0.0120 0.0160 0.0120 0.0043 8.40 11.07 6.61 '.fax is defined as the constituent insoluble in pentane at the ice point. (b) Resin is defined as the constituent obtained from ev a poration of the pentane extracts. ( c) Bi tvmen is defined as the constituent j_nsol-ublo i n "O':lntane at 220 des-: F. TARL2 II TP.S COJIW~TTR A_'rJ(''r-T OF' BITtJMEF pr THE l.I QllID PHASE IT'! THE PRESE~;CE OF SOI ID BITf.]}fP.N F'OR V.~RIOUS PSRIODS OF COFTACT Temper ature Time of Contact (hours) Bitumen Cone. of Liquid Phase ·nature of Liquid Phase At Temp. Cited After Cooling 34 24 73 !.iqu:i.d Soln Liquid Soln 78 8 Liquid Soln Liauid Soln 130 24 72 4 0.0174 (a) 0.0331 0.0533 0 .0619 0.0847 0.0805 0.0804 0.0866 0.0633 0.0841 0.0910 0.0912 0 .0943 0.1008 0.1349 0.1152 0 .1330 0.1930 Liquid Soln Liquid Soln Liquid Soln Sl. Viscous Soln Sl . Viscous Soln Yisc ous '3oln Viscous Soln Ver y Visc ous Soln Visc ous Soln Plastic }~ass 11 24 160 2 8 190 21.5 1 4 220 250 ( a) 14 1 3 11 5 Weight fraction bitumen TABLE III TH~ S'1UILIERTl1}f SOLFBTUTY C'F RI TUMEI'T nr T-STRALII'r CALCULATED ACC0RDI!'rG TO A FBST ORDER RATE EQl1ATI0r Temperature (deg F) Times of Contact (hours) Rate Consta11.t (hours-1) Equilibrium Concentration (weight fraction) 34 78 130 160 190 220 24,73 8,24 11,24 8,21.5 4,14 3,11 0.0073 0.0214 0.0426 0.0660 0.0760 o.1155 0.0700 0.0830 0.0950 0.1030 0.1200 0.1450 TABLE IV CCl1PARISOI! OF DSTERMINATIONS OF COMPOSITION OF TETRALHT-BITUMEN SOLL1TIO~TS As Prepared 0 .0513 ( a) 0.0500 0.0499 0.0499 Wei ght Fraction by Pentane Precipitation (Average) 0.0522 0.0524 (b) 0.0519 (b) 0.0508 0.0508 0.0508 0.0508 0.0511 0.0505 0.0516 0.0520 0.0518 (a) Established from gravimetric measurements made in course of preparing solutions. (b) !)uplicate determinati.ons by pentane precipitation procedure., TABLE V COMPOSITION OF BITUMEF AFT'.:<~R REPEATED EXTR ,'I.CTIOtT Carbon Hydro gen Bitumen before extraction with tetralin o.8254(a)0.0789 Bitumen di s solved at 34 deg F 0.8144 0.0789 Bitumen dissolved at 220 deg F 0.8250 0.0755 Residual Bitumen (b) o.8482 0.0772 Wt. Ratio of Carbon Fitrogen Ash to Hydro gen 0.0070 0.0058 0.0050 0.0094 0.0005 0.0002 0.0001 (a) Weight fraction. (b) Undissolv ed residue after extraction by tetr a lin at 220 deg F. 10.48 10. 52 10. 96 11.00 TABLE YI THE SEP !\.R ATION OF BJ '!'UMfilr FROM T!-1S PEtTTAf.TE-TETRAT ,l N- BITUMEN SYSTEM AT 70 DEG F A11'U ATMOSPHE?IC PRESSl:RE ( a) Weizht Fractfon Pentane 0.208 0.213 0.233 0.239 0.242 0.253 0.271 o.2T5 0.286 0.289 0.375 0.399 0.399 o.437 o.450 o.494 0.501 0.506 0.600 0.605 0.606 o.668 0.709 0.801 0.803 0.890 1/ eiE;ht Fraction Bitumen Separated Pentane Bitumen Tetralin 0.483 (b) o.484 0.527 0.547 0.597 0.632 o. 730 0.599 0.634 0.760 0.727 0.883 0.753 0.891 0.849 0.906 0.960 0.911 0. 981 0.965 0.978 1.000 1.000 1.000 1.000 1.000 0.210 (c) 0.218 0.237 0.244 o.24R 0.259 0.277 0.277 0.292 0.297 0.384 0.407 o.408 o.448 o.462 0.507 0.513 0.516 0.610 0.616 0.620 0. 679 0.719 0.809 o.8U o,895 0 .0240 ( C) 0.0153 0 .0188 0.0170 0.0155 0.0139 0.0103 0.0197 0.0133 0.0089 0.0086 0.0075 0.0076 0.0031 0.0042 0.0024 0.0010 0.766 (c) 0.766 0.744 0.739 0.736 0.727 0.712 0.703 0.6930 0.6940 0. 6074 0.5855 0.5840 0.5489 0.5340 o.4906 o.4860 o.4810 0.3896 0.3830 0.3790 0.3210 0.2810 0.1910 0 .1890 0.1050 1 Composition of the Liquid Phase 0.0021 0.0004 0.0007 0.0004 0.0000 0o0000 0.0000 0.0000 0.0000 ( e.) Data limited to sJrstem s containing a wei r;ht ratio of b i turner, to tetralin of 0 .0526. ( b) 1 ( c) ',f o ii:,;ht fracti.on of the component in the liquid phase in equ ilibrium wi t h the plas tic or solid phase. :-! ei ght fractio n of the total bitumen whic h h a s sepa rated after a period of 7 de.vs at 70 de e; Funder quiescent cond i tions. TABLE VII nrFLfTSNCJE C'F TH'S UPON '3EPA.1i./\.TIOJ\T CF BITOMEN AT LOW Pl~HTAlr:,: WEIGHT FRACTI01':S Weight Fraction Pentane Bitumen Separated in 2 hours Additional Bitumen Separated in one week Total Bitumen Separated Recovery of Bitumen in 2 hours (percent) 0.271 0.253 0.242 0.239 0.213 0.208 0.730 0.632 0~427 0.335 0.198 0.168 0.000 0.000 0.170 0.212 0.286 0.315 O.T50 0.632 0.597 0.547 o.484 o.483 100.0 ( a) 100.0 71.5 61.2 35.2 23 .6 ( a) Recovery of bitumen in 2 hours compared to the total obtained after one week. TABLE VITI THE C:C11RSCTIO!'! FOR SXTR/1.!\'EOrs BI'l''L1MEJ~ RESULTTI'TG FROM OCCLUSION OF A POR TIOJ\! CF THE LIQ,l!ID PHASE Weight Fraction Pentane Apparent Bitumen Separated ( a) Corrected Bitumen Separated Occlusion Correction (pe rcen t) 0.606 (b) 0.501 (b) 0.399 ( b) 0.286 ( b ) 0.273 0.271 0 . 253 0.242 0.239 0.233 0.213 0.208 0. 990 (c) 0.973 0.834 0.752 0.753 0 .880 0.836 0.810 0.777 0.788 0.819 0.828 0. 978 (c) 0. 960 0.753 0.634 0.599 0.730 0.632 0.597 0.547 0 .527 o.484 o.483 1.2 1.3 10.8 18.6 25.7 20. 6 32.1 35 .8 42.1 49.6 69 .2 71.7 ( a) Total bitumen separated b efore app l ying a. correction for the bit1..1men content of the occluded liquid phase . (b) Representative values from Table VT; below 0.27.3 weir,:ht fraction pentane all exper j_ments are reported in this table. ( c) Wei!Y,ht fraction of the total b itumen in the system . TABLE IX THE SEPARATION OF BITUMl"i:N AS PLASfIC PHASE FROM THE RESfRICTED DEC.ANE-TB.."'TRALIN-BITUMEN SYSI'EM AT ATMOSPHERIC rm~ SSURE Composition of System (Weight Fraction) Decane Tetralin Bitumen Weight Fraction Bitumen Separated Composition of the Liquid Phase (Weight Fraction) Decane Tetralin Bitumen 0.321 0.411 0.516 0.614 0.670 0.587 0.484 0.386 0.0093 0.0028 0.0000 0.0000 0.098 0.199 0.252 0.303 0.413 0.611 0.807 o.856 0.760 0.725 o.679 0.582 0.388 0.192 0.0459 0.0406 0.0227 0.0176 0.0050 0.0005 0.0002 0.248 0.289 0.306 0.356 0.410 0.610 0.611 0.714 0.702 o.685 0.636 0.588 0.389 0.'.,389 0.0380 0.0089 0.0088 0.0077 0.0013 0.0005 0.0003 70 Deg F 0.313 0.400 0.504 0.602 0.653 0.570 0.471 0.378 0.0344 0.0300 0.0248 0.0199 0.733 0.911 1.000 1.000 160 Deg F 0.099 0.199 0.249 0.298 0.403 0.600 o.eoo 0.856 0.761 0.713 o.667 0.567 0.380 0.190 0.0450 0.0400 0.0376 0.0351 0.0299 0.0200 0.0100 0.001 0.001 0.397 o. 521 0.837 0.973 0.996 220 Deg F 0.248 0.280 0.297 0.347 0.398 0.598 0.599 0.714 o.684 o.668 0.620 0.572 0.382 0.381 0.0376 0.0360 0.0352 0.0326 0.0301 0.0201 0.0200 0.019 0.477 0.456 0.582 0.760 0.942 o.892 TA.'S I .E X TTJ:~ ;,1ei 0ht Fraction Pentan e SEPARATION OF BI TUMSX AS PLASTIC PHASS FRC'I~ /1 ei ght Fraction 1 Separated C:ompoei.tion of the T. iqvid Phase (~ ei ght Fraction) PentR.!'.e :13itumen Tetralin 160 DEG F 200 PST l\. o.2R5 (a) 0.242 (h) 0.267 (c) 0~0267 (c) o.686 (c) 0.:586 0 •.<50 0&3~3 0.0111 0.595 o.454 0.553 220 ~SG F 200 PSIA 0.240 0.017 0.220 o.2a1 0.0373 0.722 0.520 0.322 0.651 0.591 0.843 0.600 0¥0267 0.0034 0.396 ( a) Weight fractfo:n pentane in the system. (b) 1'!ei ::;:!; t fraction of the total bi tu!'.'l.en separated as plastic phase. ( c) Wei r:h t fraction o f the component in the liquid pha se in equilibrium with the plastic phase. (d) As a resnl t of the formation of a second liquid phase at this state, the composition of the liquid phase was not determined. '!'ASL£ XI Temperature, de g F. 220 160 160 Pressure, psia 200 200 200 Pentane, wt. fr. o.4o 0.27 o._58 ')isnl8cement Agitation Bitumen A!!i t ation '?itumen Ag itation :3 i tumen Sep'd Sep 1 d (hours) Sep' d (hours) (hours) (gms) (vns) (gms) First 1 0.927 o.6 0.006 o.4 1.056 Second 4 0.004 1.1 0.014 1.2 0.013 Third 11 0.010 5.8 0.031 3.7 0.017 Fourth 23 0.018 2L5 0.045 7 .1 0.034 "1econditioned"(a)-- 0.006 0.059 0.068 11 Yo 0 . 007 0.083 0.072 centrifugat1.on 11 (b) (a) Reconditioning refers to the process wherein the displaced solution was allowed to cool to room temperature, then restored to operating temperature for two hours, centrifuged, and displaced. (h) Tl:o centrifup;ation refers to the process wherein the liquid phase was displaced into another evacuated bomb, and immediately displaced from this bomb with.out any centrifugation having been applied. TABLE XII TH'S IFVA.LIDITY OF SIMPLE SOLUTION LA.':!S FOR THE SSP.~RATIC'N OF' PITUMSF AT 70 DEG F AND 8000 PSIA Pentane Cone. Ag:i tation Bitumen Agitation Bitumen Agitation Bitumen (hours) Sep 1 d (hours) Sep 1 d (hours) Sep 1 d First Agitation 15.5 0.249(b) 19.5 Second Agitation 15 .2 0.211 21.2 Total o.46o 0.210 0.511 o.645 0.210 ( a) 1 .'l eight fraction of the total system. (b) '•Teto-ht. fraction of the totRl bitumen in the system. TABLE XIII THE SEPAR ATIOW OF BITUMr:.:'.l'r AS PLAS'T'IC PHASE AT 8000 PSIA Pentane \'/eight Fraction Di s tribution of the Bitumen Plastic Liquid Liquid Phase Phase I Phase IT 70 70 0.328 ( a) 0.535 0.539 0 .458 (b) o.645 0.210 o.489 (b) 0.355 0.000 0.153 (b) 0.000 0.860 160 160 160 o.4;54 0.558 0.606 o.429 0.111 o.41 6 0.394 0.000 0.139 0.177 0. 914 o.445 220 220 o.442 o.64o o.487 o.64o 0.513 0.360 0.000 (c) 0.000 ( C) Temperature (deg F) 70 (a) We i ght fraction of pentane in the system. (b) \•!eight fraction of the total bitumen in the system. ( c) Li quid phase II was not obtained at this state. TABLE XIV THE SEPARATIOJIT OF BITfJlvlEF A9 PLASTIC PEASE FROM THE REST11ICT'.-::'.D DSCANE-TSTRATIW-BITG'M:EE SYSTEM AT 8000 PSI Composition of System Decane Tetralin ABSOLUTE Distribution of the Bitumen Plastic Phase Bitumen Liquid Phase I liquid Phase II 70 Deg F o.450 (a) 0.607 0.0285 0.0196 0.077 o.490 160 ')Ag F o.412 0.589 0.0294 0.0206 o.408 0.510 0.559 0.160 0.253 0.530 0.625 0.717 0.201 0.062 0.176 0.221 220 Deg F o.425 o.654 0.0288 0.0175 (a) \'!eight fraction of the total system. (b) 'deight fraction of the total bitumen in the system. TABLS XV A COMPARISOY OF THE GRAVIMETRIC ANTI !\SFRACTC'MSTRIC METEO'JS FOR DET?Rf/fIJ\TIW} THE OOMPOSITT0~T OF' 'T'FS LIQPTlJ PHAS5: ( a) Component (}ravimetric Refractometric Methane (b) Decane Tetralin Bitumen 0.151 (d) 0.067 0.781 0.022 0.152 0.064 0.785 0.018 Methane (c) Decane Tetralin Bitumen 0.130 0.073 0.784 0.013 0.135 0.076 0.777 0.013 (a) Prepared by c. Yvndt. (b) Composition of system corresponds to 0.442 weight fraction methane. See Table XYII. (c) Composition of system corresponds to 0.283 weight fraction methane. See Table XVII. (d) Composition expressed as weifht fraction. TABLE XVI ULTIMATE AI"ALYSIS OF THE Trio BITC~T'-T PREPARATIONS C/H Sample 1'Ti troE:en Sulfur Ash Refined Bi t1Jmen Sample 1 O.R417a.- 0.0716 0.0080 0.0122 0.0097 Refined Bitumen Sample 2 0.8494 0.0061 0.0227 0.0136 ( a) Carbon Hydrogen 0.0752 Composition expressed as weight fraction. Mercury Ratio 11.76 0.0041 11.30 TABLE XVII C:Lt\.:.iAOT?R::rsrrrcs 0F rrr-rs RS<:;TRTCT~1J tET'.""AWS-lJECAFS- /t. Fraction Methane in System 1 \!t. Fraction Bitumen Separated Wei~ht Fraction of Phases in System 0.211a 0.3;0 o.495 0.550 o:;.665 0.757 0.842 0.949 0.027 0.140 0.599 0.099 0.157 o.459 1.000 1.000 0.0010 0 .0042 0.0095 0.0020 0.0021 0.0060 0 .0078 0.0028 0 .147b 0.283 o.403 o.442 o.466 0.500 0.544 0.598 o. 703 0.791 0.299 0.727 0.685 0.585 0.101 0.021 0.073 0.022 0.0°7 0.329 0.0114 0.0239 O.0183 0.0150 0.0026 0.0005 0.0015 0.0005 0.0014 0.0036 11 Solid TETR ALIE-BI TTJJ.nEJsT SYSTEM A.T 8000 PSIA A,Tlffi 220 DEG F. Compositions of the fnasesc Liquid Phase TetraJ.in Tetralin Methane Decane I,iquid Gas Methane Ga.s Phase lJecane 0.113 0.041 0.881 0.951 0.835 0.885 0.021 0.009 o .a.44 0.106 o:;.013 0.914 o. 720 0.522 0;493 o.489 o.451 0.336 0.299 0.171 0.073 0.074 0.256 o.459 o.492 0.508 0.549 0.663 0.700 0.828 0.924 0.581 0.737 0.750 0.766 0.827 0.839 o. 771 0.821 0.835 0.852 0.088 0.048 0.043 0.036 0.033 0.031 o .036 0.033 .024 0.017 o .35~ . 0.215 0.207 0.198 0.140 0.130 0.193 0.145 0.141 0.1.32 o.n5 0.130 0.113 0.131 0.094 0.088 0.096 0.078 0.068 0.053 (a) Prepared from bitv.men sample 1. (b) Prepared from bitumen s&~ple 2. (c) All J.lhase compositions are expressed as wein:ht fractions. o ' , . 13itumen 0.049 0.876 0.062 0.077 0.073 0.065 0.067 0.065 0.063 0.052 0.044 0.043 0.051 0.780 0.784 0.806 0.781 0.794 0.793 0.796 0.811 0.809 0.796 0.029 0.013 0.016 0.022 0.048 0.056 0.056 0.068 0.082 1.000 TABLE XVIII THE SQTJILIBRIUl' COWSTA?TS A:\'D THE SC'•LUBUITY OF BI'I'UMSJ\f FOR A RS'1TRICT? 1J METH~TE-DEC AfTFJ-TSTR AJ ,UT-BITU:ME'.'T SYSTSM AS A FUNCTION OF TBS MEAY MOLS!JULAJ'.l. 11·TSI:}HT OF THE LIQUID PHASE (a) Average Molecular Weip;h t of the L.i.auid Phase We i gh t Fraction Methane in the 1 iqui.d Equilibrium Constants fo:r Methane Decane Tetralin Solubility Ratio for Bitumen (b) 103.2 94.2 88.2 81.5 81.0 73.6 68.6 68.8 0.0529 0.0675 0.0776 0.0937 0.0961 0 .1129 0.1304 0.1309 2.88 2.47 2.28 2.03 1.99 1.86 1.72 1.72 0.0594 0.0726 0.0884 0.llO0 0.0220 0.0127 0.0164 0.0301 ( a.) 0.05 0.ll 0.15 0.12 0.17 0.17 0.20 0.15 0.03 0.0.3 0.04 0.06 0.06 0.07 0.08 0.07 Restricted to decane: tetralin: bitumen = 2: 19: 1 and condi tiona of 8000 psia and 220 der, F. (b) Solubility ratio expressed as r.; rams of bitumen in solution per r, ram of volatile material. TARLS XIX Concentration of Methane Bitumen Separated as Solid Phase Ri t \1men in ~,econd Tiquid Phase 0.108 (b) 0.173 0.245 0.2~5 0.017 (c) 0.545 0.211 0.272 0.983 (c) o.455 0.020 (d) 0.728 (e) Decane:tetralin:bitumen :a 2:19:1. (a) Restriction (b) Weight fraction of the system. (c) Weight fraction of the total bitumen in the system. (d) A second liquid phase containing 0.769 weight fraction of the total bitumen in the system was obtained at this methane concentration. (e) Althou~h a second liquid phase was not observed at this methane concentration, it may have been present since the detection of the second liquid phase is difficult in this system due to the large volatile content at appreciable methane concentrat:i.ons.