JUNE 1952
I b
PAPERS
I N THIS ISSUE
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ACTS
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PXQURES
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I
The chemical industry is still a healthy, growing young giant as these facts and figures bear witness--growthrate 10% per year compared to 3% for all indwtry over last 25 yews. 1951 sales of “chemical and allied products” up to $18.5 billion,an increase of 16% over 1950 and 325% over 1939, i m p e v e even after adjustment for dollar now worth only 45.5 cents haaed on average wholesale prim, 1935-39. Federal F&arve Board Index of industrial chemicala production six times higher than 1935-39 aveyge. Total assats of I&EC’s selected lit of 100 chemical procegs companiea up from $11.5 billion in 1939 to 530 billion in 1951. The chemical and allied products group in 1951 paid dividends at rate of 58% of net profit after taxes, while all industry averaged 48%. Expansion programs encouraged in part by govemmenGgranted accelerated amortination are under way, as example, certificates of necessity have been granted for 50% incmse in chlorine capacity by 1953. Output of many ohemimla has gmwn spedgcularly in period 1939 to 1951--synthetic ammonia from 311,000 tons to 1,772,000, sulfnric acid from 4,795,000 tons to 13,344,000, chlorine from 515,000 tons to 2,511,000, b e n e fmm 30,470,000 gallons to 265,449,000, styrene from 834,000 pounds to 706,767,000. Such increased production, not only in chemicals but other products as well, chews up mineral resources at p d i i o u s rate. Value of U. 6. mined production has jumped from 83,808,000,000 in 1939 to $13,270,000,000 in 1951. More attention must be given to problem of-d natural m u r w . Purchase of essential m i n d from other countries may accentuate further the expansion of foreigntrade in chemic& and allied producte. Since 1939 the value of exports of t h e products hm more than quintupled, while imports have nearly quadrupled.
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STAPF-INDUSTRY COLLABORATIVE REPORT
There m about 4.5 billion pounds of milk solids in buttermilk, skim milk, and whey produced annually in the dairiesof the United Statesand not used direotIy for fd.Dairy chemical by-product operations now proceas about 300,000,000 tons of thege waste materials. New processes and new markets are gradually expanding the volume of milk chemicals that can be made and sold profitably. One of the largest and most modem of the milk chemicals plants is operated by the chemical division of ShefEeld Farms at Norwich, N. Y.,starting with sweet, whole milk. This plant removes a c m m fraction for food purposes and then splits the remainii skim into m&, whey proteins, and milk sugar. Prowsing is essentially continuous. &me of the milk protein product is hydrolyd at a nearby plant at Oneonta, N. Y.,to yield a partiily d i g d nutrient. Slight variationsin operating conditions thmughout the proceae result in imp0-t changesin the nature of the products. Casein is produced in threegrades or further p r o d to yield csseinstesor devitaminiaed casein. Two grades of lactase are made as well aa a carbohydrateprotein animal food supplement. Milk protein hydrolysates are made in g m t variety by varying digestion conditions to produca the degree of hydrolysis required for a specific application. CHEMICALS FROM MILE c4.L.Uudr.A.m.u-m
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un
NUCLEATION SYMPOSIUM
Members of the ACS Division of Industrial and Engineering Chemistry explored new territory during “&t” chemical engineering symposium on nucleation phenomena. Raviews, therafore, were an important part of the sympdum coverage: thwretical diecuwions of qmntenwus nucleation, nucleation catalysis, and the kineties of the various phaee reactions provided the neceassry continuity to advanced thwry and reoent industrial applications. In the papers ’
weir 18th Annual M e e t i i Isst December in a
1186
INDUSTRIAL AND ENGINEERING CHEMISTRY
V d 44, No. 6
&g:--=---&-
published this month there are a h reporta on the dMusion cloud chamber and suggestions for its w in gss-phase nucleation studiea; on the importance of freez. ing and fragmentation nuclei in the initial formation of ice crystals and relationship of these h d q s to the forma$ion of mow in the atmosphere; and on the phenomenon of Liesegang rings of IammOniUm chloride, including isothemd experiments with x-rays, surface studies, and an inveatigationof the catalytic deet of water. Four papers on nucleation from the liquid phase include studies of some of the factors involved in crystal formation in m c m solutions; nucleation in supersaturated salt solutions; bubble formation in liquids; and the temporal development of localized plastic flow and fracturing in polymeric solids. Recent work on nucleation in solids indicate that when theory is modified to include the efiects of elastic distortion, most of the characteristics of precipitation from solid solution can be accounted for. Formation of the photographic latent image as a nucleation process IS discussed from the standpoint of electronic and ionic properties of crystals, and a modified theory is proposed to clarify the mechanism of nucleation in the decompositionof barium aside, which was originally related to latent image formation in photographic emulsions. . i
NUCLEATION..
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SYMPOEIUM OAT
.IS3
AIR P O L L U T I O ~
The nine papers p m t e d here, given partly at the section on air pollution at the XIIth International Congressof Pure and Applied Chemistry, cover subjects w i n g from descriptionsof apparatus for analysing asrosol content to a mathemstical statement of the problem of impaction of dust and smoke particles on Burface and body collectors. A filter capable of collecting macrosize samples is described; ~em8018so collected were found to contain considerable amounts of oxygewted and peroxidic organic materials. A description is given of a continuous cloud chamber for studying the relationship of foreign particles in the atmosphere whicb m e BS condensstion, freering, and s u b l i t i o n nuclei to precipitation promsea. Other papers include a description and explanstion of the sun’s spectrum as found in the lower atmosphere, a discussion of photochemical reactions which may occur m polluted atmospheres, a s u m m w of developments in the postwar period in analytical methods for sis pollutants, and a description of a pmcedure whicb measures atmospheric fluorine by analyzing raM waters and S @ moss exposures. Studies in local 8include data on sources of various impurities of the atmospbere in Lx Angeles and a study of the contributionof atmospheric pollution to ponderosa pine needle blight in the &te of Washiiton. AIR POLLUTION
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lSl9
QENERALPAPERS
c.(.b.bR..-Pmdwta
Ion excbange reaim are useful as catalysts for organic reactions h a u s e of the ease mth which they may be separated and re-used. Undesirable side reactions, such as polymerization, often may be avoided h u g h their use, and the d o n p d u c t s may be obtained free from contamination with catalyst. Becaw of these advantagw, it was of interest to study the catalytic activity of some of the newer types of anion excbange maim. T h e w of these resias as catalyste for cyanohydrin formation, benzoin condensations, diacetone alcohol formation, cyanoethylation reactions, and nitro alcohol formation is described. The techniques employed may be adapted to contiuous processes in many ~ 8 8 8 8involving relatively simple proceduresand equipment.
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CATALYSIS BY ANION EXCHANGE RESIN8 0 . d1 . 8 a k d d b .111.loL.D.c.
Ea@o&m
T-8-
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111
Evaluation
The objective was the development of a method for obtgining relative “explosion temperaturd’ of explosivesof military importance and detemining the variation of explosion time with initial temperature. A method has been developed which permits the objective evaluation of the explosion temperature as a function of time and initial temperature. This methd has been applied to the appraissl of a nnmber of the more important high explosives. These d t s are given both graphically and in tabnlar form. The method ia suitable for examination of new explosives and comparison with known explosives and givea another criterion of the stability of an explosive. The results are believed to be significant in that they give a comparative picture of the more important explosives, leading to elucidation of possible decom&tion mechanisms. They can be used in calculsting activation energies of decompoeition pmesses.
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RATESOF EXPLOPIVE DECOMPOSITIONOF EXPLOBIVES --and lrrll10911l
lune 1882
INDUSTRIAL A N D ENGINEERING CHEMISTRY
1.
1167
pliru VeMtiea
-_
The high h e velocities reported at the Bunsen b m e r flame tip are Usuauy sssnmed CO be the d t of l l v g ~heat trun8fer &&e b the central bmner stream. Both the high flame velwities and the huge heat t r a d e r &e& are questioned. E x p r ' m t d data on mixture velocity before and prcducb velocity after the h m c are reconciled by the sssumption of a ram &e&, whicb decreaees the mixture velocity hefore entering the flame and provides part if not sll of the pressure rise re, quired fortbe momentum d& Por flow through the flame. The Bame tempemtnm determined at various positions and the thermoynamic analyeis indicate that only small heat t&qr &e& m present and that the eentrsl mixture ame velocity is much lower than had been mported. Thus, the analysis providea a better understand.% of the flow mechanism of the mixture approding and entering the Bunsen burner flame tip snd indicates a metbod for evaluating this velocity on the basis of experimental data. I,
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EVALUATION OF FLAME SPEED AT BURNER FLAME TJP
L. c. Llohl7
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VUI.LL.
Ilika*p
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Production of xylenes by hydmforminghas renewed interest in the pure nitroxylenes as chemical intar* mdiites. A maximum yield of mononitro+xylenes has been obtained using the following d u e s of process varisblea: sulfuric acid-+xylene weight ratio 2.16, initii concentration of sulfuric acid 79.4%, nitric soido-xylene mole ratio 1.16, temperature 25" C., nitration time 30 minute%. The orientation is found to be 58% 3-nih and 42% 4nitm-o-qIene. The elTect of prooess variables on theyield of the mononitro compound is shown and their utility is compared with the concept of dehydrating value of the &ric acid. A new grapbical method of plotting contours of equal yield shows the interrelationship of sulfuric acid concentration and temperature; with more dilute acid higher temperatures can be used to give equal yields.
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MONONITRATION OF &XYLENE -A.
ity
RueExperimentd Btudiee of properties of h m e s in hydrogen-bromine mixtures are being made as a basis for testing various concepts of flame propagation. Data have now been obtained on burning velocities in mixtures of merent composition and at different temperatures. The burning velocity is increased as the initial $88 temperature is incFeased, but the &ect is not p m OUnoed.
Calcul&ions of changes in temperature and atomic concentration during reaction under various condions can be made from known thermodynamic and kinetic data. Quantitative calculations of burning velocities have not yet been made, but qualitative correlations of these data with observed burning velocities illustrate the importance, in understanding flame properties, of knowledge of the mechanism of reaction and rate constant8rather than of equilibrium concen@ations only. Comparison can be made of the probable effect8of heat flow and of d8usion of hydrogen a6ms or bromine atoms.
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FLAME PROPAGATION STUDIES USING THE AYDROG~N-BROMINEREACTION HuD.Cnhyu.WYIC.4ndmQ
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~mtme.?aw~inAnotMPe
Cbavanne in 1922 recognized that the fraction of petroleum boiling near 49' C. consisted of a mixture of cyclopentane and neohexane (2,zdimethylbutane), and both have ehce been individually isolated. The mixture is present in most petroleums to the extent of about 0.1% by volume. At atmhepheric premm cyclopentane and neohexane form an azeotrope containing about 85 mole % cyclopentane and boiling nea.r 49.1' C.-only 0.2' below cyclopentane and 0.6' below neohexsne. Cyclhexane forms similar azeotropes with 2,Mimethylpentane and with triptane (2,2,3-trimethylbutane). The cyclopentanc+neohexme ratio d8em widely in different naphthas; it is an easily identilied characteristic and, because of the 01-boiling mture and sseotropic hehavior of the two hydmrbons, distillations have little &ect upon it. These properties enable the mixture to be used to determine the probable sources of light gaaolies or solvent naphthas. CYCLOPENTANE AND NEOHEXANE I N PETROLEUM
-r.yMLu.IIDury.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
INDUSTRIAL A N D ENGINEERING CHEMISTRY
I.
Val. 44. No. 6
c a r b m u a materials can be converted in high &dab acidic products, intermediate in molecular Bise between coal and carbon dioxide, by M i o n with nitric acid at the n o d boiling point. Earlier work has shown that in the presence of air the consumption of oxidising acid was greatly reduced. The preaent investtgation was undertaken to determine wheuler satidactmy ratea could he attained with comhinations of dilute nitric acid and ougen gae at V i e r temperatures and pmures. Oxidation of a Pocahontas No. 3 bituminous coal has been studied over the temperature range of l l O o to 140" C., with nitric acid concentrations up to.16 M. Changes in oxygem pressure over the range 400 to 800 pounds per s q w inch gage have been found to have little effeot on rate. For the production of water?eoluble polycarboxylic acids this prooeae using nitric acid and oxygen in somewhat simpler than that using alkali and oxygen. However, the content of thple aromatic acids in higher in the latter and the presence in the products from the nitric acid readton of nitrugen-containing group might pmve didvantageous in a number of Mds of utiliition.
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OXIDATION OF BITUMINOUS COAL BY NITRIC ACID AND OXYQEN T..L&.(.Lulma ..rul
R8atkalLif. &dCapudty d .rL.
In considering possible ion exchange applications, an important factor is the potential life of the resins. For a particular resin this life depends upon conditions of the treatment and the composition of the solution being treated. A standard p d m e for teating ion exchange resins is described, and the relative performance charscteristics of 17 resins in the treatment of sugar cane juice have heen meaeured. The results &ow that several ion exchange resins paform well up to 15M) cycles, and indications are that their useful life is considerably beyond this. The anion exchaage resins loee their capacity at a much more rapid rate than the cation exchange resins. The data indicate that the better resins maintain capacity over a suflicient period of time to make them of economic value in the treatment of cane juice. It is probable that similar results would be obtained in applications of a related nature.
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ION EXCHANGE REBIN8 I N SUQAR CANE JUICE PROCESSING J . H . P - , P . ~ . ~ ~ R . T . O I I I , ~
1411
EN& and SnlvenbRedmhntPlulia
The fact that a rigid highly crosplinked m i n is produced when polybutsdiene rubber is baked at high temperatures was encountered in a general search for hestresistant electrically insulating plastic materisls. The charaderiaticsof the cross-linked resin were sufficientlyunusual to justify a fairly detailed study of ita mechanical behavior. Crosslinked polyhutsdiene proved to be a heat-mistant. solvent-resistant, d m d o n a l l y stable material. Its electrical characteristics, althongh not discussed in this paper, are equivalent to those of other bydrowbon polymers, such as polyethylene and polystyrene. However, certain fadors in its preparation make it seem u n l i l y that the reain will have more than limited commercial utilization. In studying the resin and its preparation, several points of general theoretical interest in the field of polymer structure were encountered. These include change in aeeond-order transition point with degree of cum, the shape of heat distortion curva, the i n c in~mod+us with increasing temperature, comparison of sodium and emulsion polymers, and the applicability of the kinetic theory of rubber elasticity to rigid resins ae well 88 rubbery materials. PREPARATION AND MECHANICAL BEHAYIOR OF HIGHLY CROWLINKED POLYBUTADIENE -A.U.fhnmm
Aaetic A d d by
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IUL
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The work was undertaken to obtain coimt koowledge of the phase equilibria in the condeneed system ethyl acetatewah-metic acid, so that the merits of ethyl acetate ae a solvent for the ex-on of acetic acid from dilute aqueous solutions could he evaluated. Complete data of auch nature am lacking. Data were obtained at 30' C. to e s t a h l i the binodsl curve and the tie lies for the system. The bmodsl curve compsres well with that obtained by Mim and the tie line dsta oorrelste well. The plait point was obtained by extrapolation of the conjugate l i e using the O t b e r plot. The distribution of acetic acid is seen to be mo~favnrable in the ca8e of ethyl acetate than in other solvents suoh as ethyl ether, creosote, or isopropyl ether. Jnue 1852
I N D U S T A I A L A N D HXGINEERING C H E M I S T R Y
. 11ea
r
The system k commercially important from the point of view of recovery of acetic acid from dillite aqueous klutions by liquid-liquid A c t i o n . Ethyl -acetate k a better solv& than any of thhse now xed, owing to its greater dissolving power for acetic acid. The paper not only provides the missing data but dso recommedds the use of a better solvent for i n d W recovery of acetic acid from aqueoussolutions.
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SY8TEM ETHYL ACETATEACETIC ACID-WATER AT 80' 0.
V.R.wulU.U.R.W
1~
The increasing interest in sulfur and sulfur compounds has emphasised to the chemists in the petroleum ndustry the lack of physical data on the sulfur compounds that are present in petroleum products. The present work desorik the measurement of vapor pressu~temperatumrelationships for 15 alcane sub5dce,8 alkane disulfides, 9 cyclic sulfides, s s d 3 thiophenes. The Antoine vapor preswue eqnation rn been evaluated from the d t a on each compound, and certain correlatione are then apparent between he normal boiling points and the B and C constant8 of the alkane sulfides and &&ides and their structure. Use has been made of the Antaine constsnts to calcatq the latent heats of vaporization of the various sulfur :ompoundsat their normal boiling points. The results are of particular interest, as within certain limits the calculations allow the prediction of the points of sulfur compounds which haw not ye0 been examined experimentally. In addition, the work is of value both to the chemist and chemical engineer h a u s e it allows calculations to be made lems dealing With the separation of sulfur compounds by distillation.
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VAPOR PRESSURGTEMPERATURE RELATIONSEIPS OF SULFUR COMPOUNDS RELATED TO PETROLEUM
r . T . ~ ~ , D . O . ~ ~ u . P . A . ~ .
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The sodium orthopkphatea are important industrial chemicals, yet data pertaining to their solubilities d the sodium phcaphatewater system are not plentiful and also are in disagreement. The isotherma for the sodium oxidephosphorus pentoxidewater system have been determined a t , No,goo, 80°, and 100" C. The solubilities of trisodium phosphate, disodium phospbmte, and moncium phosphate were determined from 0' to 100O'C. The conditions under which the various d u m phosphsteg, their hydrates, and complex dts o ~ be n erystalliid have been determined. The regions of crystallisation of the industrially important trisodium phosphate alkali complex have been determined. The conditions under which an alkali-free salt can be crystdlised have been pointed out.
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TEE SYSTEM SODIUM OXIDEPEOSPHORUB PENTOXIDE-WATER
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IYEIZRINB AND PUOOCESS DEVELOPMENT ~ l l l u l a u a A n o W R b h V ~ i Y
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This work wss carried out to determine the &ect of reduced pres%ureon separating efficiency, preasure dmp, and maximum allowable velocity in paaked distillation columns. There bss been little information publiied on thk subject, and some of the published Wts have been contradictory. The mterisl premted in this article e ~ ~ l s ithese n s contradictionsand gives several new concepts. Two new meth& for predicting maximum allo&dde velocity in packed Willation columns at any p e m t i i pressure are presented. Both the metho&;deacribed gave good a c c m y and are very easy to pply [to practical cases. Experimental data indicate that the separatii etsciency of some psckinga inre~ses and that of others remains constant when the pressure k reduced. Data showing the &ect of change ~
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INDUSTRIAL A N b ENGINEERING CHEMISTRY
VOl.
No. 6
in operating p m on p m drop per nnit packed height and on prewinre drop per theoretical plat. are given. A critical d u x ratio is reported for all o p e r a t i pmsnrea from 10 mm. of mercury to atmas pheric p m , below which the separation e5ciencyfallsoffrapidly.
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VARIABLES IN PACKED COLUMN DISTILLATION ATSUBATMOSPHERIC PREBSUXE
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EH4etofc.diylw.l.
The postolornve handling of canned food prcduets, principally in the p m eesing and cooling cycles, has h o m e a subject of in& inteeat. The canner is concerned not only with the hacteriolcgid aapecta of these operations but likewise with efficiency. Two conditions known to inauence the bactericidal &e& obtained in proceased item are improw retort venting, which was found in tests to result in decreased sterilizing values, and pressure cooling of conduction heating produde, which waa found to result in an increase in the sterilition &ect with increaaing time of the pressure hold. Decreases in water supply in reeent yeam have dled for more elliciency in the cooling operation. From the standpoint of time or water consumption, mal cooling waa found to be more e5cient than retort cooling and agitated cooling more scient than stgtionsry cooling. T h w tests show the extreme importance of uniform temperature distribution, especially with shorthigh temperature prowases, and indicate phssible functions of the pressure cooling cycle other than that reqnired to prevent deformed cans. A thorough check of the cooling operation may reault in considerable savings in the now dwindling water supply. I
PROCESSING Ob CANNED FOOD8 V.E.-,D.V.~&O.
r. ~ o ~ l u d i ,e A.
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1-
Rdlotbr of QuPenm..Lilit*. G a s permeabilities of plastic films are of basic importance in many applications. Selective behavior in gas separation, performance in packaging applications, and usefulness in haUwn construction me direct functions of permesbility. Permeability data & . e reported for a considerable number of commercial and experimental plastic films.1 Although these film amount to only a fraction of a rather extensive film collection on hand, they are representative of the important types. Definite recommendations for determining permeabilities in relation to temperature are presented. The signifimce of the reported data lies in their general applicability to prediction of gas separation characteristics. In addition, the data are of considerable interest to u r n of plastic films for pacpurposes. This latter use of the data, while incidental, is rather important, particularly as certain phasea of the work brought to light somewhat unexpected behavior of film properties aa a function of composition.
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SEPARATION OF GASES BY MEANS OF PERMEABLE MEMBRANES Dmvldwmlwnpl.L.br .rlKarl u..
,141
D ~ ~ o f L I . . . I u S w f wk.u a
Values of heat transfer coefficients, &, for gaa to sised Utah coal particles in a fluidied bed have been determined aa an aid in predicting r a h of heat transfer to be expected in other similar systems. An quation represanting the data satisfactorily for engineering we is & = 0.OOn GI.' D p . A statistical examination of the d e c t of diameter of the particles showad the particle diameter to have a small but definite influence on the coe5cients at high mass velocitk. A method for determining &&e surface meas for irregularly shaped particles is described. It is expected that the data preaented on vsluea for hp can be used for design purposes, and that the method for detarmining meas of solids may be useful in many casea where such determinations have heretofore not be& poasible or practical.
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GAB80LID FILM COEFFICIENT8 OF HEAT TRANSFER I N FLUIDIZED COAL BEDS 1.8.W.ul...L.h,dOot.--
VuI.LL. L T -
1-4
Batch DWibShm
Experimental studies were with the system ~heptan~methylcycloh~e-toluene in a glass column, 0.5 inch in inside diameter, packedwith a &foot height of */lrinch %age helioes. This had approximately So plat& and 60-ml. holdup at the throughput of 400 ml. per hour which waa used in all the experimenta. The holdupcharge ratio was d e d from 4.5 to 18% by using dfl-t quantitiesbf charge, while holdup remained substantidly constsnt thmughout the seriea oSdistillations. Two dflerent ternary charge compositions were used and reflux ratio waa d d from 7.5 to 1 to 60 to 1. IlUm 1852
1NDUSTRIAL:AND ENGINEERING CHEMISTRY
1191
..Acomparisowof.th6batch distihtion C U N ~af:~..vpdmentakkrnfwj.and.binsly rnmunder.idm : i d conditions of r e f l u x r a ~ sbsolote d c$srge.of eboh,component&owed thst the separation batweer4 iwo components of the b i i was eimilar to the -hn,bf.these two components in the terasry, if d y hew twommponentm were present in the teoan!.di@tUlatein appreciable quantity. Them compariwna dscrindicated that the Bhsrpness of separation betweentwo componentsis goverddby the efi&ive,holdu-pthat is, the per cant holdup based upon the absolnte e o u n t of the two the initial ternary charge. Becauee two componepts may'constitute a :barge, large @ective holdup and consequently I q e &e& on aeparstion can be expeded in multicomm n b t batch distillations, even though.holdupis with total oharge. ons studied.were the same as for binary The general &e& of holdup in the ternary iystems. The deet of increasing per cent holdup was found to be beneficial, detrimental, or of no efiect i p n sharpness of separation between componenti.of a.ternarymixture,depending upon the reflux ratio.
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EFFEOT OF HQLDUP-C34RGE- RATIO JN LABORAT6lW .DISTILLATION
~ # v L c l . Ol*r,h
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MacaRtan~aIlthIO2kFJlti.p
Vi& light (listillate fuel obtained from hiih&-crudea haa a high mercaptan content and consequently an unpleasant 0dor;which muSt be.iemovedifthis stock is to be used for domestic heating. Bench-soale and pilot plant s t u d y have led to e solvent extraction process for removing malodorous nercaptans. The Bokent is cornpod of aqueous poteasium hydroxide, methanol, and potassium cresylates. l'he extraction is imphved by low operating tempera?, the use of concentrated aqueous potassium hydmxide as a component of the soImt, and'recyole ofby-product cresylates. In pilot plant studies, 8% of the merosptens present in high& light distillate fuel were removed by twc-atage conntefcumnt ex+ ion without degradation of the color of the fuel. Extraction etsciency of the solvent after many regenem ;ionswas equal to that of fresh aolvent. Thia investigation has indicated a feasible commaMial proceas for removing mercaptans from liiht distilate fuela without colpr degradation. Operating conditiona would vary with the stack to be treated, the level f memsptan *oval d&, the availatiiiy.of other sweetening processes, and economic considerations. OF
MERCAPTANS
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F ~ ~ OLIGHT M DISTILLATE FUELS
;J.ILX,.-,~~~W-
;IIY
"9p~tnaIL.l.
The vaeup retorting of oil shale wa8 conducted to determine the &e& of reduced pressure on the retorting of oil shale, and to evalnate the prformanoe of a fluidized system when operating under vacuum. The @ect of p w on the temperature r e q e ,toproduee oil from the shale and the charach of the 'iquid &du& produced unbr vacuum olefinic nature is evolved from oil shale by A semisolid hydmcqbon of high employed by atmospheric p m m m retorta in racuum treatment i m t u s e . The ow8 a distinct melting point, ind decompoees ,npidy when heated to temperatures below the u6nal retsitinp temperafor oil We. The f l u i d i d systems were found to perform excellently under vacuum, and to require an & d i y @'amount of cluidining gas. This is considered to be due to spontaneous fluir!ir+tion produced,by the, vapors and gay8 mlved from the spsle at low pressurea. The vacuum retorting method is suggested fwa pmoedure for obtaining a stable, uniform material from od shale which muld be crscked under conWed conditions for the production of fuels and other Detroleum-type pmduota.
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VACUUM RETORTING OFOIL WALE IN A FLUIDIZED BED hL.lw nJt....d.L,dII.mp.'...............
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D.t.€os stwc+w&
111
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OLI haa
Considerable research&ort is being expended to develop a ~equenceof operation! Fpabh,of p d u c i " p which is of+ referred to as Alhata bituminous sand. Any pnnary separation of the bitumen from the aand by watW Washkg yields a crude produd hkb iri water and lolids. The National Research Conncil of Ottawa has developed a method of simultsneouslyandoOntLHlously d&yhting and coking this wet crude to produee,goodyielda of clean, dry coker distillate. This is done by :bkgingdirectlyintoafluidhdsilicaBsndbed.' ' The we of tube-type dehyhtors is eliminatsdy$ at 9temperatures used (500' C.), a product is ob;sinedthat $Em snbhntially fmm the feed. Tl$s@t&d$ one possible alternative to direct distillation d oil,fromraw bituminous sand, developed . earlier , L marketable oil from Athabaaca oil-sand
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OIL FROM ALEZ,RTABITUMEN
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1192
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W.S. P - d n
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IN D U S T R I A L A N D EN% IABERI N 0 C H E M I S T R Y
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