NLY lV52
W
c PAPERS I N T H I S
ISSUE
Mor. PonrEh. k .P h u a s
Since ita b v e r y nearly a century ago, formaldehyde hna risen rapidly in the commercial chemical picture. During the lsst 35 yeam especially, production in the United States has risen logarithmically, with new outlets appearing at frequent intervals to maintain the rapid upward trend in sal- and consumption. Since 1935, resins and plsstics have consumed more than half the nation's output in normal times, requiring an all-time high of nearly two thirds of the total supply last year. One of the more reoent entrants into the formaldehyde producing 6eld is Speneer Chemical CO.,with its 5O-ton-prday Chicago Works plant at Calumet City, Ill. The pis a Bimultsneous air oxidationdehydrogenation of methanol, using d v e r as catalyst. Reaction is carried out in the vapor phase at about 6ooo C., with singlepsas converaion of about 6% and catalyst efficiency of over 90%. Formaldehyde and unchanged methanol BIB collected by absorption; the exces methanol ia ramovd by a stripping column and returned to the process. b e d l plant dciency, from methanol at S p e n ~Pittsbw, '~ Ksn., point of origin to formaldehyde at the Calumet City shipping dock, is well over Formalin solutions containing formaldehyde and methanol in ratios of 37: 1,37:7, and 46: 1are blended to close apeci6cations for ultimate u88 in the manufactum of phenolic, urea, and melamine resins, hexamethylenetetramine, pentSerytbFto1, ethylene glycol, and a wide array of smaller volume industrial chemicals. The Spencer plant is thoronghly instrumented for virtually automatic operation and ia a model in opemtional safety and g o d housekeeping. FORMALDEHYDE FROM METBANOL R.W.W,X.D.
Wdhe.,@
1.W. MeY0.Lu.l
............................................................
IW
sTMPO8xA
Pbsphorlu and Phoaplutes
Currently, the economic status of the sulfur (and sulfuric acid) industry is backiiring to promote mwuch and proces development in fertiier phosphates, particularly superphosphates. There is renewed interest, for example, in t h e w of mixturm of sulfuric and phosphoric acids to produce intemediite &ea of superphosphatesin facilitiea now used for acidulation with sulfuric acid alone. Departmentof Agtidture experiments indicate that p m m i n g is feaaible, but water content and temperature of the reaction mixture must be cpntrolled within closer limit8 than are requimd in singleacid treatment. A laboratory study of the iron and aluminum in phosphate rods ahow8 the Muence of t h e e components on the physical &meter and phosphate solubility of the superphosphatesmade from it: Iron c a w d e velopment of citrabsoluble phosphorus with increasing age of the suprphosphate, whereaa aluminum is conducive to the development of citratainsoluble phosphorus. Another reports work on superphosphates, granulated and quick-cured in a laboratory Rotc-hum dryer; these phosphates am superior in physical characteristice to storage-cured products. Introduction of air during the drying p r o m and the use of dilute aids gives higher concentnrtions, and the resulting prcducta wiH granulate better than those made with acid of the usus1 commercial concentmtion. Development of the phosphorus industry in the United States and U B B ~of phwphorus and ita derivative! in the food industry and in detergents and pharmaceuticals are covered in a review which highlikhta the electrothermal acid procaases; a separste paper emphasize! the magnitude of the operations deigned to furnish phosphorus aud phosphoric acid to the fertdizer industry. PHOSPHORUS AND PHOSPHATES.
.............................................................................
11@
O u i t i c l t i o a d solid ends
"hie w n d section of theoretical eapects of gasirying solid fu& (the 6ret appeared in the May k u e ) presents fiveadditional studies of combustionand gasifioation reactions. A method is given of plotting flame-shhility data for binary fuels consisting of combmations of hylrlse
INDUSTRIAL A N D ENGINEERING CHEMISTRY
VQL 44, No. 1
d r o p , methsne, and carbon monoxide, so that three composite eam&bdity diagram for blow05 and thm for flashback summarhe all the limits for the three binary systems. A method of predicting by calculation burner performancewith interchangedfuelgases is given Kinetics of the combustion have been studied for the reactions which occur when cylidem of eledmde carbon are placed in h i temperature, high velocity air atresms; data indicate that the reaction rate should change from diffusion controlled to chemically controlled as the air velocity is increased ta some l i t i n g value. Other studies deal with the kinetica of the steam-wbon reaction in porous graphite t u b and of the hydrogen-osrbon monoxide reaction with an imn-copper catalyst in a tubular mador. GABIFICATION OF FUELS.
...................................................................................
P. In tests performed to d u a t e the low tempratwe properties of silicone rubbra, these rubbers were compared to natural rubber and GR8 by meaas of modulus, toraiod stiffnew, and per mt recovery data. A special cold chamber was designed for s t m t r s i n maasurements at temperatum down to -130' F.,
.IS47
plutbitr at -1900
-4-z
below that attainable with dry ice. Some types of silicone rubber did not stiffen appreciably until temperatures between -112' and -130' F. were reached. wheress both natursl rubber and G R S stiffened at -76' F. Careful control of the induction period in wnjunction with the Gebman cold flax appamtna showed that silicone rubber Type I1 may be supercooled, and crystallization is a mpid proceas. The resulta of t h w tests indicate that silicone rubbra will perform satisfactorily in a lower temperature region for applications mquiring an elastomer. A special shortterm aging technique for silicone rubber is suggested as a substitute for long-term aping.
...............................................................
LOW TEMPERATURE BEEAVIO* OF SILICONE AND ORGANIC RUBBERS
K
Dbw Cmdw
~
~
d
~.c..rr.~ u.a . Midlsnd. Mi&.
~
~
p
l
Y
u
t
i
in^
o
Because of the depletion of our national resources of petroleum and coal, attention is being given to the utilization of chemicals, such as %furaldehyde, which are available from annually recurring agricultursl byproducts. With the current wide utilization of plastic products, the production of low-cost cast plastics from Zfumldehyde %eew dedrable. Previous cast plastics, made in this laboratory by treating Zfuraldehydewith ammonia and condensing with hydrochloric acid, while excellent, had B high msidual acidity and too great a &inkage. The residual acidity baa been eliminated by the use of other condensing agenmits and shrinksge has been d u d by the addition of lignin. The effect on the characteristics of the plastic of various aminea instead of ammonia haa been studied. The plastic sirup canbe made at a low cost from Zfuraldehyde which is produced from m u s U y renewed mw materials. It can be formed by casting in simple inexphsive molds to form a bard, blsck, strung, ahiny, infusible product suitable for many u~e8. CAST PLASTICS FROM Z-FURALDEHYDE O . S . ~ , L . C . ~ n d S . T . ~ Endmeatins Erratimen$ %stion. Io- %e% . college. Ammar. Iowa
.................................................................
1-
SpedaI-Plupae lpoltoda Wood~Rnavalive
There is a definite need for a wood p m t i v e to use on such items as greenhouse lnmber, food cnrtea, and tool handles. To 6l1 these gaps in the wood p m ; ervation field a new praservative, copper Sphenylsalicylate,has been developed. When used on wood in contact with seeds or plants, no phytotoxic hazard is evident. Teste on pears and p e a c h stored in treated wooden crates show no injury to the skin of the fruit and no pickup of copper Sphenylsalicylate in the - p& fruit. T~abon 200 individuals reveal that the preservstive is nonirritating and nonsensitiaing to human skin. Extensive laboratory and field tests &ow copper Sphenylsalicylate to be an effective wood p m senrative wbich SigniIiCsntly prolongs the useful life of wood. i
7
L -
................................................................................
COPPER 8-PHENYLSAIJCYLATE
~ ~ . ~ m n d Y k b b Wood Prasarrrrtion Tabaatory. Eioobemioal ReDIroh Department. The Do- Chamid Co.. Midhnd Mioh.
m y 1952
I N D U S T R I A L A N D E N G I N E ~ R I N GC H E M I S T R Y
im
I499
Ill.karlupnlr(lri.os"--Illuld.
In order to explain the behavior of elastic materials, it is often helpful to substitute a model made up of simple mechanical components, so one esn sw what is happening as well as describe it mathematically. The model is more useful if it can be built and its performance observed. To avoid the difficultiesinvolved in building and bating such a mechanical model, the analogy between electrical and mechanical systems was employed in a devim which permits the assembly ofmodels with electrical components reacting to voltages 1)8 the mechanioal mod& do to forces. Simple linear or nonlinear models can be wambled in a short time and creep curves, s t m t r a i n chsraoteriatics, or dynamic pezformance may then be obtained. The apparatue will be used to study the types of models required to repmduce some of the unusual characteristics of elastomers,and to observe the performance of models undergoing force-time relationships not available for actual rubber t d n g .
............................................................................................
ELECTRICAL A N A L 0 0 METHOD FOR STUDYlNQ ELASTOMER BEHAVIOR
RB.-
O b d v e v Tire?
h Rubbar Co., Akron. Ohio
.lW
This study of isophthalic acid was undertaken because of the lack of detailed literature referenceson ita use in condensation polymers, and also because isophthalic acid, produced by the oxidation of mxylene, is potentislly available in very lasge quantities. Isophthalic acid is an excellent material for use in condensation polymers. Compared to phthalic anhydride in oil-modified alkyd iwh, isophthalic acid show greater reactivity and thermal stability and leas sublimation loss, and forms faster drying and more durable surface coatings. Compared to terephthalic acid in linear polyester and polyamide high polymers, isophthalic acid pmducea lower melting point resins with excellent toughnea and tensile strength characteristics. Isophthalic acid is a dibasic acid that should develop great commercial importance as a raw material for the production of plastic and surface coatings resins.
......................................................................................
ISOPHTHALIC ACID I N CONDENSATION POLYMER0
r.a.hmdm.~.aad,hm
Cdifornia Resesrch Gorp.. Riohmond. Calif.
1115
For saouring adhesion of rubber to steel, a number of generally satisfactory one- or two-coat organic cementa m e available. However, where a high-strength durable bond is required as in motor mounts, much of the industry has continued bo rely on the combination of b r w plate and adhesive. The presant investigation has been concerned with the development of a one-cost replacement for the brass-plate system. Investigation of a new series of diene-unsaturated acid copolymers has shown them to possess exceptionally high adhesion to rubber and steel. Major attention has been directed to the bubdienernetbacrylic acid copolymers, although similar products have been obtained, for example, from butadiene and acrylic acid or isoprene and methacrylic acid. Polymerbation is conducted in an emulsion system employing a sodium alkyl aryl polyether sulfate dispersipg agent and pota98ium persulfate 84 the initiator. Cumene hydroperoxide is an dective curing agent. unique adhesive properties which suggest a variety The butndiene-methacrylic acid copolymers of practical applications. It is believed that the high-strength bond results from hydrogen bonding between the carboxyl groups and the oxide a m on the steel and from the ability of the unsaturated part of the molecule to vulcanize to the rubber; metallic oxides in the stock probably also contribute to the strength of the rubber-cement bond.
..........................................................
BCTADIENE-METAACRVLIC ACID COPOLYMERS Q~I.,C.~.IL a.,.-.iau .-i.~uhr A p ~ l r e d8oienco Rm -' amh L.boraf&. C n i ~ n i t yof C i o m s t i . b a i n n a t i , Ohio
Phnollm Coxupomdm C a m Coku L.t.blllty
Mercaptsn oxidation catalyzed by copper chloride is widely used by the petroleum industry for improvkemeenes. When h i g h e r - b o i *in distillaks-zspecially thhse from high-sulfur crudtreated by thii process, the products are likely to develop color. Study of the musea underlying the induced color instability showed that trace constituentsof the oil are responsible. To identify the undesirable components of virgin distillates, polar constituents were isolated by extraction and adsorption techniques Theae materials, as well as pure compounds, were then added to a bsse oil that was mbeaquently sweetened, and accelerated aging tests wers used to determine color stabdity. ing the odor of straight-run gasolines and
1900
INDUSTRIAL A N D dNQINEERING CHEMISTRY
Vol. 4 4 Na. 1
,
I
,,':.:?
I
I
This work waa done in both batch and continuous apparatus; data obtained in the latter, a glaas benchscale unit, correlate well with plant-sc.de results. The principsl dendem are phenolic compounds, mono- and polybydricphenols of l o molecular ~ weight beiog especially harmful. Amimes have an intermediste e6ect on color stability. D d d m and mturated cyclic sulfides are essentiily innocuous. Trace amounts of oilisoluble copper compounds, resulting from reaction of copper chloridewith polar constituents, catalyze the formaticm of color in the mveetened products: thie catalytic efiect can be suppressed by washing with bssic solutions or bot water. Some sweetening catalysts containing copper salts, such as the sulfate and fluoride, give color-stable products but are leas active than copper chloride and q u i r e bigher temperatures to d e c t sweetening.
-
.........................................................................
COLOR FVRMATION IN COPPER CBWRIDE-SWEETENED DIBTILLAT88 1.oLa.Xr-d
a. h
Reamoh Dspnrnent. Standud Oil Co. (ladha). Whitins. I n d
lru
?
-8-
The increasing use of dieatma as lubricants accentuates the need for fundamental information as to the relation of oxidation stability to structure. Representative diester-type fluids were studied in an oxygen consumption apparatus. Reaction rates were found to be a square-mot function of oxygen absorbed. Activation energies calculated from the Arrbenius equation varied from 20 to 30 k g . 4 . Peroxide concentration increased with time to a maximum and then d e c d . It waa demonstrated that at all times peroxide concentration was proportional to the instantgneous d o n rate. The liquid phase oxidation of diesters is autocatalytic. The experimental actidion energy could be related to the free energy of activation, thus ma!fii it possible to rank the diesters as to stsbity. Tertiary C H groups, normally susceptible to oxidation, could be partially stabiliaed when shielded by neighbor& substituent groups. This information should be useful in the development of more stahle dieatma.
...............................................................................
OXIDATION CHARACTERISTICS OB SOME DIESTER FLUIDS c. K m y U l w-. N S S ~k u o h ~ ~ b o nwt ~ ~ . as. D. c.
.I(n
The autoignition properties of a number of D i d fuels were studied at a b pheric p m u r e using both a single-cell chamber and the three-cell Jen-h ignition apparatus with suitablemodifications. curve^ were obtained which e x p r e s s e d the mnw of positive ignition, eo01 flame,and'nonignition in termsof tempersture 8 and oxygen coneantration. The ignition curves for the several fuels studied are similar in shape, but are displaced toward lower temperature and oxygen concentration with increase in cetane number. Ignition rmryes with the s i n g l d l chamber when c o m p d with curves obtained with the Jentmch chsmber were found to be displaced to conditions of lower temperature and oxygen concentration with the inkction points more pronounced. Cool h m e s were observed over a wide range of temperature at low oxygen concentrations. Under certain conditions, suceessive cool flames are pmduced fromone dmp of fuel. 6addition to visual observation, the occurrenceof eo01 flames waa also determined by the responsa shown by a thermocouple suspended in the ignition chamber. The ignition delay was found to be independent of the type of ignition and much more dependent on temperature tban on oxygen concentration.
u
AUTOIONITION PROPERTIES OF CERTAIN DIESEL FUELS
I.Ml-
I.Luw.0..UL.rull-w.CUlUlt
N . d B u u e h hbntorr. W u h i n 8 w n 26. D. C.
.......................................................
le11
nrrwuUR d v PbcrdFrrulddyd. A long study of phenol-formaldehyde reactions baa emphasised that resinous
are the usual pmducts of such reactions, and that crystalline compoundsare the exceptions. The known fusiblephenolic resins are characterized by avemge numerical values and by having the pmpertie of m a s s with broad, indefinite melting points. Same resins have been found which have sharp melting points. Data of thia series have been basic to the production of some of the newer commemial phenoliq resina. After d e w of some of the known crystalline products obtained from phenol and formaldehyde, c k ~ i f i e dhere 88 phenols, some new tripbenolic chemicals are detailed 88 c r y d d b e products or 88 regins purified to a sharp melting point and to a definite structure. Included 88 new c r y d d b e pmducts are the 2,gbia(2hydroxyben)~enol, Z,s-bis(4hy~xyben~I)phenol,2,4bia()phenol, and 2,4b~(4-bydmxybensyI)phenol. 1952
INDUSTRIAL A N D ENGINEERING CHEMISTRY
1601,
Blenda of the men known pmducta of molecular weight 308 am g e n e d y d o u s , and by blending
these strncturee the propertiea of commsmisl phenolic resin$can be varied to cover a much wider than has been known previously.
range
........................................
PURIFIED CEEMICALE AND BESINS FUOM PEENOL AND FORMALDEHYDE ILL.A.O r& w RII r II a I,..JT...M I, Bakdita Ca. b.i& d 0-n &bid. u d &&& C&, Blmmbld. N. 3.
bthlutinxmtion mi
€Ie.rz. m9droeubom
Becsuae of the decbing fueloil market, the incrsssed me of marginal type crudes, and the higher crude runs llecessary to satisfy the unpreoedented demand for petroleum products, the refiner, facing an increasing SULID~V of residuum ~ m d ~ afmm t s wtroleum. is forced to find a new outlet for thew ~mducts. A D ~ I o ~ pincnnit vacuum I%& still, capabli of operating at p m s m s an low aa 26 microns, has &Iused in sep&t-” ing and chklacteriaingoverhead petroleum fractionsboiling above thoee produced on conventional topping and vacnum sti&. Bome such mema must be lesorted to in order to asoertsin the most economical disposition of thw heavy hydrocsrbon fractions. The d t s of this work, presented in the form of a aeries of c m and charta, illustrate the nee of well-known ohamterizationtestg and their application in pointing the way toward better utilization of petroleum residunma Flash data am presented for four topped cruden-Venemelan, Panhandle, weatern Texas, and western Iiansa. From carbon residue studies, it waa found that Panbandle crude di5ers materially in composition from that of the others. API gravity data on vacuum midunma led to pmdictions that good penetration asphslt could be made by a vacnum separation of Weat Iiansa crude, while Panhandle crude would be a good paraffinic cracking stock. This work w m to emphasize the potentialitiea of petroleum residunma which in eome instgnoes may be unrecognised sourcea of cracking feed h k , chemicals, and many rrpecialty pmduete.
................................................................................
CHARACTERIZA’ION OF PETROLEUM W D U U M S BY VACUUM FLASEINQ .ulEI.L..rdLL. 1, -.rob Divhiom, WllUm Ru -m CO.. Butlarllla O h
IQI
A l r ~ & . t ~ P y r l d b
In the fats of a national ehortspe and a diminishing supply of pyridine and quinoline, almost l,soO,ooO pounds of ni&n and n i s c i were p d u d in 1950. More readily available raw materials can be condensed e5ciently to p m d w alkyl pyridines, and these in turn can be oxidized to niacin. A oompect apparatus w88 designed for labor?tory scale study of catslytic gasphase oxidations of the alkyl pyridines in the presence and absence of ammonia. &Picoline, oxidixed over a vanadium catalyst with air, yields 17% niacin; with ammonia, trace amounte of nicotine-nitrate; and with air and ammonia combined, 6% nicotinonitzile. The method d e s c n i may also be used for the production of isonicotinic acid, the basic intermediate for the manufacture of the new antieuberouloeisdrugs, the isonicotinic acid hydrazides.
....................................
REACTIONS OF ALKYL PYRIDINES WlTE AIU AND AMMONIA IN TEE VAPOR PEASE %no& 4 h h V . M e%.nke”, N: Y.
!2ziRx2&-~%b~
Ion
~ . ( * u u t l a l . t a l
Pmvioun work haa shown the tensile strengths of unoompounded and compounded synthetic Type I11 latex films to be the =me when calculate3 on the basis of cms%-aectional area at break. The aim of this study WBS to extend the measurementsto other synthetic laticesand to natural rubber Istex. Two aynthetio lati-, Tspes V and X-370,were found to behave aa did the Type 111latex. However, the tendm at b d found for compounded and cured natural latex films were three timea higher than the corresponding uncompounded ones. In all the same compoundw formula, originally developd for natural latex, WBS employed. Them results suggest either that the synthetic latices invwtigated an,not reinforeed on compounding and curing, or that the compounding formula used, while mitable for natural latex, w88 not satiafaetory for producing reintorcement in synthetic latices. If the latter be true, then more resesro6 on compounding of synthetic latices is r e q d to obtain the optimum film propartias of such materials.
................................................................
ULTIMATE AND ACTUAL TENSILE STRENGTHS OF LATEX FILMS s &ymr B.P y..nrR ..I. C.; Iditad d &.do& C l o d a n d 6. Ohio
INDUSTRIAL A N D ENGINEERING CHEMISTRY
...I U I Vd. 44 No. 1
Bcikfs W a k n aamm8 oi naval Strr
he supply of southern hp*%ond, -which is the p m n t s o m of immm i a l steamdidled wood turpentine,is Uiining. Millions of m w of westem pondema pine stumps are an untapped potential source for commercial pmductiou and intereat in western pines- a sourceof naval storeshas recently bean I.I.II revived. The composition of the turpentine obtainable by acetone exhotion of ntumpwood and lumtmr from ponderosa pine has been dete-. The two turpentiwa m very similar to each other, but are Merent from all premnt commercial turpentines. The chief component is A'-CaIene (70%). Other components include =pinene (8%), @-pinene (a%), and myrcene (8%). Compounds present in still &r proportion include camphene, ~terpinene,Limonene, terpinolene, pcymene, and bensaldehyde. Inrwmuch ae n*-~a~ene is completely abeent fmm dl commercial Ameriean turpentines,pondemu turpentine m o t be regarded ae a simple replacement. The presem of &dieant amounts of myrcsne is notevorthy, ae this is the 6rat time myrcene, or in fact any brsncbed-chsin MJrclic hydrocarbon, has heen reported to be present in turpentine from pines.
__I
This work WBB undertaken to determine the extent of adsorption of detergents on cloth, ease of rinsing, and &ect of adsorption on soil removal in the wsshing process. Carbon 14 and sulfur 36 were used as tracers to aid in the measwemat of adeorbed material. h r p t i o n of sodium alkyl sryl d o n a t e and sodium palmitate wae u p prechble enough to deplete seriousfy the concentration of detergent in w a a h i solutions. IncressiOg temperatwe increased the rate but decreased the magnitude of adsorption. Desorption of sulfonate was more complete in W e d tban in hard water, but desorption of palmitate was grater in hard water. Wool adeorbed more palmitate and d o n a t e than cotton and retained them more tensJonsly on rinsing. Them appears to be no simple relatiomhip between adsorption and detergency. A rapid, convenient method for direct measurement of adsorption on cloth was developed. The results should be of inter& to soap and detergent manufacturers in fonhating detergent blend, to launderera in dculating consumptipn of detergenta, and to textile chin studies of behavior of cottou and wool with anionic &ace active agents.
-
.........................................
ADBORPTION IN TEE DETERQENT PROCa88 lMLv L. A.rllN Resear& orp., Riohmond. Calif.
-,p,d
............................
I U
DLIilLabr-Dlt. Inveatigstions on the exact natwe of the'complex vapor p m w function between the triple and o r i t i 4 points for the normal saturated hydroaurbons have been carried out for the establiiment of coafficients for the vapor pressunt equation developed by Frost and Kukwarf: log P = A B/T Clog T DP/T? A comprehensivetreatment of vapor pressure data found in the literature for the n o m 1 hydrocarbons up to and including n-dodecane has made the evaluation of these coefficientspossible. Thee coefficienta in turn oau be corralated with the normal b o i i i point of each hydrocarbon. Although the studies have heen restricted to the normal m t m t e d hydrocarbons, it is reasonable to expect that similisr correlations can he developed for the isomeric, olefinic, diolehic, mphthenic, and aromatio hydrocarbons. This information should 6nd extensive applioation and interest in the fields of hydrocarbon resesrch and particularly to proceases aaaoohted with distibtiou of hydrocsrbons.
+
-..
+
............................................................................. Iu.
VAPOR PRE8EUREB OF THE LIOHT NORMAL SATURATED BYDROCABBONB
-E.
North-@=*=Mh
PbttL.W -
+
Ute, Emmbr,.
IHI
Data
Among the data most used by the chemist and the chemical engineer are solubilitiesof solids in liquide and the distribution of solids and liquids between other liquids. Often such &ta rnentirely unrelsted and the expressiOns for their representation are simply empirid curves of solubilities w. temperature. The simple method previously used for correlating vapor p m u m and vapor compositions and many other Jdy lSS2
INDUSTRIAL AND ENGINEEBING CHBYISTBY
physical and chemical properties was tried to determine whether these could be used in thii reference s u b stance plot with a temperature scale based on the vapor preasure of the reference substance. It haa been found for all sy%tems plotted that the solubilitiesof organic and inorganic solida may be so represented on a standard sheet of logarithmic paper to give straight lines against a tempmture scale which is calibrated gn the X ax& from the vapor pressure of the reference substance. The slopes of the lines am the ratio of the heat efiecta of solution and the latent beat of vaporizatiou of the referenceliquid. A sharp break in the line shows transition points of the solid which might o t h e d be unrewgnked if working with solubility cnrves. A simple but baaic thermcdynamic background s u b t a n t i a h the methcd. This direct, simple, and thermodynamicallyc o m t plot allows the prediction of data for wbicb e x p i menta are not available through extrapolationand interpolation. It also is useful in codsting exprimentel data. k n a e of the aimplioity of the char&e,.-i straight lines-ple nomogram fer solubilities may ale0 readily be constructed, by methods previoudy used.
....................................................................
COBRELATINO SOLUBILITY AND DIBTRIBUTION COEFFICIENT DATA -P. 0tLmr.l. Y.Ld 8. Tuu Pdyteshnio Iwtituta of Bmoklyn. B m o k 1. N. Y.
..I884
t--mY
1
Although pine wood lignin haa found wide acceptanceaa a s t a b i k for slowbregk asphalt emulsions, very little waa known of its compatibility with asphalta from widely diflering crudes or the amounta needed to prepare satisfactory emulsim fmm them. Nor waa it known if any codation existed between crude s o w ,prooeesing variables, or asphalt properties and the eaae of emulsificationof the aapbalt. Therefore 17 aapbalta from widely ditiering crudes were emulsified, using alksli lignin 88 the stabilizer. The l i i n waa found to be compatible in every case. Satisfactory slow-break emulsions were made using resin acid soap as the emulsifier, and the formnlaa used am presented. No codation could be found between crude mnrce or asphalt properties and the ease with which they emuhilied. Data on proceesing variables were not available for comparison. Formulas and test results aa well aa some aephalt properties and crude sourea am given as a guide to further emulsification8tudies.
i
I
...............................................................................................
ALEALI LIGNIN TO STABILIZE SLOW-BREAK ASPHALT EMUL8IONS
w*A.-
Denlopmena Deprtmant. Wsst V i a Pulp & Psw? CO.. Chulaton. 8. C.
lM
,I
8terhb~tlorAfhot.Aa~tpo(.a~
Further investigation waa undertaken on the akylmemapto ketones, in order to investigate more fully the effect of various structural featurea on potency aa antioxidants. The results of the present investigation tend to support the conclusions previously reached: that mme special sterio configurationis nexxmary for antioxidant potency. The unexpected antioxidant ~ ~ p r i ority of the s-alkylmercapto ketones when compared to the analogous alpha, gamma, and delta compounda along witb other data demonstmtea this point. Additional features that lead to high antioxidant potency in alkylmercapto ketones have been pointed out and a more specific formulation to explain the antioxidant properties of the 8-alkylmercapto ketones has been advanced.
............................................................
SULFUR COMPOUNDS AS ANTIOXIDANTS R. B. T b m y , 1. A. c l h d d , l.'d,-:... h u o h an Dawlopment Labonton-. U n w e d Od ProduoU Co.. Riveraide. IU.
.18W
I,
Pine QnmDaivaUve u bd&.
This study waa undertaken in order to evaluate the polymer formed when sodium ethylmaleopimarate is substituted for the disproportionatedmsin soap in the G R S l O recipe. The physical properties of the vulcanizatea were comparable to thoae obtgmed using a commercially available disproportionatedmsin soap and the chemical stability of the latiees formed with the experimental soap appeared to be greater than that of the latiees with the conventional soap. The inhibiting efiect of conjugate3 double bonds on the polymerisation of G R S was succeasfullydinated in a rceinderived soap by the DielsAlder addition of maleic anhydride. This procedure, wbich is more selective than hydrogenation, could be applied to other pmducta containing this type of unsaturation. ETHYL MALEOPIMARIC SOAP IN a m POLYMERIZATIONS mltrP.uI r . L . y o ~ , ~ R . v . L . - ~ Uni-tu ef ASren. A h a . Ohio.and 8mtban asnioad Raarsh Iabontorn New Orl-,
.................................................... La.
'1604
IRDUSTRIAL AND ENGINEERING CHEMISTRY
........lnr Vol. 44 No. 1
Wriefs P l u o r i a a t a d H ~ b o a ~
Vapor-liquid equilibria were determined for five binary fluorinated hydmmfh 8 p h U to provide fnndrunental engineering information. The sptems studied included: CFaCl, CFfil,; CFJICI, C F A F C F x ; CFBCl, cyclic CPa; CFfils, CF,--CFCFa; and CFfil,, cyclic C,F* Anslysea were made, for the most part, by determining the vapol: density of the samples. The maas spectrometerwaa used to d y z a the & e m CFICL, CFs==ClWF+ The Van Laar equations gave a fitof the experimentaldata within the limits of the analytm Two positive wotropes, CF,HCI, C F 4 F C F I and CFfiI, CFf==CFCF& m m diecavered. The vapor pressure C ~ of B C F 4 F C F I and cyclic C P Swere also determined. The results obtained are interesting from both the theoretical and the practical viewpoint. No p u b Lished data are available on vapor-liquid equilibria for highly fluorinated &ems. These data can he used in practical engineering operetions and am of interest with regard to the theory of vapor-Squid equilibria and the formation of seeotropes.
r(
=:+oF.e-.............................................................................................
VAPOR-LIQUID EQUILIBRIA OF 00ME FLUORINATED FNDROCABBON BYETEMS Nernoum ' .& CO.. Wilmmpton. Del.
s
w.ctir.801-t:
.lW
3-neptanol
In certain industrial hydrocarbon oxidation prowma the products derived from the processes contain alcoholsand acids. The purpose of this work was to evaluate the &wtivenw of 3-heptsnol as a selective mlvent in separating ethyl alcohol from water solutionsand acetic mid from water wlutions. Ternary liquid equilibrium data at 25" C. were determined for the two ~ystems,3-heptanol-watetic acid and 3-heptanol-water-ethyl alcohol. The tie-line data were analysed by three common?y accepted oorrelation methods. These data Bhould be of interest to the chemical industry engeged in the manufactureof o x i d d hydmcarbons in which separation difliculties are encountmd. Depending upon a number of factors, 3-heptanol may or may not be suitable as a solvent for extraction of ethyl alcoholor acetic acid from aquww eolutions. TERNARY LIQUID 0Y0TEM0 h . ,d . a n U & ~ & , Alutm. Tor
vu
-.
..................................................................
lea
II.tlucnJltuu9.owsywtem at 100 P.
A knowledge of the phase behavior of ternary hydrocarbon mixtmw ad& m a W l y to the experimantal background upon which the &ective prediction of the thwmodynamic properties of complex hydrocarbon m i x t m can be based. At present the fund of such knowledge ia inadequate for accmatepredictions covering the properties of complex mixhues of lighter hydrocarbons under many conditions found in practice. The d t a of a study of the phase behavior of the methane-wbutandecane system at 40' F. are reported and represent the completion of a rather extended study of this ternary system. From these data and earlier experimentalinvdiations , the critical p"8ure (see cut) and temperature were estimatedfor a wide range of compositions. These d t s ipdicate rather Simple systematic changea in these properties with change! in composition. The present study eatends the range of tempraturea at which the phase behavior of the methane-nbutane-decane system is known. The addition c,f,information nt a fourth temperature ai& in indicating more sdequately the deet of tempatvre upon t4e compositionof the cuexisting pbasea and upon the values of the critical preesure and composition. Such doQ, now available from 40' to at least 340' F., are useful in determining the applicnbility of prediction uas to the estimation of the properties of the phases of more complex hydrocarbon mixtures of specificis&& in the petroleum industry.
P
..................................................................
PHASE EQUILIBRIA I N HYDROCARBON 0YSTEMS
a.a.-+
8.a.h
udW.W.L.~..... h a d e n s 4, Calif
California Instltuta 01 T&OIOW,
1 ~ 1
N,E-R,O Vapr Rarue Data Extendd
This vapr premre study was carried out to secure data whieh migbt serve as the basis for designing equipment for the concenhtion of aqueous hydrazine solutions. The data obtained include vapor premre-compositiou curves and q/diegrams coyering the sub atmospheric range from approximately 125 to 700 mm. of mercury. The existence of a hy&&e-vater areotrope is again demonstrated and the close similarity of the c m ab dl pmssmw is noted. Id9 Is52
INDUSTRIAL AND ENGINEERING GHEYISTBY
aplls
The data preaented in this investigation BIB the first extensive ones to he published over the range md. They should be helpful in the degign of equipment and the development of procem for the msniplllation of aqueous hydrasine solutions.
...............................................................................................
VAPOR PRE@SURE-COMPOSITION MEBUREMENT8 ON AQUEOUS HYDRAZINE 80LUTION8 I a BI.~.. Cdwe d St. ThoSt. P d . Minn.
.
CYOlllgEElNO AND pPOCES# D
W
.im
I
~ ~ l r o l s S I I n . . r w l r
The author bas combined his knowledge of 12 year's industrial experience with data previously prsepted to describe, for the first t i ,the modern industrial acetone-butanol fermentation of sugarsand some of,the problems involved in the process. blation and hsndling of cultures, plant operations and equipment, yields of products obtained. conditions of the p,and contamination problems are discussed in detail. The type of information presented should be valuable to teachers of bacteriology, biology, chemistry, and chemical engineering and to anyone interasted in the field of fermentation.
............................................................................................ 0. N. Y.
ACETONEBUTANOL FERMENTATION OF SUQARB
-aC
h P5er C Ca ho. B-kbm
~rn
-
Dye 'Uh.mi&'
d llor
.
The literature contains almost no relible information on the spread of initial stable turbulence in t u b . Dye studied were undertaken, therefore, to Bstablish the visual chamte*cs of l a b - t u r b u l e n t transition in t u b having a practical level of disturbance at their entrance. Initial turbulence was obse~edin the exact,cente.r of the fluid atreamat flow rates approximately half lls peat lls t h m reported by inveatigatom of fluid friction. The turbulent core expanded with i n c h flow at a rate which was dependent on a characteristic velocity at the core boundary. In the turbulent portion of the stream, spiral eddied were obe8rved which were amplified by i n c h flow untd disturbance eddied were cset 05 at about 2100 Raynolds number. The disturbance eddies became more stable a8 full turbulent conditions were approached. The preaeplt data BIB of basic signi6cance to the prediction of h a t and maea transfar rates in process equipment operated in the transition flow range. Examplea arc short tubular heat exehangers or those hsndlingfluidsof high viscosiey. The reaults al#o begr directly on the general problem of turhulent momentum exchange.
.
...............................................................................
=
LAMINAETURBULENT TRANSITION I N SMOOTH TUBE8 -& 1.s. nudg.. Ckme& Imtituts of T a o b r d w . P i t t e b d . P r
I
U
I
Q
E
O
d
~
h
L
~
~
..IW
~
The purpoee of the present work wlls to develop meana of producing polymers of datively high molecu. Isr weight fromd y available olefinssuch lls propylene and 1-butene. E t hbeeufoudpssible to polymerize the m o n d ~ l e t h y to h producta of datively high molecular might by proper choice of catalyst, promoter, and other d o n conditions. Them conditions mditierent from thcae which have been used to obtain high molecular weight polyiaobutylene. S ~ o s l l yit, is found e t i a l to use a promoted aluminum bromide catalyst with a high promoter concentration,and a low o l e h feed rate,and to operate within a tempersturn range-c ' ic of the monomer. In the continuous poly-
meriaation of l-butane a maximum molermlsr weight hobtgied at -3.5' C. The polymer products made available fromthis work are useful 88 additives or blendhg agents to impmpe the viemeily index of lubricating oils.
.- Oil................................................................... Ca. Ino.. Paulabom, N.J.
POLYXERIWTION am-tuqa&-OF MONOALKYLETHYLENE8 U.LI
10
Bwooy-Vmum hbontona. &w-V.ooum
N%P b a d meld
lW6
In a aeamh for a prsatical method of maldng phenol, the cablytic d e h y d m t i m of cyclobexaool and cyclohexaoonewasstudied. The most sstkfaetory catslyeta found were made from nickel, copper, chromium, and alkali metal INDUSTRIAL AND ENQINEERING CHEMISTRY vd. 44 No. 7
griefs. sulfate, supported on an inert carrier. With these catelystsbfWoC. phenol yialds better than 86% were maintained during operatiug periods of well over 100 horn. Catalysts that had begun to kea theEr .otiviqY were fdly regenerated by oxidation and reduction; no permaaeat I& of actiVity WBB obmrved in mverfd months' operation. The catalystswen? found to be equally adaptable to the dehydmgenation of substituted hydmammatios to the correeponding phenols. The phenol produced over these catalyata can be m o d by simple distillatian; this ie @ble only when very high yields are obtained, becsuse of formation of an aseotmp.9 with o y d o h o n e containing about 76% phenol. Together with a cyclohexane oxidation p,tbb metbod &era a prsctioal mute to phenol production.
-
.................................................. W. V L
PEENOLB BY DEEYDROOENATION IL a CLH..CI. z . y a w.-,ds.t.Raamb .nd Davdopmnt eprtm-t, &bide .ad Carbon CbarmOJ. Co.. b u l b
*box
I-
Dedqa Data
The purpose of this inve8tigation waa twofold: to determine the &eat ofintraparticle daiustOn in moving bed adsorption systems, with the idea of placing the deeign of such adsorberson a rational baeis; and to investigate one of the possible ratedetennining step in the adsorption of a solute from a solution. The effect of intraparticle ditIusion in the phenol-water-mbonsy6tem waa choeen. For cylindrical carbon pllrtielesusing the phenol-water systam the experimental data codd be fitted almost exactly to a set of theoretical equations derived on the baais that ditTu6ion inside the partial& wea the controlling factor. In the study that ditiusioninside the particles waa the controlling lactor. In the dndy of moving bed adsorption systems, formulae for two simple CBB~S,linear equilibrium and hear betias, have heen derived. The design of an adsorber will depend criticaUy on the value of the difiu%ivity,and the results obtained seem to indicate that experimental determinstion of ditTu6ivitiesin pomns madia is For the design of adsorption equipment it is essential to know the ratesat which adeorpdion taLes place. This phenomenon is complicated by the many possible rate pmnocessas which may be taking place hdtmeously and successively. This paper throws some light on two of th-inbpartiiole ditiusion and m%sstnu3b fer at the partisle d a c e . I n the design of adsorhem inbpartide ditTnsi0~1annot bepaegleoted; rlesigw neglecting either d W o n or m&$8 transfer will he underdesigned. The um of an over-all &el%ent might b dangerous in such a ease.
v.
.....................................................
INTRAPARTICLE DIFFUSION IN ADSORPTION BYSTEM8 MJ -w x. .u(r w d a. ku~.r UniwkW of Mi-. ,~Iinnesx&, ?+I.
......
/
im
.
HydmIy& of mixed hardwood chip to sugars and the conceutmtionof resultant sugar solutions to m o k for animal feeding were investiigsted through operation of a pilot plant that had a capacity of about 1.4 tons of dry-wood subBtssce per batch. The pilot plant equipment included (a) a wood hog for chipping of cordwood; (21) a Monel digester in which the wood chips were hydrolyzed with I I dilute sulfuricacid at high temperature and pressure; (c) neutralieig tanks in which the dilute sugar solutions were neutralisgi with either l i e or limestone and the slurrieswere settled; (d) a submerged combustion evaporator to concentrate the dilute sugar solution to 25% m o k ; and (e) a vacuum evaporator for further eoncentration of the 25% m o b mesto a reducing sugar content of about 45 to 50%. h a 1departures from the M a d i n wood sugar p r o m were tested in the c o r n of pilot plant operation, and several operating difficultieswere identified and resolved. The &eat on the time of hydrolysis, on the yield and concentrationof reducing sugars, and on the operability of the pilot plant of the following variations in procedure and pmeess variables were evaluated: temperature and dnration of a holding perid; uee of a recyeli pmedure; tii&mperatum Behedule and maximum temperature of percolation; rate of percolation; and acid concentration. In a p r o m based on the pilot plant resnltq hardwood chip can he converted to molasses with a net yield of 1470 pounds of 50% molasses (125 gaUom) per ton of dry-wood s n b h c e . An investment and production & estimSte is preeented for a plant to w e 50 tons of dry-wood subetgnce per day for a Memphis, Tm.,location,and the cost of production of molasses is compared with market price of blackdmp m o b aud of corn.
.,
EYDROLYSIB OF WOOD UBlNO DILUTE BULPURIC ACID Ia(*L.1,1.A.4J.D.-
mm-
w
VSIISY
hb~ ~, . mA I .. .
AU~~OAW,
.................................................................
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1YU
1Wl
