J . M . H A R R IS O N A N D L L O Y D BERG Gulf Research & Developm ent Company, Pittsburgh, Pa.
A n u m b e r o f c lo s e -b o ilin g b in a ry h y d r o ca rb o n sy ste m s
P
RECISION fractionation of petroleum demands a thorough knowledge of the behavior of the constituent hydrocarbons upon distillation. The constantly increasing demand for pure hydrocarbons makes it necessary that vapor-liquid equilibrium data for such systems be known. Furthermore, present-day methods of design calculation for handling nonideal systems indicate that, with the determination of more vapor-liquid equilib
rium data, it will be possible to design equipment for azeotropic and extractive operations with as much precision as is now obtain
able for the distillation of regular mixtures.
Various hydrocarbon types have been discussed and their data tabulated (S, 4, 7, 0), but the number of binary hydrocarbon systems for which equilibrium data are known remains relatively small. The difficulty or impossibility of obtaining certain close- boiling pure hydrocarbons will of necessity limit the extent of an investigation designed to secure desirable distillation data.
There are some hydrocarbons, however, which are obtainable in the pure state and for which there is no published information concerning distillation behavior. Some of these compounds have been investigated and are reported in this paper. Included are the following close-boiling systems: 2,2,3-trimethylbutane- cyclohexane, 2,2,3-trimethylbutane-benzene, benzene-cyclohex
ene, 2,2,4-trimethylpentane-methylcyclohexane, and cyclohex- ane-cyclohexene.
Each of the hydrocarbons was purified by _____________
refractionation in a glass laboratory column 4 feet long, 1 inch in diameter, and packed with Vi-inch stainless steel carding teeth, calibrating about forty theoretical plates at total reflux. With a reflux ratio of 25 to 1, a heart cut was made of each hydrocarbon; the properties are shown in Table I as compared to values from the literature.
The vapor-liquid equilibrium data were ob
tained in a modification of the apparatus de
scribed by Othmer (6). A 50-ml. sample of one hydrocarbon was charged to the still, and mixtures with various successive additions of the other hydrocarbon were allowed about 2 hours to reach equilibrium. Vapor and liquid samples were removed, and their com
positions were determined by refractive index in a Valentine refractometer, reading to
0.0001. Refractive indices were obtained on weighed mixtures of the hydrocarbons so that mole fractions of the samples could be read from a refractive index-composition curve for each sys
tem. The vapor temperature in the still was determined by a calibrated 75-mm., immersion precision thermometer accurate to 0.1° C.
A Z E O T R O P I C S Y S T E M S
The experimental and calculated data for the 2,2,3-trimethyl
butane-benzene system are shown in Table II. An azeotrope is formed at 75.6° C. at 736 mm. (76.6° C. at 760 mm.) and con
tains 56.7 mole % aromatic. The equilibrium diagram is illus
trated in Figure 1; the temperature-composition curve (tempera
ture corrected to 760 mm.) is given in Figure 2. Figure 3. is a plot of the relative volatility as calculated from the data. The consistency of the data is shown to be satisfactory upon inspec
tion of the activity coefficient curves of Figure 4, as suggested by Carlson and Colburn (1). The equations of Smith (8) which were used to obtain the vapor pressures of the pure hydrocarbons at various temperatures were:
118 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 38, No. 1
2,2,3-Trimethylbutane: logl0 p = 6.7996S2 — 1204.997 226.615 + i Table III contains the data for the 2,2,3-trimethylbutane- cyclohexane system. An azeotrope is formed between these two hydrocarbons at 79.45° C. at 744 mm. (80.15° C. at 760 mm.) and contains 47.8 mole % paraffin. The vapor-liquid equilibrium diagram, the temperature-composition diagram, the relative vola
Figure 1 (L eft and Above). Equilibrium Diagrams The following vapor pressure equations for cyclohexane and cyclohexene, derived from data obtained in this laboratory, jrere used for the pressure range of this investigation:
Cyclohexane: logi0 p = 7.13289 1505.15 273.18 + f Cyclohexene: log10 p = 7.09845
-¿ t o. l o t
Data for benzene-cyclohexene system are presented in Table IV and the equilibrium diagram, relative volatility plot, and ac
tivity coefficient curves are shown in Figures 1, 3, and 4, respec
tively. An azeotrope is formed between these two hydrocarbons at 78.9° C. at 740 mm. (79.8° C. at 760 mm.) and contains 65.7 mole % aromatic. This composition is somewhat lower than that previously reported by Lecat (5).
In order to verify the compositions of the azeotropes, three samples of each system were run in a Podbielniak Heli-Grid column at a reflux ratio of about 200 to 1. A sample correspond
ing to a composition slightly below the approximate azeotrope and then a sample with a composition just above the azeotrope were run in the column. A small overhead sample was removed from each distillation and analyzed by refractive index. The change in composition between the charge and the overhead was plotted against the charge composition. A straight line connect
ing these two points indicated the azeotropic composition at the line of zero composition change. A third sample was then made up to the indicated composition and charged to the column. An
RELATIVEVOLATILITY
overhead of the same composition as the charge proved the existence of the azeotrope at the given composition.
The assumption of a straight-line relation for hydrocarbons appears to be valid, provided the total range of composition change is not greater than 6-10%. Table V contains the data from the distillations which establish the azeotropes between 2,2,3-trimethyIbutanc and benzene, 2,2,3-trimethylbutane and cyclohexane, and benzene and cyclohexene. Figure 5 illustrates the method of locating the true com
position of the azeotrope between 2,2,3-trimethylbutane and cyclohexane.
Ta b l e III. Da t a f o r Sy s t e m 2 , 2 , 3 - Tr i m e t h y l r u t a n e- Cy c l o h e x a n e a t 744 Mm.
° C. butan e hexane butane hexane butane hexane butane hexane V ola tility
8 0 .1 1 .0 0 0 0 .0 0 0 1 .0 0 0 0 .0 0 0 744
MOL FRACTION 2 .2 .3 -TRIMETHYLBUTANE IN LIQUID
1 2 0 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 38, No. 9
Mole Fraction in Liquid Mole Fraction in Vapor Temp., 2,2,4-Trimethyl- Methylcy 2,2,4-Trimethyl- Methylcy
Temp"., Mole Fraction in Liquid Mole Fraction in Vapor
° C. Cyclohexane Cyclohexene Cyclohexane Cyclohexen
Data for the systems 2,2,4-trmiethylpentane-methylcyclohex- ane and cyclohexane-cyclohexene are given in Tables VI and VII, respectively, and the equilibrium diagrams are included in Figure 1. No azeotropes were detected in these systems.
The system 2,2,3-trimethylbutane-cyclohexene was investi
gated, but the results were inconclusive. It could not be ascer
tained definitely whether an azeotrope existed although the data seemed to indicate none.
T a b l e V. P O D BIE LN IAK -CO LU M N VER IFICA TION OF AzE OTR OPIC Com po sitio n s
Hydrocarbon Mole Fraction.
Hydrocarbon 1
No. I No. 2 No. Charge Distillate Change
Benzene 2,2,3-Trimethyl- 1 0.532 0.567 + 0.035
butane 2 0.6-15 0.567 -0 .0 4 8
3 0.567 0.567 0.000
2,2,3-Trimethyl- Cyclohexane 1 0.424 0.460 +0.036
butane 2 0.525 0.491 -0 .0 3 4
3 0.478 0.478 0.000
Benzene Cyclohexene 1 0.626 0.657 + 0.031
2 0.69S 0.657 -0 .0 4 1
E v e n t s d u r i n g t h e M o n t h , o f I n t e r e s t t o
processed. ~~Go6drich Chemical acquires ITycar Chemical Co.~'~Civilian Production Administration says supplies of most strategic metals now on market are adequate for industrial needs. ~~Directors of Celanese Corp. and Tubize Rayon sign agreement to merge Tubize into Celanese. ~~Reynolds Metal submits 5-year lease offer to RFC and Surplus Property Administration for government-owned aluminum plant at Hurri
cane Creek and for reduction plant at Jones Mills, A rk.~~C PA again places controls over tin imports.~~Ernest F. Fullam and Albert E. Gessler, Interchemical Corp., at annual meeting of Electron Microscope Society report development of rotating knife that attains speed of 700 miles an hour and simplifies making cross sections of material for electron microscope. Members of American Physical Society propose special international con
ference of United Nations to regulate military use of atomic bomb.~~Development of liquid chemical propellents that give pilotless bombs a speed of 250 miles an hour in 160 feet revealed as one of chemical warfare’s secret projects.
! De c e m b e r 3 . Arthur V. Davis, chairman board of Aluminum Co. of America, says Department of Justice’s aluminum program will destroy growth possibilities of aluminum industry.~~Van- nevar Bush, director Office of Scientific Research and Develop
ment, tells Senate Special Committee on Atomic Energy big powers should make preliminary agreement on control of atomic energy before UNO receives jurisdiction, is not pessimistic, and thinks coming of bomb will stop great wars.
11 De c e m b e r4. Secretary of Commerce Wallace at mass meet- ing in Madison Square Garden says atomic energy constructively applied to raise standard of living for all peoples would do more to eliminate war than any control over atomic bombs. ~ ~ T . S.
Hauschka, biologist Institute for Cancer Research at Lankenau Hospital and associate director Marine Experiment Station at Institute of North Truro, Mass., makes public appeal to J. R.
Oppenheimer and his associates on atomic bomb project to refuse further to develop nuclear energy until international machinery for its control has been set u p .~ ~ R F C discloses plans are almost completed for halting all production of alcohol for butadiene and closing down 3 plants converting petroleum into rubber.
Allied Control Council publishes laws designed to smash I. G.
Farben trust forever and to outlaw German military training in any guise. ~ ~ V ictor Chemical Works develops chemical which its president, August Koclis, says will simplify and improve dyeing of nylon and lower its cost.~~Eastman Kodak’s sub
sidiary, Recordak Corp., announces machine which simultane
ously photographs front and back of a document reducing its area by 1000 times on narrow 16-mm. film.
If De c e m b e r 5. Paul Goedrich, research scientist, Rutgers University College of Pharmacy, at meeting of Proprietary' Association of America announces development of new series of
compounds, sulfa-iodines, for external wound treatment.
Socony Vacuum Oil announces new motor oil that will reduce operating costs and prolong engine life of automobiles. ~ ~ Karl T. Compton, president Massachusetts Institute of Tech
nology, in letter to Secretary of War, says Army’s destruction of Japanese cyclotrons was “ an act of utter stupidity” , that largest was used in medical research and none could make bombs.
J. R. Oppenheimer, former director of Los Alamos Laboratories, appearing before Special Senate Committee on Atomic Energy, says cost of atomic bombs compared with battleships is so small that they raise serious problem as to value of capital ships. ~ ~ H. A. Bethe, physicist of Cornell University, testifying before same committee, says atomic bombs of present type or any type now in sight will not produce high enough temperatures to cause nuclear chain reactions either in atmosphere or in water.
f De c e m b e r 6 . Twenty-five more German scientists arrive for special scientific work in U. S .~ ~ S . A. Goudsmit, head of military intelligence mission sent to Germany to learn enemy’s work on atomic energy, tells Special Senate Atomic Energy Committee, German scientists despaired of developing atomic bomb in a century and had abandoned idea of using it in recent war.~~Philip Morrison, former University of Illinois professor, who helped assemble atomic bombs, testifying before same com
mittee tells of totality of destruction in Japan. ~~Crawford H.
Greenwalt of du Pont, speaking at Atomic Energy Panel of NAM’s Congress of American Industry, says solution to engineer
ing problems in converting atomic energy to industrial use is in sight. ~~H arold Vagtborg, president Midwest Research Insti
tute, in report to ACS says scientific research which since 1880 has created 15 major industries and 15,000,000 jobs is developing into a billion-dollar-a-year industry.
If De c e m b e r 7. SPA recommends to Congress that 7 of 13 government-owned magnesium plants be taken out of production.
~ ~ S ta te Department announces meeting of foreign secretaries of U. S., Great Britain, and Soviet Union has been scheduled for Moscow Dec. 15 for exchange of views on atomic energy among other things. ~~Eugene P. Wigner, testifying before Special Senate Atomic Energy Committee, says other nations could find out any “ relevant” secrets of atomic bomb production in about 9 m onths.~~N. Y. ¡Section ACS, representing more than 4000 chemists and chemical engineers, demands nonpolitical control of proposed federal aid to scientific research.
De c e m b e r 8. Admiral King in report reveals marshaling of scientific brains for military purposes long before war began.
De c e m b e r 9. Metro-Goldwyn-Mayer and Hal Wallis Pro
ductions announce plans for immediate production of separate feature-length motion pictures about atomic bomb.~~Ernest O.
Lawrence, cyclotron inventor, says cyclotrons many times as strong as those in use will be ready in 1946.~~University of Rochester says not an employee of the thousands engaged in atomic bomb production in hundreds of plants was^ injured by radiation or kindred phenomena.
121
122 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 38, No. 1 1f De c e m b e r 10. Celanese Corp. acquires new plant at Belvi-
dere, N. J., on which $10,000,000 will be spent. ~ ~ A rm y and Navy Departments announce preparation for joint tests of atomic bombs against warships. ~""Carnegie Endowment for Inter
national Peace sets up committee of inquiry and research on atomic energy.~~Imperial Chemical Industries announces purchase of more than 3500 acres of land in Northeast Yorkshire to develop large-scale production of heavy organic chcmicals.~~
Office of Publication Board, U. S. Department of Commerce, says large number of scientific and industrial reports obtained in Germany and German-occupied countries are available.
1f De c e m b e r 11. Celanese Corp. acquires 1200 acres in N. C.
for construction of cellulose acetate and celanese yarn plant at cost of more than $10 million.""'"-Interagency Policy Committee on Rubber announces that public hearings on rubber require
ments and supply, production costs of natural and synthetic rubber, and related subjects will be held in Washington Jan.
8, 9, and 10.~~R F C offers for sale as war surplus government- owned magnesium plant foundry at North Bergen, N. J . ~ ~ Investigations in DuPont’s rubber laboratory at Deepwater, N. J., supplemented by road tests indicate that neoprene has advantages in vibration-absorbing applications for automobiles,
■'--"'-Goodyear announces development of airplane gasoline tank made of nylon.~~Compulsory licensing, of patents would react against small manufacturer and retard progress of research in drug industry Theodore G. Klumpp, president Winthrop Chem
ical, tells American Pharmaceutical Manufacturers Association,
If De c e m b e r 1 2 . New antimalaria drug, metachloridine, be
lieved to be more effective than either quinine or atabrine, is undergoing field tests, E. II. Northcy, administrative director of Stamford Laboratories, American Cyanamid Co., says in report to North Jersey Section A C S . A l v i n M. Weinberg, chief, theoretical physics section, Clinton Laboratories, Oak Ridge, Tenn., tells Special Senate Committee on Atomic Energy, Navy powered by atomic fuel will travel 1000 ft. under water as fast as today’s surface vessels. ~~Bernard Bernstein, Army’s chief cartel investigator, tells Senate Kilgore Committee I. G. Farben has greater war potential than ever and must be destroyed.
If De c e m b e r 13. Solvay Process announces early construction of research laboratory at Syracuse. """""Liquid Carbonic reveals details of projected $8,500,000 expansion program here and abroad. ~ ~ W h ite House discloses President Truman proposed projected Anny-Navy test of atomic bomb against warships.~~
Ross Gunn, Naval Research Laboratory, at Special Senate Atomic Energy Committee hearing, says atomic power would be of great value for submarines, greatly increasing their under
water operations.
f De c e m b e r 1 4 . Harold C . Urey, at Town Hall Meeting in N. Y., urges postponement of atomic energy production until control over manufacture of atomic bombs is assured.
If De c e m b e r 1 5 . ACS circulates petition among its local sections supporting Magnuson bill dealing with federal support for scientific research and education.
If De c e m b e r 17. B. F. Goodrich installs cold room to test rubber and synthetic rubber compounds at temperatures down to 90° below zero."-""Sun Chemical announces acquisition of Warwick Chemical.
f De c e m b e r 1 8 . SPA forbids sale to Aluminum Co. of America of aluminum metal in any form from which aluminum will be extracted unless sale is approved by SPA and bans Alcoa from purchasing surpluses except with Administrator’s approval.
H. C. Urey, speaking before representatives of 50 national organizations, says atomic bomb dropped midway between N. Y.’s financial district and uptown section would wipe out both areas."-"-John Simpson, University of Chicago scientist engaged in atomic development, says U. S. atomic bomb plants
are working 24 hours a day.~~Monsanto announces new series of plastics from which-street markers or door numbers that glow visibly 6 to 8 hours after exposure to sunlight or other illumi
nation are fashioned. ~ ""H . L. Derby, president American Cyanamid, says $200,000,000 will be spent by chemical industry in next 3 years on plant expansion.
1f De c e m b e r 19. Herbert E. Smith, president U. S. Rubber, predicts rubber industry next year will increase production by 66% as compared with 1939.~~Industry survey conducted by Plastics Materials Manufacturers Association shows more than
$107,000,000 will be spent by 22 manufacturers in next 18 months on new facilities for production of plastics. "-""'Senator Tom Connally announces Senate Foreign Relations Committee will begin hearings Jan. 21 on Anglo-American oil agreement.
De c e m b e r 20. ACS elects W. Albert Noyes, Jr., chairman Chemistry Department, University of Rochester, President for 1947.~~SPA’s report on disposal of plants indicates govern
ment-owned synthetic ammonia war plants could be disposed of so that 250,000 tons of nitrogen could be produced annually.
If De c e m b e r21. General Aniline & Film installs.world’s largest paper-coating machine in Johnson City, N. Y .~ ~ T . G. Monta
gue, president Borden Co., says company plans to spend about
$3,000,000 in 1946 for improvement and replacement. '■""--'Du
Pont announces construction will start in spring on $2,000,000 addition to its Toledo, Ohio, formaldehyde plant.
If De c e m b e r24. Crude rubber reaches U. S. from Far East con
signed to RFC for apportionment.
If De c e m b e r25. S. C. Moody, general manager Calco Chemi
cal Division, American Cyanamid, reveals contracts have been let for construction work on its new Willow Island, W. Va., plant.
If De c e m b e r26. Foreign Ministers of U. S., Great Britain, and Russia agree to ask General Assembly of UNO to turn over to the 11 nations on the Security Council the problem of studying and making recommendations for (a) exchanging basic scientific in
formation for peaceful ends; (b) controlling atomic energy to assure its use only for peaceful ends; (c) eliminating atomic weapons from arsenals of national states, and safeguarding United Nations from violations and evasions of international atomic energy agreements."-""CPA announces special priority assistance to penicillin producers and builders of new plants to increase penicillin output. ~'~Chas. F. Kettering, in charge General Motors research, heads committee of 26 leading Ohio scientists comprising subcommittee of Ohio Postwar Program Commis
sion. "-""'Secretary of Interior Ickes announces liquidation of Petroleum Industry War Council and Foreign Operations Com
mittee. ~~Industrial Rayon enlarges staff to handle plans for new $25,000,000 plant. """"War Department honors 45 research chemists of Princeton University who worked on atomic bomb project."-"-Four corporations and 7 individuals file action in Federal Court to recover $5,500,000 damages for use of patents in development and manufacture of stainless steel.
1f De c e m b e r27. Foreign Ministers of U. S., Great Britain, and Soviet Union reach wide area of agreement on machinery to con
trol atomic bomb. """"Victor Chemical completes plans for elec
tric furnace plant in Florida to make elemental phosphorus."-""
Two hundred scientists including 5 Nobel prize winners offer to cooperate in drafting national science legislation.
U De c e m b e r 2 8 . President Truman assures Congress that atomic secret will be kept until safeguards operate.
*! De c e m b e r 29. International Relations Committee, Ameri
can Association of Scientific Workers, backs Big Three for con
trol of atomic energy.
*,] De c e m b e r 31. Charles L. Parsons retires as Secretary and Business Manager of Am e r i c a n Ch e m i c a l So c i e t y.
January, 1946 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 69
We know . . . and you know, to o . . . that despite the amazing progress that has been made in the development o f refining processes, still further improvements lie ahead.
Our confidence is supported by past achievements . . . the contributions which Universal scientists and technologists have already made, including such processes as thermal cracking, catalytic cracking, polymerization, alkylation, isomerization, hydrogenation, dehydrogenation, and others . . . processes which have resulted in doubling the potential yield o f gasoline from a given volume o f crude.
That is why, in Universal laboratories, research and experi
mentation continue unabated . . . why Universal technolo
gists carry on their relentless search for methods o f providing still greater efficiency and economy in the refining o f petro
leum products. We feel that not only are these improve
ments possible, hut essential in order to keep pace with changing conditions and accelerated demands. It is to this end that we are dedicated and that, we believe, is a factor well worth considering in your plans for the future. Universal builds for today . . . and tomorrow.
u m v e r s r l o n p r o d u c t s l o m p n n v
3 1 0 S . M I C H I G A N A V E N U E C H I C A G O 4, I L LI N O I S , U. S. A.
U N I V E R S A L S E R V I C E P R O T E C T S Y O U R R E F I N E R Y
I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 38, No. 1