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composition is considerable. Only a t approximately 3663 E”. for the component n-tetradecane are all values the same for all compositions, The greatest percentage deviations from mean values for n-tetradecane and 1-hexadecene are found a t the lower extremities of the logarithm K-temperature curves where the naphthalene content of the system is greater. Deviations up to 15% are observed for 1-hexadecene in this region. In compariEon, the curves for naphthalene show greater deviations where the n-tetradecane and 1-hexadecene percentages are greater. Such conclusions would be expected because of the widely differing structure of the aromatic naphthalene as comliared to the paraffin and olefin. I n general, it can be concluded that at a pressure of 200 mm. of mercury absolute:
1. The presence of naphthalene in a n-tetradecane-I -1iesadecene so1ut)ion increases the value of the equilibrium constant for 1-hexadecene. 2. The presence of naphthalene in a n-tetradecane-l-hesadecene solution below 366” F. increases the value of the equilibrium constant for n-tetradecane; above 366” F. the opposite is true. 3, The presence of n-tetradecane in a naphthalene-l-hexadecene solution increases the equilibrium constant value for naphthalene, Comparisons with the Van Winkle generalized chart, ( 1 6 ) for solut,ions of higher niolecular weight paraffins and olefins (Table I X ) show fairly close agreement a t higher temperature values. St lower temperatures, n-here the naphthalene content of the mixture is greater, generalized percentage deviations from the mean values obtained in this work are a t a maximum. In general, the deviations indicate that naphthalene affects the generalized equilibrium constants for n-tetradecane and 1hexadecene according t,o the prior conclusions 1 anti 2. h-OMENCL4TURE
A B
= empirical eonstant
b
= constant in Li and Coull correlation
=
empirical constant
‘2 5
y y
= = = =
Vol. 46, No. 2
absolute temperature mole fraction in liquid phase mole fraction in vapor phase activity coefficient
Subscripts 1 = naphthalene 2 = n-tetradecane 3 = 1-hexadecene LITERATURE CITED
(1) Carlson, €3. C., and Colburn, A. P., IND. ESG. C H m r . , 34, 3819 (1942). (2) Dodge, €3. F., “Chemical Engineering Thermodynamics,” pp. 550-63, Yew York, blcGrar~--HillBook Co., 1944. ( 3 ) Egloff, G., “Physical Constants of Hydrocarbons Polynuclear
Aromatic Hydrocarbons,” A4CSNonograph Series, 1’0:.4, pp. 77-83, New York, Reinhold Publishing Corp., 1947. (4) Fuson, R. C., “-4dvanced Organic Chemistry,” pp, 286-9, S e w York, John Wiley and Sons.Inc., 1950. (5) Griswold, J., and Dinividdie, J. A , , 1h-n. ENG.CHZM.,34, 118891 (1942). (6) Cruse, W.A , , and Sterens, D. R . , “Chemical Technology of Petroleum,’’ pp. 64-5, Ken. York. IIcGraw-Hill Book Co., Inc.,1942. (7) ‘Hildebrand, *J. H., “Solubility of Sonelectrolytes,” ACS N o n c graph aeries, 2nd ed.. pp. 41-9 New York, Reinhold Publishing Corp., 1936. (8) Jones, C . A , , Schoenborn, E. A I , , and Colburn, A. P,, Iso.ENri. CHEM.,35, 666-72 (1943). (9) Jordan, B. J., and Van Winkle, AT,, I b i d . , 43, 2908-12 (1Y51). (IO) Keistler, J. R., and Van Winkle, AI,,Ibid., 44, 622-4 (1952). (11) Kirk, R. E., and Othmer, D. F.. editors, “Encyclopedia of Chemical Technology.” 5’01. 7, p. 605, New York, Inter-
science Encyclopedia. Inc. (1951). (12) Li, T. M., and Coull, J.. S. I n s f . Petroleum, 34, S o . 297. 692.704 (1948). (13) Rasmussen, R. R., and Van Winkle. M., IND. EXG.C H G M 42, , 2131-4 (1950). Stull, D. R., Ibid., 39, 817-50 (1947). (14) (15) T’an Winkle, AI., Petroleiim Refiner, 31, No. 2 , 111-16 (1952). (16) Thite, R. R.. TTans. A m . Inat. Chem. Engrs., 41, 539-54 (1945). (17) Wohl, K,,Ibicl., 42,215-50 (1946). for review LIarch 12, 1963. .kCCEPTED Noiwmber G , 1953, Abstracted from thesis submitted b y S.H. Ward in partial fiilfillment of tf.e requirements ior the degree of doctor of philosophy. Material supplementary to this article has been deposited as Document number 4145 with t h e d D I Auxiliary Publications Project, Photoduplication Service, Library of Congress, Washington 2 5 , D. C. -4 copy may be secured by citing t h e Document number and by remitting S2.50 for photoprints, or $1.73 for 35mm. niicrofil~n. Advance payment is required. Make checks or moncy orders payable to: Chief, Photoduplication Service, Library of Congress. RECEIVED
Clo = naphthalene Clr = n-tetradecane Cie = 1-hexadecrne K = equilibrium conetant in terms of concentration = constant in Li and Coull correlation k P = vapor piessure P r = total pressure
Separation of Oxyge pounds by Water Extrac C. S. CARLSON, P. 1‘. SMITH, JR., AND C. E. MORRELI. Standard Oil Development Cv., Linden, .V. J .
C
OLIPLICSTED aqueous mixture? of organic compounds ai e obtained from such processes as hydrocarbon spthrsis, hydrocarbon oxidation, olefin hydration, and oxonation. Perhaps the most complex mixture is produred b y hydrocarbon synthesis, which has been described (12). A typical analysis of the organic portion of the aqueous phase obtained from hydrogen and carbon monoxide over an iron catalyst is given in Table I. This mixture is obtained as a dilute aqueous solution. Conventional fractional distillation can be employed to produce a concentrate or eeveral fractions consisting primarily of mixtures of aqueous azeotropes. These mixtures represent a major
source of chcmicala, such a” alcohols, aldehydes, ketones, esters, and organic acids. Recovery of theqe materials in a state of marketable purity is very difficult. Some of the problems have already been outlined (6). All the compounds listed in Table I, except acetaldehyde and propionaldehyde, form binary azeotropes with other materials present in the mixture, especially vater. I n addition, tertiary azeotropes ale possible. Consequently, complete purification of many of these chemicals cannot be accomplished by conventional fractional distillation. T o accomplish the isolation of the maximum number of pure
February 1954
INDUSTRIAL A N D ENGINEERING CHEMISTRY
351
carried out in the three stills.
Illustrative data for a charge
TABLEI. OXYGENATED COMPOUNDS FROM HYDROCARBON containing 7 mole % ethyl alcohol, 3 mole % isopropyl alcohol, SYNTHESISOVER ALKALI-PRONOTED IROXCATALYST and 90 mole % water are s h o r n in Table 11. In these runs the (Anhydrous basis) Anhydrous oBoiling Point, C. Neutral organic compounds, 79.4 wt. % 20.2 Acetaldehyde 48.8 Propionaldehyde 56.1 Acetone 57.1 Methyl acetate 64.7 Methanol 75.7 Butyraldehyde 77 . . ..1 Ethyl acetate 78.3 Ethyl alcohol 7 9.6 Methyl ethyl ketone 82.4 Isopropyl alcohol 8 2 .5 tert-Butyl alcohol 97.2 n-Propyl alcohol 99.5 see-Butyl alcohol 102.3 Methyl propyl ketone Valeraldehyde 103.7 108.1 Isobutyl alcohol n-But 1alcohol 118.0 119 to 138 hIixeBpentano1s Higher esters Acids, 20.6 wt. % 118.1 Acetic 141.5 Propionic 163.5 Butyric
wt. % 3.1 4.4 8.0
1.8
1.8 0.4 2.7 40.6 4.3 2.8
