INDUSTRIAL AND ENGINEERING CHEMISTRY
October 1952
TABLE11. DERIVATIVES FROM
SUGARSFOUND IN
HYDROLYZATES
Observed Melting Point, O C. 200-202 201-202 200-2024
c.
Derivative Diphenylhydrazone
Dextrose known Dextrose: from sorgo
Phenylosazone
209-210 206-208 207-209“
204-210 (6,9)
Galactose, known Galactose, from sorgo
Methylphenylhydrazone
187 186-1 87 186-187a
187-191 (4, 6)
Xylose
Cadmium nate
Dextrose known Dextrose: from beets
Phenylosazone
204-207 200-202 200-205a
204-210 (6, 9)
Arabinose known Arabinose: from beets
Diphenylhydrazone
202-203 202-203 202-203”
204 (6)
bromide-xylo-
(characteristic boat-shape crystals)
Galactose known Galactose: from beets
Methylphenylhydrazone
188-189 188-1 89 188-1 89=
Mannose known Mannose’from beets
Phenylhydrazone
188-191 188-191 188-191“
a
Mixed melting point from above derivatives.
identification. The four sugars from the hydrolyzed gum from sorgo were proved to be those identified chromatographically. From the beet gum dextrose, mannose, galactose, and arabinose were identified and proved. None of these sugars was found in the gums prior t o hydrolysis. Both sorgo and beet gum gave indications of having no uronic acids. They were not entirely soluble in boiling water. Thus the alcohol-insoluble material, or materials, might better be called mucilages than gums, since Jones and Smith (IO)indicate that gums contain uronic acids and are water-soluble, but there are mucilages which do not contain uronic acids and are not entirely water-soluble. All the sugars found in this study have also been found in mucilages (IO). Except for some starch in the sorgo it is not known exactly what polysaccharides are present in the gums, nor is the nature of the nonpolysaccharide fraction known. This study shows, however, that the gums interfere in the crystallization of sucrose, that enzymes do reduce the effect somewhat, and that hydrolysis produces simple sugars. It is hoped that knowledge of the specific sugars involved will eventually lead to an enzyme treatc ment effective in increasing boiling rates in beet liquors and that
a better enzyme treatment can be found for sorgo liquors.
Melting Point from Literature,
Sugar Arabinose, known Arabinose, from sorgo
204 (6)
(6)
ACKNOWLEDGMENT
The authors wish to express their thanks to R. M. McCready, Western Regional Research Laboratory] U. S. Department of Agriculture, for guidance in chromatographic analysis; W. Z. Hassid, University of California, for helpful suggestions; H. A Barker, University ol California, for a sample of Torula mmosa used in fermenting out dextrose from the hydrolyzate; and to Harry Gehman, Corn Products Refining Co., for samples of glucuronic acid and glucuronolactone used in the chromatographic analyses.
H E assembly described was developed to permit the filtrat,ion of an alcoholic solution issuing from an autoclave a t a temperature of about 110” C. and a pressure of 30 pounds per square inch. It is also applicable to aqueous solutions under the same conditions. The working up of the reaction product was formerly delayed by some hours as the solids, which had to be filtered first, could be removed only after the whole charge had cooled to about 70” C. The autoclave, like many experimental autoclaves of small size (4liters), was,not equipped with a cooling coil. It had t o be 1
Present address, 27 Tynte St., North Adelaide, South Australia.
LITERATURE CITED
(1) Assoc. Official Agr. Chemists, “Official Methods of Analysis,” 7thed., No. 20.28, p. 327, 1950. 187-191 (4, 6) (2) r w , NO. 22.34, p. 348, 1950. (3) Barker, H. A,, personal communication, March 195-200 (9) 12, 1951. (4) Beilstein’s “Handbuch der Organischen Chemie,” Vol. 31, 4th ed., p. 312, Berlin, Julius Springer, 1938. (5) Brown, C. A., and Zerban, F. W., “Sugar Analysis,” 3rd ed., pp. 685-8, New York, John Wiley &Sons, 1941. (6) Cotton, R. H., Norman, L. W., Rorabaugh, G. O., and Haney, H. F.. IND. ENG.CHEM..43.628-35 (1951). (7) Gillette,’E. C., “Low Grade Sugar Refining,” p. 47, California and Hawaiian Sugar Refining Corp., 1948. (8) Hough, L., Jones, J. K. N., and Wadman, W. H., J . Chem. SOC., 1702-6 (1950). (9) Huntress, E. H., and Mulliken, S. P., “Identification of Pure Organic Compounds. Order I,” p. 77, New York, John Wiley &Sons, 1941. (IO) Jones, J. K. N., and Smith, F., “Advances in Carbohydrate Chemistry,” Vol. 4, pp. 243-83, New York, Academic Press, 1949. (11) McCready, R. M., personal communication, Jan. 25, 1951. (12) Sherwood, S. F., IND. ENG.CHEM.,15,727-8 (1923). (13) Van Hook, Andrew, Ibid., 36,1042-7 (1944). (14) Van Hook, Andrew, personal communication, Aug. 7, 1951. (15) Ventre, E. K., Sugar J . , 3, No. 7,23-30 (1940). (16) Walton, C. F., Jr., and Ventre, E. K., Intern. Sugar J., 39, 430-1 (1937). (17) Wiley, H. W., U.S. Dept. Agr., Div. Chem., Bull. 2 (1883). (18) Willaman, J. J., and Davison, F. R., IND. ERG.CHEM.,16, 60910 (1924). RECEIVED for review May 2, 1952. ACCEPTED May 19, 1952. Presented before the Division of Sugar Chemistry a t the 121st Meeting of the AMERICAN CHEMICAL SOCIETY, Milwaukee, Wis.
Filtering Superheated Alcoholic Solutions T
2417
A. W. BILLITZER’ Beckers P t y . , Ltd., Dudley Park, South Australia
emptied and the reaction mixture heated up again in order to be filtered through a hot water funnel. Splashing and tearing of the filter paper in the suction funnel were factors militating against the batches being run out practically a t the reaction temperature (110’C.) as soon as heating was stopped. There were also high losses of alcohol through the vacuum in the filter flask; these losses increased with the air temperature. Splashing wae eliminated by fitting the Buchner funnel with a splash cover. This consisted of a truncated cone made from copper sheeting. To prevent damage to the filter paper by the
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY lower edge of the cone, it was turned outward. Also, to permit the filter cake to spread evenly, outlets were cut into the lower edge of the cone. These outlets were equilateral triof the cone in height,, angles about spaced evenly around the base. A piece of Klingerit about l/s of the diameter of the Biichner funnel, T, as placed in the middle of the filter paper a? a protective baffle. Asbestolite or asbestos sheeting could aleo be used but Klingerit can easily be cut out with a wad cutter andis durable as
Vol. 44, No. 10
undor suction. Then the Klingerit baffle is placed in the middle of the filter paper and t,he whole covered with the fiplash cone. Suction must be applied before the actual filtration begins. All flames in the vicinity must, of course, be extinguished before the autoclave charge is run out should this contain alcohol. If, during the filtration, the alcohol should distill too quickly into the condenser trap and start to choke the condenser, suction can be interrupted for a moment at the upper end of the condenser. Some 300 filtrations under the conditions described have been carried out succeesfully with the assembly described. The reflux trap facilitate8 recovery of most of the akohol evaporat,ing in the filter flask. About 280 ml. of a total of 2 Mers of QOyc alcohol are lost by evaporat'ion in the funnel.
well. The dimensions of the splash cone and the baffle depend on the size of the Buchner funnel used. The funnel should be chosen so that not more than I/S of its height is filled by the filter cake; otherwise it will be difficult to remove the cone. FILTRATION PROCEDURE
The outlet tube, which reaches to ACKNOWLEDGMENT Lhe bottom of the autoclave, is proThe writer desires to record hi* vided with two valves. The main valve regulates, approximately, the grateful ackiiowledgment, for permission to publish this paper, to thP pressure of the issuing solution. The Figure 1. Diagram of Filtering second valve, located nearer the end managing director of Beckers, Pty , Arrangement of the tube fitting into the splash Limited, in whose research labocone, regulates the amount of Soluratories at Dudley Park, South tion being run into the Biichner funnel. Before the funnel it: Australia, this work was carried out used, the filter paper must be moistened--e.g., witjh wat,er-ACCEPTBD nIsY 26. i s a . R E C E I ~ for~ review, ~ Soreniber 27, 1961.
J
J
d
r ROBERT B. ANDERSON, JULIA" FELDZIAN,
AND HENRY H. §TORCH
E'. 5'. Rureuri of Mines, Synthetic Fuels R e w a r c h Brunch, Rruceton, P a .
ROCESSES for the hydrogenation of carbon monoxide to alcohols may be divided into two groups. The first of these, in which the catalysts are difficultly reducible oxides (catalysts containing copper oxide are exceptions to this generalization), includes the methanol synthesis, the higher alcohol erynthesis, and the is0 synthesis. The second group includes variations of the Ii'ischer-Tropsch synthesis over iron catalvsts. Both types of syntheses were discovered in the period 1920-28 The methanol and higher alcohol syntheses were developrd rapidly into practicaI commercial, processes. The is0 synthesis which may be considered a variation of the higher alcohol synthesis, was discovered in 1940. Although the Fischer-Tropsch synthesis using iron catalysts was discovered in 1923, catalyst and process development proceeded slowly and large scale processes employing iron catalysts for the production of hydrocarbons or of alcohols did not appear feasible until about 1940. By intensive research on the Fischer-Tropsch synthesis over iron catalysts, in Germany during World War IT and in the United States since the war, several attractive synthesis methods have been developed. Ifeither the is0 synthesis nor the FischerTiopsch process with iron catalysts haa been exploited commer-
cially, except that the Hydrocol plant a t Brownsville, Tex., employing a fluidized iron catalyst, is reported to be in operation This represents the first commercial use of the Fischer-Tropsah synthesis with iron catalysts. The hydrogenation of carbon monoxide to alcohols may IJ? expressed by Equations 1 and 2 or combinations of them: 2n HE (n
+ n CQ = C,,IIZ~+IOH + ( n - I)H&
+ 1) Hz + (2% - 1 ) CO
=
CnR2n+10H f (n
-
(1)
1) Con ( 2 )
The thermodynamics of these rttactions have not been complet'eiy investigated, as indicated by a recent summary of available data (33). The equilibrium constants of Equations 1 and 2 decreaw rapidly with increasing temperature, and the temperatures at which the equilibrium constants equal 1 may be taken as the upper limits at which sizable yields of alcohols may be obtaincrl at low operating pressures. For reactions 1 and 2 , respectively, these temperatures are 238' and 318" C. for ethyl alcohol, 316" and 358' C. for 1-propanol, and 330" and 378" C. for 1butanol. For methanol, Equations 1 and 2 are identical and thr equilibrium constant is unity at 1.46" C. Thua, at any giver]
