Showing papers in "Industrial & Engineering Chemistry Chemical & Engineering Data Series in 1956"

Nonaqueous Solvents for Sucrose

Abstract: Sugar has the highest potentiality a s a raw material for the chemical industry both because of its enormous availability, and because the field of industrial applications is almpst unexplored. Reaction media for sugar a re required which will not react with themselves or interfere with the desired reaction. Almost no suitable solvents for sugar were known. The literature of sugar solubilities in nonaqueous solvents has been surveyed and summarized. Determinations of solubility of sugar in 14 solvents at various temperatures have been made. A relationship involving the meltingpoint of sugar and the dielectric strength of the solvents has been determined. The rapid emergence of sucrochemistry a s a new field of research and industrial application requires information on possible reaction media. Water has been the most studied sugar solvent. For many applications water is unsuitable since it may itself react, i t may prevent o r interfere with the desired reaction, o r it may not be a good solvent for the other reactants, Someprevious studies of other solvents a r e recorded, especially for their physicochemical interest. Many of the results found i n the literature a re in very poor agreement. Often, determinations were made at only one temperature so that comparisons wi th other results a r e impossible. Equilibration times have varied wi th different workers from 5 minutes to240 hours. In some cases no attempt was made to obtain saturated solutions. Finally, polarimetric measurements, frequently dsed for determination, a r e subject to e r ro r since the specific rotation of sugar varies with the solvent. The solubility of sucrose in ethanol and in aqueous ethanol was determined by Scheibler (42), Lindet (30), Schrefeld (45), Pellet (36), Urban (53), lludson and Yanowski (21), and Reber (40). Grossman and Bloch (11) prepared a solution of sucrose in formic acid. Karcz (24) and Strohmer and Stiff (52) determined the solubility of sugar in glycerol. Other studies in glycerol were made by Browne and Randle (3), Fey, Weil, andSegur ( 8 ) , and Segur and Miner (48). Methanol was tried by Scheibler (43), Lindet (30), Gunning (13), and Lobry de Bruyn (32). Sherry (50), and Fitzgerald (9) found that sucrose dissolves readily in methylamine. Wilcox (59) made a similar observation for isopropylamine. Vogel(56) reported that suga r is insoluble in piperidine. Schukarew (46) used a dilute solution of sucrose in aqueous propionitrile for critical temperature tests. Fey, Weil, and Segur (8) reported 1.9% by weight for the solubilityof sugar in 99% aqueous propylene glycol. Pyridine has been much favored a s a solvent. Wilcox (58), Holty (18), Kahlenberg (23), Cohen and Commelin (5), Grossman and Bloch ( l l ) , Koenig (27), and Dehn (6) have published determinations of the solubility of sucrose in pyridine. Sherry (50) found sucrose to be insoluble in sulfur dioxide. Schiff (44) dissolvedsugar in both hot and cold acetic acid of 97 to 100% concentration. A French patent (51) claims the separation of sucrose from molasses by its insolubility in acetic acid particularly after adding ethyl acetate o r benzene. The solubility of sugar in acetone and i n aqueous acetone mixtures is reported by Krugand MacElroy (28), Herz and Knoch (16), and Verhaar (55). Solubility determinations in aqueous andin anhydrous ammonia have been published. by Wilcox (59), Sherry (50), and Fitzgerald (9). Wilcox (59) found high solubility for sugar in allylamine and in amylamine. Plato (38) reported that s u crose is insoluble in benzene. Helferich and Masamune (15) found only 0.08% sucrose dissolved in boilingdioxane. Lang (33) prepared a solution containing 40.q0 by weight of sucrose in monoethanolamine. The solution did not reach saturation. Altogether 19 solvents a re listed in this literature survey. However, only pyridine has any interest for sucrochemical applications. The remainder a r e either too poor solvents o r enter too readily into competing reactions. Hence, the present data a r e on a very different group of solvents. Some consideration was also given to aprocedure for solubility determination which would yield results of practical accuracywith relatively little consumption of time and effort.

Waste Pickle Liquor. Ferrous Sulfate-Sulfuric Acid-Water

Abstract: D a t a for the ternary system ferrous sulfatesulfuric acid-water a r e presented for Oo, 27O, 40°, 60°, and looo C. Such data a r e helpful in solving the problem of recovery and utilization of waste pickle liquor. E r r o r s in existing data for binary and ternary systems a r e a lso discussed. The steel industry has worked assiduously to solve the technical problem of recovery and utilization of waste pickle liquor. Numerous processes have been prcJposed (8, 10, 11, 13, 16,23,24). Many of these call for the separation by crystallization of ferrous sulfate in various hydrated forms from the waste solution. To have complete information for engineering calculations, data for the system ferrous sulfate-sulfuric acid-water should be available over the complete range of sulfuric acid concentrations and from Oo to looo C. This paper presents such solubility data. An enthalpy-concentration diagram for the system ferrous sulfate-water has previously been prepared (20). The amount of waste pickle liquor produced annually i s not known definitely, Hoak (12) estimates it to be in excess of 600 million gallons, and Hodge (14) estimates it from 500 to 800 million gallons. The concentrations vary with pickling processes; typical analyses a r e given by Hodge. In modern continuous s t r ip picklers a typical analysis would be 7% sulfuric acid, 15% ferrous sulfate, and 78% water. Bramer and Coull ( 5 ) estimate nearly a billion gallons of waste pickle liquor annually with an average composition of 5% sulfuric acid and 15% ferrous sulfate.