336
I K D U S T R 1 A L A N D E S G IS E E K I N G C H E M I S T R Y
test increased slightly as the temperature of pressing was raised. The color of the oils after the test was much lower than before, until the critical temperatures (50' to 65" C.) of pressing were reached and nonbreak oils were no longer produced. Above these critical temperatures the color of the oils after the break test increased very rapidly. It is interesting to note that these critical temperatures were raised as the moisture content of the beans was reduced. With beans of 4, 6, and 8 per cent of moisture the critical temperatures were approximately 6 5 O , 55", and 50" C., respectively. Table I1 shows the effect of temperature of pressing and moisture content on the per cent of oil left in the cake. Retter yields were obtained a t the higher temperatures, although satisfactory yields were obtained a t temperatures close to 65" C. These results show that it is possible to obtain a satisfactory yield of a nonbreak oil by controlling the moisture content of the beans and the temperature of pressing. These results may not be entirely comparable with those obtainable in an oil mill where large hydraulic presses or oil expellers are used.
SUMI\IARY A nonbreak soy-bean oil is one that when heated to a temperature of 600" F. shows little or no precipitate and bleaches to a colorless or a very pale yellowish colored oil. The soy-bean oil produced by the expeller or hydraulic press when heated to 600" F. develops a dark color and a darkcolored precipitate and is a break oil. For many commercial purposes n nonbreak oil is desired. -4study of the effect
Vol. 25, No. 3
of moisture content and temperature of pressing on the quality of the oil was made. Changes in moisture content from 0.0 to 8.0 per cent and in temperatures of pressing from room temperature to 100" C. had no effect on the iodine number of the oil. With beans of 4 per cent moisture content there is a gradual small increase in color before the break test with increase in temperature of pressing. The color after the break test is much lower than before the break test until the critical temperature of pressing (about 65" C.) is reached and the oil becomes a break oil. Then the color after the break test rises very sharply with increase in temperature of pressing. The critical temperatures of pressing a t which break oil< result were raised as the moisture contents of the beans were reduced. Although these results may not be entirely comparable with those obtained in an oil mill where large hydraulic presses or oil expellers are used, the results show the important effect of moisture content of beans and temperature of pressing upon the quality and yield of the oil. LITERATURE CITED (1) I m . Oil Chem. SOC.,Official Methods of Chemical Analysis, 1929. (2) Morse, W. J., U.S.Dept. Agr., Farmers Bull. 617 (1930). (3) Pallauf, F., Chem. Umschau, Fette, Oele, Wachse Harze, 37, 21 1
(1930). RECEIVED September 10, 1932. Presented before the Division of Agricultural and Food Chemistry a t the 84th Meeting of the American Chemical Society, Denver, Colo., August 22 t o 26, 1932. These data are from a thesia submitted by R. L. Smith t o the Graduate School of Purdue University in partial fulfilment of the requirements for the degree of master of science, June, 1931. This work was supported by a fellowship from the Lafayette Milling Company, Lafayette, Ind.
Removal of Positive Ions by Electroosmose Apparatus EDWARD BARTOW AND MILOA. FRY,State University of Iowa, Iowa City, Iowa
T
HE relative concentra-4t rates of 20, 25, and 30 liters per hour, the nesium c h l o r i d e ; mixture of tion of negative ions in positive ions sodium, calcium, and magnesium calcium chloride and magnesium different parts of a typichloride; and mixture of sodium are satisfactorily removed by the apparatus studied. chloride, calcium chloride, and cal electroosmose apparatus has The removal of sodium is uniformb' greater than magnesium chloride. been studied and r e p o r t e d by calcium and magnesium, and removal of calcium I n each trial t h e m a c h i n e Bartow and Perisho (1). The was run a t three rates: 20, 25, experiments have been continued greater than that of magnesium. and 30 liters Der hour. Samwith positive ions, using the same ples were taken from five parts apparatus and the same technic. The apparatus and the process used have also been described of the machine: sample 1 from feed water; 2 from the third by Illig (S), Behrman ( 2 ) , Marie (C), and Patin (J), and the cell; 3 from the sixth cell; 4 from the ninth cell; and 5 from purified water (the overflow from the tenth cell). Thus description need not be repeated. The object of the experimental work was to determine the fifteen samples were analyzed in each series; since each series rate of removal of some of the common positive ions and to was run in duplicate, a total of 210 samples was analyzed. About 200 milligrams per liter of the positive ion were study the effect, if any, that two or more ions might have used in the experiments with the single salts; 100 million each other in a solution. grams each in the mixtures of two salts; and five equivalent EXPERIMEKTS WITH S O D I C M , CALCIUM -4ND weights when three salts were combined. In each sample >fAGP;ESIUM the residue was determined by evaporation to dryness. Sodium, calcium, and magnesium are the ions found in Sodium was determined by the removal of the other ions and largest quantity in water which must be treated by some evaporation to dryness; calcium, by precipitation with amsoftening process; therefore the chlorides of these elements monium oxalate and weighing as the oxide; magnesium, were chosen for the experiments. Solutions were made by precipitation with microcosmic salt and weighing as the from chemically pure salts and distilled water. Tests were magnesium phosphate. Difficulties similar to those described by Bartow and made with sodium chloride alone; calcium chloride alone; magnesium chloride alone; mixture of sodium chloride and Perisho (1) were experienced. The drip nozzles would plug calcium chloride; mixture of sodium chloride and rnag- up, and frequent adjustment was required to procure a uni-
I N DUSTR IA L
March. 1933
A\
N D EX GINEER ING CHEMISTRY
OF 1. REMOVAL
SODICM CHLORIDE BY OSMOSE hl.4CHINE
TABLE
ELECTRO-
TABLEv.
20
NESIUM
Feed water
25
--Current
SAMPLE
11.5
P.p.m.
P.p.m
P.p.m
515 179 200 76.6 45 23.5 6 2.9 1 0.8
517 178 190 64 40 17.4 5 1.6
514 174 226 73.5 48 13.2 8 2.0
Na
Cell 3
13.75
Residue Na Residue Na Cell 9 Residue Na Purified water Residue 0 0 Na 0.0 1 HEEULT:There was rapid removal of sodium from the first cells, but as the solution became more dilute there was more resistance in the solution and the removal was slower. Cell 6
OF 11. REMOVAL
T.4BLE
CALCICM CHLORIDE
(Approximately 200 p. p. m.) REMOVAL -Rate (liters per hour)-
20 SAMPLE
>OTRCE
Feed \rater
25
-Current
30
7.75
9.0
11.25
P.p.m. 656
P.p.m.
P.p.m.
O F .bf AGNESIUM 111. REMOVAL
634 211 340 54.7 50 4.2
20
SAMPLE
1.6 3 1.5
the removal
30
19.5
20
P.P.~. P . v . ~ . P . v . ~ . Feed water Cell 3 Cell 6 Cell 9 Purified water
Residue Mg Residue
m
Residue Mg Residue MMg Residue M g
835
840 199 510 109 3 17 64.5 28 35 15 20
200
509 107 311 63.4 40 37 17 19.2
Cell 3 Cell 6 Cell 9
838 200 512 110 310 70.8 30 35.2 19 19.1
RESULT: Removal of magnesium was not as complete nor as rapid as that of sodium or calcium. Also the conductivity of the solution remained higher as compared to that of sodium and calcium.
T.4BLE
SAMPLE
--Current
8
P.p.m. Feed water
(amperes)-
11.75
13.25
P.p.m.
P,p.m.
Residue 629 637 600 Ca 103 100 104 Na 100 99 98 Residue 182 200 294 Cell 3 31.3 45 37.3 Ca Na 21.5 36.8 34 Residue 46 72 82 Cell 6 12 16.1 Ca 4.7 Na 4.5 10.9 5.7 Residue 26 16 15 Cell 9 Ca 0.9 0.93 3 Na 0.98 2.0 3.4 Purified water Residue 9 6 0 Ca 0.0 0.7 1.0 Na 0.0 1.0 2.0 RESULT: The removal of both calcium and sodium ions was increased in the presence of each other. Sodium ions were removed faster than calcium ions.
30
CALCIUM CHLORIDE AND KESIlJM CHLORIDE
20
Cell 3 Cell 6
Purified water
Residue Ca Mg Residue Ca M g Residue Ca MI3 Residue Ca Mg Residue Ca
25
--Current
SAMPLE
Feed water
MAG-
30
(amperes)?
10
15
P.p,m.
P.p.m.
P,p.m
1082 100 102 450 31.9 41.0 290 14.2 11.5 90 4.5 4.9 52
1100 103 105 482 35.7 44.5 235 16.4 17.5 80 4.3
1095 100 104 438 35 40 336 17 19
6.0
48 1.0 1.8
0
1.5
Mg
17.5
100
6.4 3.8 60 1.2 2.0
RESULT: In this mixture calcium tended to come out faster than when mixed with sodium. Calcium came out more rapidly than the magnesium ion. O F SODIUM CHLORIDE, CALCIUM TABLEVII. REMOVAL CHLORIDE, AND MAGNESIUM CHLORIDE
(Approximately five times the atomio weights divided by the valence each of sodium, calcium, and magnesium) REMOVAL --Rate (liters per hour)--
20
SOURCE Feed water
Cell 6
SOURCE
(amperes)--
VI. REMOVAL OF
SOURCE
(Approximately 100 p. p. m. each of calcium and sodium) REMOVAL -Rate (liters per hour)-
30
25
14 19 22 P . v . ~ . P . v . ~ . P.a.m 907 876 789 100 102 100.7 101 99.7 101 300 336 245 30.4 29.4 20.8 38 51.4 25.7 80 110 128 1.4 8.6 8.68 4.5 8.8 21.0 36 52 80 0.0 5.0 5.5 1.5 4.25 9.4 24 37 51 0 0.8 0.79 0 2 3.2
(Approximately 100 p. p. m. each of calcium and magnesium) REWOYAL -Rate (liters per hour)-
CeU 3
25
20
--Current
Mg Residue Na Mg RESULT: In this mixture sodium and magnesium ions come out more rapidly than either sodium or calcium in a mixture of sodium and calcium chloride. Sodium came out more rapidly than magnesium. Purified water
TABLEIJ-. REMOVAL OF CALCIUM CHLORIDEAND SODIUM CHLORIDE
20
Na
Cell 9
(amperes)-
15.75
Residue Na Mg Residue Na Mg Residue Na Mg Residue
CHLORIDE
25
-Current
Feed water
6
(Approximately 200 p. p. m. magnesium) REMOV'LL -Rate (liters per hour)0 Tli C E
SAMPLE
SOVRCE
(amperes)-
664 Residue 214 Ca 213 Cell 3 Residue 347 323 Ca 49.0 44.9 Ceil:6 Residue 45 34 6.7 Ca 8.4 10 5 Cell 9 Residue 2.7 2.3 Ca Purified v ater Residue 3 0 2.0 1.7 Ca RESCLT: The removal of calcium followed the same course as of sodium. but c*alciumwas removed much faster than sodium. T.4BLE
CHLORIDE
30
(amperes)-
8.0
Residue
REMOV.4L O F SODIUM CHLORIDE -4ND bI.4G-
(Approximately 100 p. p. m. each of sodium and magnesium) REMOV.4L -Rate (liters per hour)-
(dpproximztely 175 p. p. m. sodium) REMOIAL -Rate (liters per hour)SOURCE
337
25
30
-
Current (amperes) SAMPLE 15 21 23 Atomic Atomic Atomic wt. P , o . m . wt. P . w . ~ . wt. P . v . ~ . Na 5 115 5 115 5 115 Ca 5 100 5 100 5 100 Mg 5 60 5 60 5 60 28.7 1.45 19.8 1.25 33.3 Na 0.9 Ca 2.2 43.9 2.05 40.3 2.8 55.3
Mr Ns
2.45 0.35 0.85 1.0 0.15
17.7 7.8 17.5 10.6 4.5 11.8 6.3 0 4.3 5.1
2.6 0.4 0.9 1.0 0.2 0.25 0.3 0 0.1 0.15
31 7.9 16.7 11.7 4.3 4.3 10
2.7 0.6 1.9 1.9 0.35 0.5 0.45 0.2 0.3 0.3
33 14.5 27.4 16.4 8.5 9.6 5.6 3.9 6.4 4.5
Ca Mg Na Ca 0.5 Mg 0.55 Purified water Na 0 0 Ca 0.2 2.5 Mg 0.25 3.6 RESULT:In a mixture of these ions the sodium ions came out the fastest, followed by calcium, and then magnesium. When run a t faster rates, the magnesium tended to come out faster than the calcium ions, but this may have been due to rise in temperature. Cell 9
form rate of wash. The hard rubber partition warped, causing a variation in the size of cells. Iron was dissolved from the iron tanks and pipes, and settled in the cells. When the chloride-ion concentration was high, the canvas bags were attacked. A more rapid washing would prevent this trouble. The results obtained are shown in Tables I to VII.
338
INDUSTRIAL AND ENG INEERISG CHEMISTRY
CONCLUSION At rates of 20, 25, and 30 liters per hour the positive ions sodium, calcium, and magnesium are satisfactorily removed. In the sixth cell, excepting in the experiment with magnesium chloride where the removal is only about 60 per cent, there is a removal of more than 90 per cent of the positive ions. I n the ninth cell the water is nearly equivalent to distilled water. At the rate of 30 liters per hour the removal is not quite as good as a t the lower rates. In the mixtures the removal of sodium is uniformly greater than calcium and magnesium, and calcium greater than magnesium. The residue in some cases is higher than the sum of the
Vol. 25, Xo. 3
compounds. This does not interfere with the comparison of the relation of the removal of the ions under consideration. LITER.4TURE CITED (1) B a r t o w , E., and Perisho, F. W., I X D . ENG.CHEM.,23, 1306-9 (1931). (2) Behrman, A. S., Ibid., 19, 1229 (1927); J. Chem. Education, 6 , 1611 (1929). (3) Illig, K., 2. angew. Chem., 39, 1085 (1926). (4) Marie, R., Science et ind., 12, 96 (1928). (5) P a t i n , P., Chimie & industrie, 19, 205 (1928).
R E C E I V ~August D 29, 1932. Presented before the Division of Water, Sewage, and Sanitation Chemistry a t t h e 84th Meeting of the American Chemical Society, Denver, Colo., AuguRt 22 t:, 26, 1932.
Rapeseed Oil Air-Blowing in Presence of Catalysts B. P. CALDWELL AND GEO. H. DYE, Polytechnic Institute of Brooklyn, Brooklyn, N. Y. Results of blowing rapeseed oil under regulated A discussion of autoxidation of oils and fats conditions of temperature and air rate in the pres- through the formation of unstable peroxides is ence of a number of catalysts, as indicated by vis- supplemented by determinations of peroxidized cosity measurements, are given. The catalysts are bodies, the largest amount (expressed as hydrogen metal soaps, fatty acids, and a variety of other peroxide) occurring at the period of the blow when substances. Marked increase is obtained with all properties are most rapidly altering: no peraluminum oleate, erucic acid, oleic acid, and blown oxidized bodies are detected toward the end of the rapeseed oil. With anthranilic acid, hydroquinone, blow. I n addition it appears that no peroxidized phenyl hydrazine, and cobalt linoleate the reactions compounds are detectable when a n y of the catalysts is employed. are depressed. A comparison of the properties of free fatty acid No difference in the effect of dried and saturated obtained by fractionally distilling the mixed free air is detected. Some values are given f o r the changes produced fatty acids of linseed oil at 0.20 mm. pressure by blowing olein and oleic acid. The viscosity in- with those of Holde's erucic acid shows good agreecrease for the former is quite like that of rapeseed oil, ment, so that this method of obtaining large quanand the increase is slight in the case of oleic acid. tities of quite pure erucic acid is recommended.
I
N CONTINUATION of work by one of the authors on the bodying of rapeseed oil (6),results are here presented of a study of the blowing of the oil in the presence of homogeneous catalysts. For this purpose small experimental blow tanks were constructed of iron pipe, 15cm. in diameter, 45.5 cm. long, capped on both ends, and lagged with magnesia asbestos. Each was provided with pipes and cocks for filling and emptying, with electrical heater controlled by a thermoregulator inserted in a mercury well, and was fitted with air inlet tube and thermometer. The rate of air flow was determined by means of a flowmeter. Although air-blowing results in changes in many of the physical and chemical properties of the oil, the effects of the several catalysts employed were here judged exclusively through changes in viscosity. The oil used was Ravison rapeseed oil. All viscosities were measured with the Saybolt instrument a t 100" C., and the results are given in seconds for a 60-cc. sample. The first blows were made without added catalyst a t rates of 22.6, 45.3, and 67.8 liters of air per minute per 3.8 liters of oil (0.8, 1.6, and 2.4 cubic feet per minute per gallon) a t 154" C. (310" F.), 166" C. (331" F.), 181" C. (358" F.),
186" C. (367" F.), and 200" C. (392" F.). The results are given in Figures 1 to 5. It can be seen that the rate of bodying increases with increasing air rate a t constant temperature, and with temperature a t constant air rate. It was decided to adopt as standard conditions of blow a temperature of 160" C. (320" F.), and an air rate of 22.6 liters per minute per 3.8 liters of oil (0.8 cubic feet per minute per gallon). Long has stated that moisture conditions affect the bodying of oils: and Sabatier reports that direct oxidation of oils is retarded by moisture. Blows were made under identical conditions with air saturated with water vapor and with air dried over calcium chloride. Figure 6 shows as nearly identical results as could be expected in runs extending over 12 hours. No depressing effect of moisture was noted. The catalysts employed were mostly metal soaps and free fatty acids. The soaps were added in amount to supply the metal a t 0.1 per cent of the weight of the oil. Unless other concentrations are stated, this concentration will be understood. The soaps used (Table I) were lead linoleate, manganese linoleate, manganese resinate, cobalt "rapate," cobalt linoleate, aluminum oleate, aluminum palmitate, manganese linoleate plus aluminum oleate (0.05 per cent of each metal).
