HALLIGAN ON A M E R I C A N MOLASSES FEEDS. SUMMARY.
( I ) A slight change in the method of determining total tartrates, consisting in employing a 4-inch Riichner funnel instead of a Gooch crucible for collecting the crop of crystals] was found necessary when dealing with hot pressed Concord grape juice. ( 2 ) The Scuppernong grape juices were considerably less rich than the other varieties in all constituents except total acid, and two out of the three varieties analyzed contained sucrose. ( 3 ) The maceration of the cold-pressed Concord juice for sixteen hours had little effect on its composition. (4) The hot-pressed Concord juices were considerably richer in solids than the cold-pressed, and this difference was due to slight increase in ash, total acids and total tartrates, an increase in nitrogen and decided increases in undetermined solids, and tannin and coloring matter. (5) The Catawba grape juice was similar in composition to the cold-pressed Concord, but higher in total acids, total tartrates and protein. ( 6 ) A method of using litmus due to C. S. Ash was found very useful. This method consists in employing a litmus which has been thoroughly exhausted with hot alcohol, and using a dilute neutral solution placed in small drops on a white glass surface as an outside indicator. ( 7 ) With red grape juices using phenolphthalein it is shown that it is necessary to run a blank side by side with the sample being titrated in order to detect the change in shade due to the indicator. ( 8 ) When dilute solutions of the commonly occurring organic acids were titrated, litmus was found to indicate from 96 to 99 per cent. of the acids, the amounts shown by phenolphthalein being taken as IOO per cent. ( 9 ) When grape juice low in tannin and coloring matter was titrated, litmus indicated from 96 to 98 per cent. of the acids present. ( I O ) Il'hen juices high in tannin and coloring matter were titrated, but from 85 to 90 per cent. of the acids apparently present were indicated by litmus. After removing the tannin and coloring matter litmus indicated from 96 to 97 per cent. of the amounts of acid shown by phenolphthalein. (11) Litmus is to be preferred to phenolphthalein in the titration of total acid in products containing appreciable quantities of tannin and coloring matter since by its use these substances are not appreciably titrated.
44 =
AMERICAN MOLASSES FEEDS: THEIR MANUFACTURE AND COMPOSITION. By J.
E. HALLIGAN.
Received February 2 5 , 1909.
The manufacture of molasses feeds in this country started about twelve years ago and since that time the demand for this class of feed has steadily increased until to-day it is one of' the standard mixed feeds found on the American market. On account of the popularity for such a feed many mills are turning out molasses feeds exclusively. The capacity of the mills vary from 50 to 500 tons per day, and they average about IOO to 150 tons a day. There are several different methods employed in conipounding these feeds for the trade, among which may be mentioned the following: I . The molasses is mixed with the primary products (such as grain, chopped hay, etc.), without subjecting any of the materials to heat. 2 . Cold molasses is added to the kiln-dried primary products and thoroughly mixed. 3. Hot molasses is mixed with cold primary products. 4. Hot molasses is mixed with artificially dried primary products. Some manufacturers vary the above-mentioned methods by artificially drying their mixtures after the molasses has been thoroughly incorporated with the balance of the feed. The temperature to which the molasses is heated varies in different factories but it is generally just warmed, although the best results are obtained when the molasses is brought to the boiling point. Of the above methods, No. 4 has given fine results, both in lowering the moisture content and in preventing the feed from decomposing when put on the market. I n the manufacture of wet feeds method No. 3 is often followed. It is difficult to secure a good mechanical mixture when a small quantity of molasses is employed unless the molasses is heated before introducing it into the balance of the feed. The heating of the molasses before mixing allows of a more even distribution and drives off some of the water present in the molasses. Those feeds manufactured by using small amounts of cold molasses are liable to be lumpy and especially is this true when finely ground products such as cottonseed meal, rice polish, etc., are contained in the feed. &lost factories use a mixture of beet and cane molasses. There are some concerns that employ
442
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y .
either beet molasses or cane molasses entirely. When a mixture of beet and cane mdasses is used the beet molasses generally predominates as the cane molasses is used to render the feed more palatable and to give it a pleasant aroma. I n such cases when a mixture of beet and cane molasses is customary the cane molasses is often diluted with about 15 per cent. of water. The cane molasses is warmed and the molasses and water thoroughly mixed. The manufacturers claim they dilute the cane molasses to insure a more even distribution, but in all probability the water is added to reduce the cost of the feed as such feeds are not usually dried after the molasses is added. Beet molasses is never, or hardly ever, diluted with water as it is already fairly thin when delivered. There are many combinations of materials introduced in these feeds, governed principally by the intelligence and honesty of the manufacturers. The location, demand, ease of obtaining and price of the feeding materials that go to make up the finished product are also important considerations in the selection. Cottonseed meal, malt sprouts, dried brewers’ grains, distillery products, rice bran, rice polish, rice hulls, corn, corn chops, corn bran, ground corn-cobs, ground corn-stalks, corn pith, wheat products (generally wheat screenings), dried beet pulp, oats (generally off-grade oats), oat hulls, finely ground or chopped hay (usually leguminous hays, such as alfalfa), straw, flax brands (including all weeds, dust, dirt and screenings from the flax seed as well as part of the shell and fiber of the flax), elevator dust (including grain smut, all sorts of brushings and cleanings, such as dust, grain rust, etc.) , sweepings, grain screenings, refuse from flouring mills, cockle seeds and bran, ground peanut shells, weed-seeds (ground and unground), chaff from pipe factories and similar products are used in these feeds. Some manufacturers use high protein concentrates such as cottonseed meal, dried brewers’ grains, distillers’ grains, etc., to fortify their feeds and they add inferior materials such as rice hulls, weed seeds, ground corn-stalks, elevator dust, grain screenings, ground straw, oat hulls, unsound grains of corn, etc., as a filler. The whole mixture is then concealed by the addition of molasses. It is possible for a manufacturer to pdt out such a feed as mentioned above and have it run as high in chemical composition as a feed made up of entirely high-grade products. There are many molasses
July, 1908
feeds on our market composed of good clean standard products, but the molasses offers an excellent chance for the use of inferior materials by the unscrupulous manufacturer. There are some people who do not sell a feed made up of the same feeding products all the time, but they change their mixtures two or three times a year, as they are sometimes unable to obtain the primary products a t a price enabling them to sell at a profit. Others substitute materials to improve their feed or to increase their profits. Some high-class feeds have been offered to the trade and after a demand has been created lowgrade materials have been substituted for the pure products that originally made up the feed. There are two general classes of molasses feeds sold to our feeders, namely, horse feeds and dairy feeds. Poultry and calf feeds are also manufactured but these are exceptional. Most of the manufacturers prefer to handle the horse feeds because of the greater profits. The quantity of molasses employed in these feeds varies from 10-60 per cent. Those feeds carrying 25 per cent. or more of molasses are usually classed as wet feeds (provided they are not artificially dried), and those containing less than 25 per cent. of molasses are termed dry feeds. There are many feeds that contain more than 25 per cent. of molasses which are subjected to a drying process and these are classed as dry feeds. Wet molasses feeds are generally sticky and of darker color than other molasses feeds, due to the large amount of molasses present. I n the North, some of the wet feeds form a hard cake in the cold weather and in such cases i t is necessary to thaw them out before feeding. Below are a few analyses of wet molasses feeds: WET MOLASSES FEEDS. I. 11. 111.
............. ........ ............... ...............
Protein. Ether extract Carbohydrates........ Fiber. Water Ash
.................
12.88 15 95 2.75 0.54 0.74 43.33 36.94 49.45 19.23 21.16 10.86 16 41 18.47 ’16.10 9.81 4.89 8.80 11.69
IV. 6 52 1.79 51.92 14.97 14.20 10.60
V. 15 60 3.82 45.32 12.01 16.65 6.60
I. and 11. Chopped alfalfa and about 5 0 per cent. beet molasses. 111. Malt sprouts, brewers’ grains, cottonseed meal and 30-40 per cent. cane molasses. IV. Off-grade corn, cut straw, light oats, oat hulls and about 30-40 per cent. cane molasses. V. Brewers’ grains, malt sprouts, rice hulls, light oats, oat hulls, grain screenings, about 30-
HALLIGAN ON AAdERICAN MOLASSES FEEDS. 40 per cent. beet molasses, and cane molasses.
1-20
per cent.
DRY DAIRY FEEDS.
Those molasses feeds sold as dairy feeds usually run high in protein and they are often fortified with some protein concentrate. The following analyses show the coinposition of the principal dry dairy feeds found on the American market. I. Protein . . . . . . . . . 13.90 Ether extract... . 3.10 Carbohydrates 52.44 Fiber . . . . . 16.46 Water ..... ... 7.20 A s h . . . ... . . 6.90
. .. . . .. ....
11. 17.80 3.32 52.03 8.76 10.23 7.86
111. 16.22 4.73 51.17 11.36 9.20 7.32
IV. 14.35 3 .OO 48.96 15.06 10.68 7.95
. . .. .
Protein.. . . . Ether extract.. Carbohydrates . F i b e r . . . . . . .... Water.. . . . . . . . . A s h . , . ... . . . . .
.
I. 1 1 .68 3.70 56 67 10.29 1 1 .97 5.69
11. 11.98 5.89 51.79 11.15 11.05 8.14
I11 11.56 4.77 59.18 6.00 11.83 6.66
IT’. 11.06 1 .75 49.73 22.37 9.18 5.91
screenings and dirt from the flax seed as well as part of the shell and fiber of the flax), elevator dust, light oats and hulls, cottonseed meal, about 25 per cent. beet molasses and 5-10 per cent. cane molasses. XI. Corn products, distillers’ products, cottonseed meal, elevator dust and about 35 per cent. beet molasses.
V.
VI. 17.13 5.09 46.87 11.86 11.97 7 .os
17.00 4.49 50.17 11.15 11.30 5.89
I. Corn, brewers’ grains, malt sprouts, cottonseed meal, rice hulls, weed seeds, about z j per cent. beet molasses and 5-10 per cent. cane molasses. 11. Off-grade corn, light oats, oat hulls, wheat screenings, malt sprouts, cottonseed meal, barley beards and screenings, about 2.5 per cent. beet molasses and 5-10 per cent. cane molasses. 111. Corn, off-grade oats, oat hulls, malt sprouts, brewers’ grains, cottonseed meal, barley residues, rice hulls, weed seeds, about 2-30 per cent. beet molasses and 5-10 per cent. cane molasses. IV. Corn, dried brewers’ grains, malt sprouts, elevator dust, wheat and buckwheat screenings, about 2j-30 per cent. beet molasses and 5-10 per cent. cane molasses. IT, Cottonseed meal, wheat screenings, light oats, oat hulls, off-grade corn, weed seeds, about 20--25 per cent. beet molasses and 5-10 per cent. cane molasses.
VII. 18.94 3.27 50.86 10.17 10.99 5.77
VIII. 18.31 6.63 49.38 8.30 9.72 7.66
IX. 14.26 3.14 53.93 9.82 11.60 7.25
X. 16.14 5.12 43.41 20.30 8.10 6.93
XI. 16.10 3.96 48.77 11.18 12.15 7.84
DRY HORSE AND MULE REEDS.
Those feeds sold for horse and mule feeds carry more carbohydrates and less protein than the dairy feeds, as the accompanying analyses show : I. Distillery products, ground corn-stalks, ground corn-cobs, light oats, oat hulls, cottonseed meal, weed seeds, about 25 per cent. beet molasses and j per cent. cane molasses. 11. Corn chops, rice bran, rice polish, cottonseed meal, and 1j-30 per cent. cane molasses. 111. Corn chops, wheat bran, cottonseed meal, alfalfa, and 15-25 per cent. cane molasses. IV. Corn chops, cottonseed meal, Lespedeza hay (chopped), and 2 0 per cent. cane molasses. V. Dried brewers’ grains, chopped alfalfa, corn chops, cottonseed meal, elevator dust, and 25-30 per cent. cane molasses. VI. Chopped alfalfa, corn, oats (off-grade), barley and about 2 j per cent. beet molasses,
V. 12.69 5.80 55.23 9.12 9.72 7.44
corn-stalks, ground corn-cobs, VI. Corn, ground off-grade oats, barley, cottonseed meal, distillery products, elevator dust, weed seeds, about 25 per cent. beet molasses and 5 per cent. cane molasses. VII. Brewers’ grains, malt sprouts, cottonseed meal and 2 j-30 per cent. cane molasses. V I I I . Corn, rice bran, rice polish, cottonseed meal and 15-30 per cent. cane molasses. IX. Corn bran, oat hulls, light oats, off-grade corn, elevator dust, wheat and buckwheat screenings, malt sprouts, distillery residue, about zj per cent. beet molasses and 5-10 per cent. cane molasses. X. Flax brands (including all weeds, dust,
443
VI. 10.78 2.42 61.95 8.06 12.00 4.79
VII. 8.84 2.80 53.91 12.75 12.69 9.01
VIII. 12.48 3.26 53.01 13.89 11.26 6.10
IX. 11.13 7.26 54.96 8.47 11.62 6.56
X. 12.00 6.50 51.52 10.32 11.31 8.35
XI. 13.70 5.42 40.43 20.92 12.85 6.68
VII. Corn, light oats and hulls, sweepings and per cent, cane molasses. VIII. Light oats, corn product, wheat screenings, cottonseed meal, linseed meal, weed seeds, about I j - 2 0 per cent. beet molasses and 5-10 per cent. cane niolasses. IX. Corn chops, chopped alfalfa, rice bran, cottonseed meal and I 5-25 per cent. cane molasses. X. Dried brewers’ grains, chopped alfalfa, rice bran, elevator dust, corn chops (off-grade), cottonseed meal and I j-30 per cent. cane molasses. XI. Distillers’ grains, cottonseed meal, flax brands, weed seeds, elevator dust, about 25 per 2j
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T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y . July, 1909
cent, beet molasses.
molasses, and 5-10
per cent. cane
F O R E I G N MOLASSES F E E D S .
The analyses of a few German molasses feeds and the Toury peat-molasses combination is given for comparison :
ucts, such as previously fermented corn, etc., and by improper drying of the feed. Oftentimes cane molasses ferments on the plantations before being purchased and when such fermented molasses is put into a feed without proper treatment, the usual result is the deterioration of the feed. The simple
ANALYSESOF GERMANMOLASSES FEEDS.
Protein . . . . . . . . . . . . . . . . . Ether extract. . . . . . . . . . . . Carbohydrates.. . . . . . . . . . Fiber.. . . . . . . . . . . . . . . . . . Water.. ................. Ash.. . . . . . . . . . . . . . . . . . . .
Ia. 12 71 1.88 48 02 12 00 18.33 7.06
IIU.
14 65 4.44 53.58 3.41 17.69 6 23
IIIU.
11.31 4.67 56.40 5.52 16 50 5.60
1. Palm oil meal and molasses-average of two analyses. 11. Corn germ and molasses-average of three analyses. 111. Wheat bran and molasses. IV. Wheat bran, blood and molasses. V. Brewers’ grains, blood, bran and molasses. VI. Dried cossettes, blood and molasses. VII. Cocoanut cake and molasses. VIII. Dried cossettes and molasses. I n all probability the above feeds contain beet molasses entirely. a. Ware-Cattle Feeding-page 294. b. Ware-Cattle Feeding-page 283. c. Ware-Cattle Feeding--page 260.
(d). Water 19.00 per cent., ash 8.91 per cent, sugar 3 1 . 7 0 per cent, soluble substances 20.93 per cent, insoluble substances 19.46 per cent. This molasses fodder consists mainly of 24 per cent. peat and 76 per cent. slightly steamed diluted molasses. d. Ware-Cattle Feeding-page 265. THE TOURY PEAT-MOLASSES COMBINATION
AMERICAN MOLASSES FEEDS.
One per cent. or less of salt is put into some of these feeds to make them more palatable. On account of the acidity of Louisiana molasses, due to the use of sulphur in the manufacture of sugar from the cane, feed manufacturers sometimes Oeutralize this acidity by adding lime-water or sodium hydrate. It has been found impracticable to use lime-water as the lime separates out and shows in the feed. There has been considerable trouble experienced with molasses feeds on account of fermentation setting in and spoiling the feed. Some manufacturers have eliminated this trouble almost cornpletely by proper and careful manufacture. Fermentation is caused by using unsound primary prod-
IVb. 24.62 1.04 53.02 7.02 7.33 6.97
Vb. 25 .OO 0.14 50.98 9.77 8.51 5.60
VIb. 29.55 0.22 50.89 6.24 8.53 4.57
VIIa. 15.25 2.19 49.90 3.07 20.85 8.74
VIIIC.
8.90 0.35 59.45 14.40 9.00 7.90
warming of fermented molasses is not sufficient but it must be brought to a boil to arrest the fermentation completely. When a mixture of beet and cane molasses is employed and the diluting of the cane molasses with water is practiced, the result i s generally a spoiled feed, due to fermentation. One manufacturer told me that he had to discontinue the use of beet molasses in his wet feed as fermentation invariably set in and decomposed the feed. As a whole, it is a safe policy to boil the molasses, be i t cane or beet, as such procedure tends to arrest fermentation and it also results in driving off a great deal of water, which keeps down the moisture content. A one-hundred pound sack of feed, composed of a mixture of dried brewers’ grains, malt sprouts, cottonseed meal and 35 per cent. cane molasses, was left on a wharf, which had a roof but was open on all sides, for two months, on the banks of the Xississippi River a t Baton Rouge, Louisiana. At the end of that time this feed was in perfectly sound condition. There was some loss of moisture but otherwise no change took place in the feed. The test was fair for there were three heavy rains during the period and considerable damp weather. According to a test run by a large manufacturer of molasses feeds, cane molasses seems to have better keeping qualities than beet molasses. This test took place in the middle west in the summer. The beet molasses was kept in a tank and drawn on from time to time without complete emptying, and the tank was filled a t frequent intervals. In the course of one month fermentation set in. The same test was tried with cane molasses under the same conditions and i t took three and a half months for fermentation to start, necessitating the thorough cleansing of the tank. This manufacturer says: “often the tank containing the cane molasses does not ferment until the end of four months but the
OLSON Oh‘ A RAPID METHOD OF H Y D R O L Y Z I N G STARCH
445
method as officia1.l While this method gives fairly satisfactory results, it still has the disadvantage of time when compared with the method which will be discussed in the following pages. IVhere two and one-half hours were required to hydrolyze starch it is now possible to accomplish this in about four minutes. Preparation of Samples.-Before discussing this method, it is deemed advisable to give a few suggestions as to the preparation of the samples to be hydrolyzed. Too much stress cannot be laid upon the importance of securing a uniform, representative sample. The material should be finely ground and thoroughly mixed. In case of some substances, e. g., oats, etc., it is preferable after the first grinding to separate the hulls from the starchy material and grind separately, thus insuring a more uniform mixture. Method of Hydrolysis.-Place in a 500 cc. Kjeldahl flask one gram of material. Tap the neck of the flask in order to settle the fine particles adhering to the sides. Mix with this weight ten cc. of distilled water and rotate slowly and steadily (one revolution per second) so as not to wash any of the sample too high up on the sides of the flask. Next cautiously add 6 cc. of sulfuric acid (specific gravity 1.84) and rotate somewhat more rapidly than in the first instance. After the acid and material have been thoroughly mixed hold the flask in one hand over a flame about two inches high and rotate about one revolution per second at first and then as the mixture increases in temperature rotate with an accelerated motion up to five revolutions per second. Continue rotating at this rate until the mixture becomes nearly LOUISIANA STATEEXPERIMENT STATION, BATONROUGE,La. transparent. At this stage add IO to 15 cc. of ________ distilled water, continue rotating and heat again, this time to boiling, cool, neutralize with sodium A RAPID METHOD OF HYDROLYZING STARCH. hydroxide (using phenolphthalein as indicator), B y GEO. 4.OLSON. cool again, transfer to 2 5 0 cc. volumetric flask, Received May 3 , 1909. fill with distilled water to mark and proceed acNumerous methods for the hydrolyzing of starch cording to one of the recognized methods for have been devised in the past, among which may dextrose determination. be mentioned Sachsse’s,l Llarker’s,z G ~ i c h a r d ’ s , ~ >Votes o n Manzpu1atzon.-The hydrolysis comand others. Chemists who have tried these methods mences with the addition of acid. I n case of know what a long and tedious procedure it is to cereals, bran, shorts, etc., a slight coloring is first wash and hydrolyze materials according to any one observed, then a milkiness, and finally the solution of them. After a futile attempt to find a method becomes almost transparent, varying in color from that would give concordant results, the members straw to a light brown. A further heating inof the A. 0. A. C. finally adopted the Sachsse tensifies the color, and if this process is continued ’ Chem. Ceniralbl., 1877, p. 7 3 2 ; Journ. Anal. Chem., 11. 1 5 3 . too far there is danger of caramelizing a part of the
beet molasses will not keep more than a month under our conditions.” The use of beet or cane molasses, or a mixture of both in varying proportions, in molasses feeds, is a problem yet to be determined by many manufacturers. Keeping qualities, palatability, effect on the animals and popularity of the feed are some of the problems to be considered. Just about twelve years ago Louisiana blackstrap was a nuisance and the sugar planters had a hard time to dispose of it. On account of its value for feeding purposes the demand has become SO great that i t is now selling for $19 to $ 2 1 per ton retail, perhaps the highest figure i t has ever reached. Louisiana blackstrap has been so scarce that some of our feeders are purchasing second molasses for feeding purposes. The time is coming when our manufacturers of commercial molasses feeds will be forced to obtain some of their supply of cane molasses from the. tropical countries. On the whole, there is a bright future for molasses feeds even a t the high prices feeds are carrying. It is possible for manufacturers to put out wholesome feeds free from adulteration with inferior products and make a good profit. I n the past two years there has been a great improvement in this class of feed,and some concerns have been forced to go out of business on account of flagrant adulteration of their feeds. The time has come when .only those feeds that are pure and honest mixtures will meet with success, as adulterated feeds even if they do have a high chemical composition, most always show poor results on the animals to which they are fed.
Chem. Z e i t . , IX,3 1 9 ; Ztschr. anal. Chem., 24, 617. Bull. d. 1. S O C Chim. . d . Parts [31, 7 , 554.
U . S . Depi.
of Agr
, Bur. of Chem., Bull. 107 (rev. ed.), p . 53.
