Sept., 1921
T H E .IOliRAVAL O F IA7DL;STRIAL ii D LITGI-1-E C R ISG CH EA\IIST R Y T.4BLE
I1
hind of Fat CXHYDEOQES.4TED O I L I I S D R O G E S 1 T E D CIL Date of baking Dec. 31 Dec. 31 Dec. 10 Dec. 12 Dec. 13 Dee. 17 Date of test Jan, 2 Jan. 2 Dee. 13 Cec. 14 Dec. 16 D e r . 19 SI so '70 68 80 Temp. 01 d o u g h , "F. 50 Temp. ai' room, O F . 10 72 80 SO 78 i6 Temg.Lr oven, Q F . 463 465 465 466 452 465 38 45 55 39 35 48 Humidity, per cent Breaking strength, Lhs. (14 tests) (14 t?sts) (14 t?stn) (18tests) (18 tests) (17 t e s z ) 3.69 3 '75 4.13 3.75 3 84 High 3.88 2 8s 2 88 3.13 2.94 3 13 Low 3.50 3.28 3.26 3 21 3.E4 3 72 A vel'age 3.71
It is obvious that there are no great differelices in the individual cakes. The general arerages check very closely. An accuracy of 1 to 2 per cent is readily attainable. After the coiiditioiis h a w been standardized it is not necessary to use more than thirty cakes for each tzst. ' Similar series with other oi!s, nnhydrogeiiated and hydrogenated, seem to sh0.s that hgdrogenatioii results in greater shorteiiing power. Measurements have been inaclss of tlie shortening power of the following oils and fats : Lard Lard compsund Buttes Cottonseed oil Cottonseed oil, hydrogenated Coconut oil Cocznut oi., h:;drJpenatezl
Corozo (cohune nuti oil Corn oil'
Olive oil Peanut oil Peanut oil, hydrogenated Rapeseed oil Soybean oil
I n all the comparatire breaking tests made on vaiions oils and fats, lard is the best shortening agent; hence it is use:? as the standard. I t s breaking strength will vary aecordiiig to the conditions of standardization, and each operator must determine the value to be used as a standard. The shortoineter value in pounds is arbitrarily taken as 100 per cent. All other oils and fats having less shortening power will have a greater shortoinater value. This weig!qt in pounds of the standard divided by the weight in pounds of any other oil or fa,t will give its relative shortening value. Experiments determining tlie crushing strength are not included in this article, but the same relatioiiship holds.
799
CLASSIFICATIOP;01 FLOTX~ By liolding all other ingredients constant aiid varying the flour usnd it is possible to arrive a t a satisfaetory classification of flours.' A few result; on flour are showii: CLASSIFICATIOS OB FLOUR
BRWXIXG8 T R D N Q T l I Lbs.
Soft n-inter Soft minter Soft nintes Soft winter l~lediumn-inter Medium ninter Medium n5nter Strong winter Strong n-inter Strong winter Spring Spring Snring
2 49 2 33 2 48 2 42 2 69 2 79 2 78 3 ni 304 3 07 3 39 3 39 3 09
DEFISITIONOF SHORTENSWQ Thai cake which requires the least load to measure its breaking strrng,h is the shortest, that, which requires the heayie-t h a d is tlie least short. The b e s t shortening is that material which when baked in a do~-igli gives to the product :L ininimum breaking styength arc1 a ininimum crushing strength. SUMMARY
I-Apparatils has been devised which will measure the shortening value of different oils and fats and mixtures of them. 2-Shoitening has been defined in terms of measurable units. 3-Lard has been found to be the best shortening agent. &Partial hydrogenation of a n oil increases its shortening power. 5--A method has been suggested whereby flours may be classified. Further n-ork is being done alcng this line.
A Process for Producing Palatable Sirup From Sugar Beets By Sidney F. Sherwood 3FFlCn OF s U G h R - P L 4 K T ISVDSTlGATlONs,
B E R B ~ OCF
P L 4 N T IKDU-TRY,
The S u g a r B e e t (October 1906) refers to tlie \tir> objectionable flai-or aiid odor of sirup prepared from sugar beets and states that during the preceding fifty years numerous experiments had been inade t o eliminate this, but that all of the processes suggested were worthless. The same journal ( J a n u a r y 1908) contains a brief note stating that "excellent" sirup is made from beets i n Belgium and Germany by cooking the beets in mater for several hours, pressing out the juice apd evaporating directll- to sirup of about 75 per cent solids; the statement is made also that about 70 g. of suliuric acid are added t o the extract from 1 0 0 k. of beets. I n 1917, C. 0. Townsend and W. C. Gore" described a process. the essentials o€ which consisted in reducing the beet roots to thin slices, extracting t!ic sugar by m e a i i ~of hot imter, drawing off tlie sugar solution €rom the beet chips, and subjecting it to slow and long continued boiling and constant removal of scums during the process of evaporation. Acceptable sirup could be produced by the process recommended, but in a great many cases the odor nnd flai-or TT as highly ol?jectionable, while the sirup mas a1x-a.m ~ e r ydark in color. I n January 1919, the writer suggested iiiiprovements in the process, the use of \%-hieli Received J u n e 0, 1cJ21. " Sugar B e e t Sirup." U. S . D e p a r t m e n t of A4griculture, lial-?ne?s' Bullettir, 523 (1917).
DDPLI~TVEXT O F .\GRICULTURE,
~'AsHINGToY,
D.
c.
resulted in marked improvement in the quality of the sirup produced. These suggestions vTere attached in printed form to copies of the bulletiii sent out thereafter, and included thorongli ripeness of the beet, removal of the top and upper green colored portions, removal of the skin, perniitting the slices to fall directly into water of sufficient depth to prevent access of air and consequent oxidation and darkening of the slices, and direct evaporation to sirup. John 31. Ort and James R. Vithrom, mho investigated the preparation of beet sirup, n-ere iinacquainted with the fact that this improved process had been offered a t the time they presented the results of their investigations before the Division of Industrial ai?d Ecgiiieering Chemistry at tlie 57th Meeting of the American Chemical Society, B~iffalo,K. Y., April 7 to 11, 1919, but refer to it in their publislied article,I and state that the precautions used are similar to those used by them and that the results obtained shoulcl be better than in the case of the original method. They triad many chemical and mechanical processes fo! c,larificatioii and removal of objectionable odor and flavoi aiid state that none of them resulted in marked improvement in flavor. Identical results have been obtained by the writer in using inally similar processes, and it is concluded that it is not advisable to suggest chemical processes a t all f o r use where the sirup is to be produced upon a small I THIS JOCRSAL, 1 2 ( 1 9 2 0 ) , 154.
800
T H E JOURNAL O F IA'DC'STRIAL A N D E N G I N E E R I N G C H E M I S T R Y
scale, and that any mechanical processes suggested should be of the simplest sort. Ort and Withrow conclude that various published processes for making palatable sugar beet sirup do not consistently fulfil all claims made f o r them, that the sirup should not be evaporated in copper kettles, that, in the case of immature beets, the fla~7orwill be improved by preliminary storage, etc.
I N P R OPV RO ~C E S ~ The frequently occurring unpleasant and objectionable odor and flavor of beet sirup made by the original process is quite similar t o that of beet molasses, though, of course, very much less pronounced. While the use of the modifications noted above resulted in marked improvement in the characteristics of the sirup, the objectionable odor and flavor was not always entirely absent and the work has been continued at intervals. Koting that beet molasses is a product resulting from the evaporation of juices and sirup under reducecl pressure, it was considered that the characteristics of the sirup might be improved by scme process of heating under pressure, and many experiments were made relative to processes of blowing air, steam, and superheated steam through juice, semi-sirup, and finished sirup ; heating juice, semi-sirup, and finished sirup under pressure and at temperatures greater than the normal boiling point of finished sirup (105.5O t o 106.5" C.), etc. As a result, the following process, for which a government patent1 has been issued and the use of which is free to any citizen of the United States, was developed early in 1920, and is suggrrted as one affording the production of a satisfactory sirup from sugar beets : The beets are washed and the tops, upper green portions, and skin or peel removed. The beets are sliced, permitting the slices t o fall directly into warm water of sufficient depth (an excess is avoided) to prevent access of air to the slices, heated t o about 80" C. for about an hour, and the extract drained off and strained t o remove fine particles, etc. This extract, or a similar extract prepared in any other manner, is placed in an autoclave-or other container which may be sealed-provided with a controlled outlet for blowing off steam and ordinarily with a pressure gage and thermometer, heated t o 108" to 110" C. -corresponding t o a pressure of approximately 21 lbs. to the sq. in.-and maintained a t this temperature for 1 hr., blowing off a considerable quantity of steam a t approximately 15-min. intervals. The extract is strained to remove the slight quantity of coagulated material and evaporated directly to sirup, removing the very slight amount of scum that forms. Ordinarily this treatment serves t o remove the objectioilable odor and flavor, though the temperature, length of time of heating, and intervals for blowing off steam are not necessarily confined t o the ones mentioned, but may be varied. Thus, in a- number of instances, successful results have been obtained by heating to 110" to 112" C . f o r 0.5 hr. with constant blowing off of steam, the sirup in every instance being of a lighter color than those from a heating period of 1 hr. Sirups from a second extraction of the slices were quite acceptable, though they possessed a somewhat stronger flavor and their appearance was somewhat inferior. Numerous lots of sirup have been prepared by the process from beets grown in southern Michigan and in each case the characteristics were satisfactory in that they were of an amber color, the unpleasant odor and flavor Tvere absent, and the cloudiness was no greater than in average cane or sorghum sirup. ( I n several cases the sirup was perfectly clear.) Sirups such as cane, sorghum, maple, 1 U. S. P a t e n t 1,370,372 (March 1, l 9 2 1 ) , Sidney F. Sherwood.
Vol. 13, No. 9
etc., possess characteristic flarors, and the after-taste of any one of them may be disagreeable t o a person mho is accustomed to any other one. Beet sirup possesses a fiavor quite distinct from any other simp, the first taste being agreeable and very meet, while the after-taste is faintly similar t o that of hoarhound, and expressions of opinion from numerous persons indicate that, as in the case with other sirups, it is agreeable t o some persons and not agrceable to others. YIELDAND COIIPOSITIOSOF SIRUP The yield of sirup varies, depending upon the sugar content of the beets. I n the experimental x-ork, the yield fcom 100 lbs. of beets averaged slightly over 2 qts. for a single extraction, and 1 qt. f o r a second, o r a total of slightly over 3 yts. The beets were sliced with a large knife, and a somewhat larger yield would undoubtedly have been obtained with a slicing machine affording thinner slices. The debris (top, peelings, etc.) amounted to 40 to 50 per cent of the weight of beets. This material, and also the extracted slices, affords a valuable food f o r cattle, chickens, etc. The evaporation was continued until the boiling point reached 105.5" to 106.5" C., the thermometer not being permitted to touch the bottom of the evaporating vessel. The following is the composition of a nuniber of sirups : BEET S I R U P Ash Direct (Not as T o t a l Solids Carbonate or (RefracUndetometer) termined Sulfate) P e r cent P e r cent P e r cent 1.39 69.92 3.57 1.54 2.94 68.87 1.20 68.87 2.86 1.13 70.87 2.96 1.52 3.31 71.82 1.56 3.65 70.87 1.33 11.77 2.77 1.25 69.82 2.43 1.37 70.29 3.00
C O b f P O S I T I O N OX'
Reducing Sugars (As Invert Sugar) P e r cent 3.43 3.32 2.43 3.10 3.01 2.60 2.39 1.54 2.78
APPLICATION T O HONEPRODUCTIOX OF SIRUP The object of these investigations has been directed entirely to processes for the production of palatable sirup from sugar beets on a small scale, as in the home, and the heating may be carried on in a very satisfactory manner in the ordinary pressure cookers used in a p e a t number OP homes. I n fact, one of these cookers was used frequently f o r preparing the experimental sirup. With beets a t $7 per ton, the cost of 100 lbs. would amount t o only 35 cents, and sirup could be produced at small cost if, as in the case in the home, the value of time and labor were not included. I t is considered not improbable that a t some time beet sirup may be produced profitably on a factory scale-utilizing the by-products as cattle feeding material-especially in certain sections of the West, admirably suited for the production of beets but situated f a r from a beet-sugar factory and in which the available agricultural land is insufficient t o support such a factory. I n this connection it is worthy of note that the consumption of beet sirup i n Gerinany iii 1916 to 1917 amounted to 20,000 tons (probably metric).l DECOLORIZISG In connection with the study of the process, experiments were made to ascertain the effect of infusorial earth and decolorizing carbon. The treatment o€ hot semi-sirup containing 45 to 50 per cent solids with 3 per cent of its weight of infusorial earth, filtration under pressure, and direct evaporation t o sirup resulted in sirup of an improved degree of clearness as compared with untreated sirups. Treatment of the filtrate with decolorizing carbon resulted in sirup of somewhat lighter color, but the differ1 Berthold Block, (1920), 282
"
Beet
Sirup,"
Through J .
fabr. sucre., 6 1
Sept., 1921
T H E J O U R N A L OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
ences between these sirups and sirups from treatment with Obviously such infusorial earth alone were not great. processes would not be practical f o r use in small-scale operations, though they mould probably prove advantageous in the Case of factory production. The writer has not had a n opportunity to consult the book by Berthold Rlocli on beet sirup manufacture alld use, but a r e ~ i e wof it makes no mention of superheating processes, though a brief reference1 t o the manufacture in Germany of sirup from beets states that coarse pieces of ~ . 3 hrs., beets a1-e treated wij,h steam at 100” to 1 0 4 ~for the developresulting in remoyal of bad ,,dor alld flal or merit of a flavor of vanilla. Subsequent to working out the above process, the -writer became accjuailzted with a patent issued to H. S. Alexander2 covering a process for producing a n ‘‘ edible ” sirup from sugar beets in which the beets are cooked before pulping for 0.79 to 1 5 lirs., ixeferably by steam under pressure and at a temperalure of 110” to 130” C., shredded, pressed, and the juice filtered and evaporated to sirup; and also one issued to P. Kestner3 covering a
801
process f o r evaporating beet juice in an evaporator until sirup of the desired concentration has been produced and then heating under pressure €or a very brief period l o remove objectionable odor and flaT-or. As an example, he states that sirup that would boil a t 120” C. under atmosPheric pressure is heated under pressure until the temperature reaches 130” C., more or less, and the sirup is then cooled at once by releasing the pressure. H e states that it can be maintained a t this high temperature for a few secolids only or the sirup will Ice caramelized (burned). The nriter‘s process is beliered t o be 1nore satisfactory than either Of these, in that the introduction into the extract of semi-soluble and suspended material from cooked aiid pulped beets is al-oided and actual filtration is rendered unnecessarg, while the danger of scorching is eliminated.
COSCLUSIONS 1 - ~simple and satisfactory process is described Tv~lere.. by the objectionable odor and flavor of beet sirup is eliminated and a palatable sirup produced. 2-The compojition of several sirups is given, -
A Study on the Oil Bromide ‘Test of Linseed Oil’ By Thomas A. Davidson 31, Eastbourne Gardens, Monkseaton, Northumberland, England
The valuation of linseed oil as a drying oil is still carried out by indirect methods. The iodine value test estimates constituents of a nondrying nature, a s well as those impaiting drying properties to the oil, The hexabromide test applied t o the oil, a s described by Hehner and Mitchel1,z would seem to have fallen into desuetude, whereas renewed attention h a s from time t o time been given t o the test as applied l o the separated f a t t y acids. Lewkowitsche would appear t o have set the fashion by stating t h a t a f t e r “very extensive practice i t is preferable to apply this t e s t t o t h e isolated f a t t y acids.” The drying properties of linseed oil are due t o the glycerides of linolenic acid, and not t o linolenic acid itself. The attention given t o the hexabromide test upon t h e isolated f a t t y acids has no doubt been due t o the assumptioii t h a t linolenic acid was present in linseed oil a s the siniple glyceride, trilinolenin, l o which it bears a simple relationship. There is good reason for doubting t h a t linoleiiic acid is present a s a simple glyceride, as the eviclence which the author has to put fonvard suggests t h a t i t exists in linseed oil as a mixed glyceride. On this accourit, and until the composition of the linolenic glycerides has been placed beyond doubt, i t is desirable t h a t the test be applied to the oil direct, and not t o the isolated f a t t y acids. After considerable work on the insoluble bromoglycericles, the author is satisfied t h a t the chief reason for comparative disuse of the hexabroinide test since Hehner and Mitchell’s paper appeared h a s been the difficulty of obtaining the bromo derivative a s a clean, free powder, when dried. To differentiate between t h e two tests i t is proposed t o use the t e r m ‘[oil bromide” for the insoluble brominated glycerides, and “hexabromides” for the insoluble’brominated acid, hexabromostearic acid. While i t is desirable t h a t the oil bromide t e s t should give the full theoretical yield of the linolenic glyceride as it does on difderivative, such a result-depending ferential solubilitie‘s-appears so f a r to be impracticable.
I t is of greater importance t h a t the tesl, carried out under specified conditions, should be capable of giving consistent results in the hands of different workers and have only a small experimental error; and t h a t the precipitate be of reasoilably constant composition. The test proposed here should satisfy these conditions, and has the advantage of a considerable saving of time over the hexabromide t e s t on the isolated f a t t y acids. It should not take much longer to carry out than the determinalion of the iodine value, but its results should prove of considerably greater value a s a n indication of drying power. The oil bromide yields in this test a r e higher than any in t h e literature, and undoubtedly the proposed method applied to the poorer drying oils, such as hempseed and poppy-seed oils, will give higher results than any so f a r recorded for them. The investigation whose results are now being presented was carried out in the intervals of routine work and olher research work from 1907 to 1910, and is not as complete a s the ahthor would wish. Since t h a t time, no opportunity of completing the investigation has offered itself, and the author considers i t desirable, without delaying furlher, t o place on record his results, which, giving an improved method of preparation, go f a r enough to point out the road to complete success for any further investigation.
PURPOSE OF INVESTIGATION The purposes of the investigation where: I-To find out what was wrong with the test
as described by H e h n e r and Mitchel1.l and the causes of the large experimental enor. 2-To ascertain the most convenient method of separating the oil bromides from the reaction mixture. 3-To discover a means of separating the oil bromides as a loose, dry, granular powder. 4-To determine the most reliable and convenient method for the estimation of bromine in the oil bromides. 5-To gain some information as to their properties and cornposition. 6-To formulate the most suitable working conditions to insure maximum yield and maximum purity. ~~
1J. fab. sucre., G 1 (1920), Z E . 1 . 2 Brit. P z t e n t 133,744 (October 13, 1919).
3 Brit. patent 135,235 (November 27, 1919).
Received January 11, 1921. 5 A N A L Y S T 23 (18981, 310. 6 Chemical &chnology o foils, Fats ar.d Waxes, 1909, I, 384.
4
