664
W. W. BINKLEY AND M. L. WOLFROM
none by the Clemmensen procedure was found to give the pinacolone, 1,2,2,2-tetra-p-fluoro-
Vol. 69
phenylethanone-1. RECEIVED JULY 31, 1946
LAWRENCE, KANSAS
[CONTRIBUTION FROM THE CHEMICAL IAABORATORY OF THEOHIO
STATE
UNIVERSITY]
Recovery of Sucrose from Cane Blackstrap and.Beet Molasses BY W. W. BINKLEY’AND M. L. WOLFROM The crystallization of sucrose from the juices determine the non-sucrose constituents of the of the two main plant sources, the sugar cane and fractions herein separated. the sugar beet, constitutes a major industry. Experimental After all of the sucrose has been removed by crysCane Blackstrap Molasses.-The cane blackstrap motallization procedures to the extent that is fea- lasses was produced in Cuba by the Cunagua Central of sible, there remains a mother liquor which is known the American SugaroRefining Co., New York, N. Y.6 as molasses. That from the sugar cane, com- It was stored a t 8-10 . This molasses was obtained from a mixture of 7 5 4 0 % Javan varieties POJ 2714 and POJ monly known as blackstrap, is used mainly as a 2878 and 20-250/, Cuban stock termed Crystalina. source of alcohol. Various attempts have been Anal. (yooriginal molasses) Solids, 82.3; ash, 5.5; made to recover further amounts of sucrose from s ~ c r o s e 3, ~2 ; reducing sugars (as invert sugar),* 15; d , blackstrap molasses after prior removal of the 1.468 g. per ml. a t 25”; color, nearly black; taste, burnt reducing sugars with invertase-free yeasts (Olivar- sweet. Adsorption of Cane Blackstrap Molasses on Clay.ius process2), lime (Battelle process3) or barium amount of 50 g. of the above cane blackstrap molasses hydroxide (Holven process4). None of these meth- An was diluted with 25 ml. of distilled water. A smooth ods havc. proved commercially successful. The paste was prepared by the addition of 25 g. of a mixture molasses from the sugar beet, however, is proc- of 5 parts (by wt.) of clayYand 1 part of “Celite”lo to the essed in various ways t o recover further sucrose. diluted molasses. This paste was suspended, employing agitation, in 500 ml. of absolute ethanol. The niethocls employed rest upon the separation good Sucrose Separation from Cane Blackstrap Mo!asses.of sucrose as a chemical derivative, generally a The molasses-clay-“Ce1ite”-ethanol suspension was metallic saccharate, from which the sucrose is re- added a t the top of a 7-9 by 11-12 cm. columnll of a mixture (250 g.) of 5/1: clay/‘‘C?lite” in a 2-liter percolator generated. arranged to permit the collection of the effluent without In the work herein recorded, we wish to report interfering with the operation of the column. The the application of chromatographic procedures Chromatogram was developed with three liters of 95% to the recovery of sucrose from cane or beet mo- ethanol (the azeotrope). A total of 11.87 g. of sucrose lasses, To this end, the molasses was adsorbed on (74.2% of that present) of excellent purity was obtained concentration of the effluent. The residual sirup oba native clay and the chromatogram was devel- on tained on solvent removal was sweet and highly palatable. oped with dilute ethanol. From the effluent The nature of the effluent was investigated by collection in (Table I) the sucrose was readily crystallized as a nine fractions, data on which are given in Table I. Fraccolorless, high purity product. From the cane tion 2 was light green in color; fractions 3 to 8 were a golden color; fractions 8 and 9 were nearly colorless. blackstrap molasses, there was recovered 74% of Fractions 2, 3 and 4 had strong, pleasant, rum-like odors the sucrose present; from the beet molasses, the and it was obvious that the characteristic flavoring subrecovery wa’s93%). The nature of the effluent was stances were concentrated therein. The other fractions further investigated by collecting it in the series had virtually no odor. The residual sirups obtained on removal were sweet and highly palatable. of fractions tjhown in the table. Fractions 2, 3 and solvent Beet Molasses.-The beet molasses was produced by 4 (Table I) of the effluent from the cane molasses the Michigan oSugar Co., Saginaw, Michigan.’* I t was possessed a strong, pleasant and rum-like odor. stored a t 8-10 . The residual sirups from the sucrose crystallizaAnal. (70origitial molasses) Solids, 81.2; ash, 2 . 0 ; ~ raffinosez72.2; reducing sugars, absent; tions with the cane molasses were highly palatable. s ~ c r o s e ,46.6; The procedure employed in this work is an ad- d , 1.416 g. per ml. a t 25 ; color, brown. of Beet Molasses on Clay.-An amount of aptation to the materials in hand of the general 50Adsorption g. of the above beet molasses was adsorbed on 30 g. of chromatogra.phic procedures developed in this clay as described above for cane molasses. La bor;itory5arid especially thosesbemploying clay Sucrose Separation from Beet Molasses.--The chromatogram was developed as described above for cane blackas an adsorbent. Further work is in progress to ~~. . . _ _ ~ (1) Sugar Research Foundation Associate of The Ohio State University Research Foundation (Project 190). (2) H. DeF. Cllivarius, U. S. Patents 1,730,473 (1929), 1,788,628 (1931). (3) E. E. Ba-telle. U. S. Patents 1,044,003 (1913), 1,044,004 11913). (4) A. L. Holven, U. S.Patents 1,878,144 (1933), 1,878,145(1933). (5a) W. H. McNeely, pi. W. Binkley and M. I,. Wolfrom, THIS JOURNAL, 67, 527 (1946); (b) B. W. Lew, M. L. Wolfrom and R. M. Goepp, Jr., i b i d . , 67, 1865 (1945); 68, 1449 (1946); (c) L. W. Georges. R . S. Rower and M. L. Wolfrom, i b i d . , 68, 21139 (1946).
( G ) We are indebted to Mr. Louis A. Wills of the above company for this material. (7) Modified Clerget method. (8) Munson-Walker method. (9) Florex XXX. manufactured by the Floridin Co., Warren, Pennsylvania. (10) No, 535, manufactured by Johns-hfanville Co., New York, N Y. (11) Column dimensions refer to the adsorbent. (12) We are indebted t o Mr. Geoffrey S. Childs of the above company for this material.
DIFFUSIONSTUDY OF LIGNINSULFONIC ACIDS IN SULFITE WASTELIQUOR
March, 1!347
EFFLUENT FRACTIONS FROM
TABLE I CHROMATOGRAM OF MOLASSES ON CLAY
THE
Sucrose
I
Volume of Type ( J f molasses
E'ractiun
Cane blackstrap
1 2 3 4 5
6 7 8 0
Total Beet
1 2 3 4 5 6
fraction, ml.
0.3
.3 .6 5.9
-
3670 270 190 200 210 230 390
27.4 0.2 .2
.2
180-182
10.61
180-182'
$66.8'
179-181
c 5, water
g.
.. 180-182
--.
[a1280,
c 5, water
0.11 .17 .16 .45 .37
..
~
4-65.9'
1.26
f66.7"
0.05 .44 .68 .90 2.46 1.87 1.97
... 0.05 .l5
strap molasses. 'The effluent mas collected in eleven fractions. Data on these fractions are listed in Table I. Fractions two and three of Table I had a strong, unpleasa n t odor characteristic of beet molasses; all of the fractions were nearly colorless. A total of 21.7 g. of sucrose (93.3% of that present) of excellent purity was obtained on concentration of the effluent. The residual sirups obtained on complete solvent removal were unpalatable.
Acknowledgment.--Ke are pleased to acknowledge the assistance in this work of Mr. John Kolbas.
[COX TRIHUTION FROM PVLP hl11,LS
C.
...
1.4 .30 2.8 1.44 2.92 4.9 I -170 5 .
