.
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fining with sulfuric acid are the most toxic to foliage. The sulfonation test, therefore, seems to offer the most reliable test of the probable toxicity of a petroleum distillate of any of the methods of examination thus far tried. All the oils of the first group, classified as very toxic to plants, contain large percentages of chemically active oils (sulfuric acid-soluble), seven of them containing oyer 40 per cent;
Vol. 18, No. 2
the average of the second group is less; the average of the third group is still less; and the average of the fourth group, the safe oils, is the least. The sulfonation test is, therefore, proposed as a Iaboratory method for the examination of petroleum distillates for the estimation of their degree of refinement, and their probable toxicity to foliage.
Subjection of Molasses Treated with Zeolites to the Steffens Process’ By F. R . Bachler AMERICAN BEET SUGARCo., OXNARD, CALIF.
OLLOWING a series of experiments made by the auLaboratory experiments with thin and thick juices were thor to determine the technical and commercial possi- highly successful and promised greatly to advance the art of bilities of removing and recovering potash from beet making sugar. I n the same year Claassenj critically reviewed molasses with the help of natural and artificial zeolites, the the work of Rumpler and Gans and admitted that a considerquestion arose as to how a beet molasses thus treated would able exchange of bases had taken place, but that these juices, respond to desugarization by the Steffens process. now greatly enriched by calcium salts, not only possessed a The base-exchanging power of zeolites, so successfully and far greater viscosity than the untreated juices but that conwidely applied in the softening of water where it is desired centration of treated juices to the point of crvstallization to replace calcium and magbecame almost impossible nesium salts with those of owing to the presence of sodium, can under proper these lime salts. InvestigaA short rCsum6 is given of the efforts, described in conditions be also applied in t i o n of t h e problem by the literature, to introduce natural and artificial replacing the various soothers, including small-sized zeolites into the sugar industry. f a c t o r y t e s t s , confirmed dium and potassium salts of The causes of past failures are recalled; a new angle sugar solutions with the Claassen’s view. of the subject is presented by the author, who subjects corresponding lime sal&. Theory molasses not treated and treated with zeolites to the The first observations in Steffens process. A11 attempts in the past this direction were made by Procedure is described in detail, and analyses are to apply zeolites to the Rumpler,* who established given that seem to support the author’s viewpoint that purification of sugar soluthe fact that the potassium molasses freed of its potash contents with the help tions centered on the treatand sodium c o n t e n t s of of zeolites gives superior results when subjected to ment of beet thin and thick sugar-beet thin juices were Steffens process. juices. By treating mog r e a t l y r e d u c e d if they lasses with zeolites Drior to were allowed to percolate subjection to the Steffens through - lavers of c e r t a i n clays. Rimpler3 later found that this phenomenon was desugarization process, the author is guided by the thought due to the action of zeolites. He proved that sugar solu- that the resulting base-exchange reactions will not only tions thus treated were purified to a certain extent. Some change the character of the molasses but influence its belarge-scale experiments were made in several German sugar havior, sugar yield, etc., during the Steffens desugarization. Obviously the removal of all or a large part of the sodium factories, but the results were unsatisfactory owing to the low and potassium salts will influence the purity of the molasses. exchange power of the zeolites employed. Later, after success in producing a synthetic zeolite of high By “purity” in sugar factory terminology is meant the per exchange power, Gam4 used his artificial product, Permutite, cent sugar contained in the dry substance of a sugar prodanew to solve the problem of removing potassium salts from uct, the interpretation of the term being the higher the purity beet sugar solutions. His Permutite had the approximate the greater the value of the product because of the greater composition of Si02 34.00, A1201 25.00, Na20 14.75, and H2O yield of crystallized sugar obtainable therefrom. This point 25.40 per cent. By treating this material witJh a calcium of view must, therefore, not be overlooked when judging the chloride solution he converted it into a calcium permutite, value of a purification process. One may also expect that the removal of sodium and po“which contained but little Na20.” Gans concentrated his efforts on the purification of beet thin and thick juice be- tassium will cause profound chemical changes due to the cause he agreed with Rumpler that the purification of a setting free of the acid radicals with which sodium and posugar solution should logically be attempted in the first tassium in the molasses are combined. It is a fact that all stages of the manufacturing process in order to increase the the alkali salts of a molasses are soluble. When treating a yield of crystallized sugar by reducing the quantity of melasso- molasses with a calcium zeolite it is possible that the liberated acid radical may combine with the calcium set free from genic nonsugars. the zeolite, to form an insoluble calcium salt. Such a re1 Received August 12,1925. :Deul. Z u c k n i n d . , 16, 585, 625 (1901). action would, of course, be a step in the right direction, that
F
a 4
Z. Ver. deut. Zuckerind.. 68, 788 (1903). Ibid., 67, 206 (1907).
6
Z. Ver.
deut. Zuckerind., 67, 931 (1907).
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Table I-comparison of Original Molasses with Zeolite-Treated Molasses A-Original molasses as used for all experiments B-Same molasses after diluting preparatory to Steffens process but before zeolite treatment C-Same as B, but after zeolite treatment. Solutions I3 and C were filtered prior to analysis -SOLUTION A---SOLUTION B-As O n dry As On dry found substance substance found Item Per cent Per cent Per cent Per cent 1 Moisture 14.20 86.57 2 Dry substance 85.80 100.00 13.69 100.00 3 13.99 Dry substance by refractometer 87.72 102.23 102.19 4 Dry substance by Brix spindle 92.40" 107.69 14.55 106.28 5 Direct polarization 48.20 56.18 7.70 56.24 7.82 57.12 6 Clerget polarization 48.96 57.06 1.665 12.16 7 Carbonate ash 10.40 12.12 Sulfate ash 10 per cent 12.07 14.07 1.922 14.04 8 Total nonsugars referred to dry substance, Clerget 9 4.205 30.72 polarization, and carbonate ash 26.44 30.82 2.540 18.56 Organic nonsugar by difference 16.04 18.70 10 Nonsugar coeEicient = Clerget polarization 1.85 11 1.86 Total nonsugar
+
Organic
=
Clerget polarization Organic nonsugar
14
Impurity coefficient =
Total Clerget polarization
15
Inorganic coefficient =
ash Clerget polarization " loo
16
Impurity coefficient
17
FeiOa Ca Mg K Na
18
19 20 21 22 23 24 25
:
