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Bibliographic Series



No. 5



MOLASSES



ARTHUR D. LITTLE, Inc,

CHEMISTS AND ENGINEERS
CAMBRIDGE, MASS.




CAMBRIDGE, MASS.
1920



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CoUpgp of Idtbfral Arts

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READING LIST

ON

MOLASSES



Compiled by
CLARENCE JAY WEST \ S %h>

Information Department
Arthur D. Little, Inc.

Cambridge, Mass.



CAMBRIDGE, MASS.
1920



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copyright, 1920
Arthur D. Little, Inc.



THE MURRAY PRINTING COMPANY
KENDALL SQUARE, CAMBRIDGE






TABLE OF CONTENTS

Page

Introduction 5

Composition 5

Uses 6

Sugar 6

Alcohol 6

Food 7

Fuel 8

Fertilizer 8

Other Uses 8

Statistics 8

Bibliography 11

General 11

Composition 15

Analysis 20

Recovery of Sugar 28

Fermentation 31

Uses 34

Fertilizer 34

Foods and feeding-stuffs 36

Miscellaneous 47

Abbreviations Used 48



MOLASSES



Introduction

Molasses is probably the most important by-product of the
sugar industry. It is also of interest from a chemical point of view
and because of the variety of ways in which it has been utilized.

Molasses is the final mother sirup obtained in the crystal-
lization of sugar. The manufacturing processes of the sugar
industry may roughly be divided into two. The first is the puri-
fication of the juice obtained from the cane or beet, in which
lime, carbon dioxide and sulfur dioxide are the principal reagents
used, and the concentration to a sirup. The second is the frac-
tional crystallization of the sifup or *' thick juice " to obtain the
sugar. In this vacuum pans and crystalHzers are employed to
produce crystals which are separated by means of centrifugals.
The impurities, organic and inorganic, present in the juice (usu-
ally termed "non-sugars") prevent the crystallization of a cer-
tain part of the sugar; it is this final mother liquor which is
molasses. It contains all the soluble impurities of the original
juice, not removed in the process of purification, together with
the sugar associated with them. The importance of molasses is
seen when it is realized that from 15 to 25% of the sugar present
in the original juice is found in the final molasses.

Distinction is sometimes made between a " true " molasses,
which is a mother sirup from which no more sugar can be crystal-
lized out under the most favorable conditions and a "commercial'*
molasses, which is obtained in manufacturing processes. Under
efficient operating conditions, the two are practically the same.
Low-grade cane molasses is often spoken of as blackstrap molasses.

Composition

The following analyses are average values for cane and beet
molasses :

Cane Beet

% %

Water 20 20

Sucrose 30 50

Raffinose Present

Invert Sugar 32 Trace

Ash 6 10

Organic (non-sugar) 12 20

Sugar: non-sugar 3:5 5:3

Sugar: ash 5:1 5:1



g MOLASSES

The ash is interesting because of its high potash content
and the very low soda content. Even in the presence of a large
excess of soda salts in the soil, the sugar cane assimilates potash
if available; and if not, it withers and dies. The potash content,
which depends upon the nature of the soil, varies from 2 to 6%.
During the war, because of the high cost of potash, serious attempt
was made to recover this potash, and a plant was erected in
California. The molasses was first fermented, the alcohol dis-
tilled, the yeast separated and the waste or slop evaporated to
about 30° Be, and then burned in a reverberatory furnace. About
4 to 6% ash containing 36 to 38% potash was obtained, which
was sold as such to the fertilizer industry. With the return to a
normal price the process will probably not be a profitable one.

The non-sugar portion includes gum, organic acids (amino-
acids) nitrogeneous bodies, caramel and other products of decom-
position of the sugars. Betaine is isolated in considerable quantity
and is used for medicinal purposes.

Uses

Sugar. Various processes have been developed through
which the sugar present in the molasses may be recovered.
These processes consist either in removing some of the impuri-
ties so as to increase the ratio of sugar to non-sugar present, or
in precipitating the sugar as an insoluble compound, by the use
of barium, strontiiun, or calcium oxide. These salts are then
decomposed with carbon dioxide, when sugar and the correspond-
ing carbonate are obtained. The barium process is in operation
at Wallaceburg, Ontario, while the lime process (Steffen process)
is used by the Great Western Sugar Co. The strontium process
is used in Germany. Of the three processes the barium yields a
product of the highest purity (93%) as compared with 88% for
the strontium and 81% for the calcium process. On the other
hand, the recovery of bariimi oxide from the carbonate involves
an expensive electric furnace installation. In spite of the lower
purity of the product from the calcium process, it would seem
that this is the most satisfactory method for the ordinary factory.

Alcohol. One of the important uses of molasses is for the
production of industrial alcohol. Formerly, it was also used for
the manufacture of rum. Since the sugar is present in a fer-
mentable form, it requires no preliminary treatment, such as is
necessary in the case of grain and potatoes. The molasses is
simply diluted to a suitable concentration (17 to 22%), acidified
with sulfuric acid, inoculated with yeast, and allowed to stand at
an initial temperature of 18°C. (65°F.) for 48 to 96 hours, when
the fermentation is complete. The yield is about 3.75 gallons of
95% alcohol per 100 pounds of molasses, or about 75 gallons per ton.

The following tables give the amount of molasses consumed



INTRODUCTION



Molasses used
Gallons


Rum produced
Gallons


2,900,376


2,253,624


3,833,578


2,844,313


3,943,301


2,908,898


3,653,755


2,881,414


1,860,361


1,526,743


1,000,425


816,103


-OLOGNE Spirits




Molasses used


Spirits produced


Gallons


Gallons


39,392,697


20,587,200


*119,467,918


39,736,548


77,034,173


58,052,924


*108,843,878


82,460,340


*116,167,599


83,293,277


*122,498,268


75,407,357



during the past five years in the production of rum and cologne
spirits :

Rum



1910
1915
1916
1917
1918
1919



1910
1915
1916
1917
1918
1919

♦Includes dilute saccharine liquid.

At the present time the abnormal price of industrial (de-
natured) alcohol makes this a very attractive proposition.

Food. The impurities of the sugar cane have a pleasant
aromatic flavor and raw cane sugar and cane sirups are common
articles of himian diet. Beet sugar molasses, while not suitable
for human consimiption, is used as a cattle food.

According to Deerr, the use of molasses as a cattle food
originated with an observation by Hughes that the interior pith
of the sugar cane was capable of absorbing large quantities of
molasses, affording a product which could be shipped in bags;
this was called " molascuit." Various other absorbents have been
used, among which may be mentioned peat, sphagnum moss,
bran and various kinds of meal, beet pulp and alfalfa. Molassine
meal is composed of beet and cane molasses absorbed on sphagnum
moss, while Xtravim feed contains cane molasses only. There
are some fifty or more mixed feeds on the market, all of which
contain more or less molasses. The amount of such feed pro-
duced each year is roughly estimated by "Sugar" at 2,000,000
tons; the molasses content varies from 10 to 50%.

Molasses as such is not a complete food, since it contains
only about 0.15% nitrogen. Its food value lies in its sugar con-
tent. It is generally recognized that the salts of molasses have a
distinct value in stimulating the appetite and the digestion, so
that larger amounts of forage are eaten.



8 MOLASSES

Typical analyses of molasses feeds follow:*

Protein Fat Fiber

Sucrose 16.50 3.50 12.50

H.& S.Alfalfa 19.50 4.20 12.35

International Dairy 18.94 5.98 11.72

Purina 17.83 3.09 17.18

Cloverleaf Horse 9.58 1.89 12.05

Algrave Horse 11.64 4.56 9.78

Xtravim 5.24 0.50 4.95

Green Cross 9.50 2.25 7.19

Molassine Meal 8.82 0.63 6.25

♦Selected at random from Control Series, Bulletin 3, Mass. Agr, Expt. Station,
Amherst, Mass.

Use as Fuel. Molasses is occasionally used as fuel to sup-
plement that afforded by bagasse. The simplest way is to let
the molasses fall onto the bagasse on its way to the furnaces.
It may also be atomized and burned in a special furnace. Actual
determinations by Atwater have given a value of 6956 B.T.U.
per pound of dry matter; or of 4500 B.T.U. when the 25% water
content is not removed. Air dried wood gives from 4500 to 5000
B.T.U., bagasse with 45% water 4500 B.T.U., petroleum 16000-
17000 B.T.U. and anthracite coal 15000-16000 B.T.U. per pound.

If the ashes are returned to the soil, most of the potash is
made available as plant food.

Fertilizer. Many experiments have been carried out to
determine the fertilizing value of molasses. The results thus far
are conflicting. One set indicates that molasses aids the nitrogen-
fixing organisms in their work, resulting in an increase in the
nitrogen content of the soil and in increased crops. Another
study has shown that the continued addition of glucose to soil
bacteria in vitro retards the activity of the nitrifying and ammo-
nifying organisms and accelerates that of the denitrifying races.
The truth is still to be determined.

Other Uses. Blackstrap molasses is also used in the leather
industry and in the preparation of shoe blacking and leather
dressing.

Statistics

Statistics on the world production of molasses are very diffi-
cult to obtain. The following figures are taken from the July,
1920 issue of Sugar.

** The total amount of cane molasses produced in the United
States during the season of 1918-1919 was 28,049,000 gallons,
according to the United States Department of Agriculture, of
which 16,101,650 gallons was blackstrap. The amount of beet
molasses obtained from the manufacture of beet sugar is prac-
tically negligible, since' the introduction of the Steffens process in
beet sugar factories, and no figures are available for this product.



INTRODUCTION



9



Practically all of that which is obtained, however, is used for
feeding purposes.

" The only available figures for production in foreign coun-
tries are for Porto Rico during the season of 1918-1919 when
18,000,000 gallons were produced, practically all of which was
blackstrap. It is estimated that about 22,000,000 gallons will be
obtained from the present crop. The production of molasses in
Cuba during 1918-1919 was estimated at 198,588,800 gallons,
all of which may be regarded as blackstrap.

** Imports of molasses into the United States for 1918-1919
are as follows:

Gallons

Cuba 124,254,663

Porto Rico 15,118,678

Hawaii 11,065,996

Other countries —

(Central America, Mexico, Peru and other
South American countries, Dominican Republic
and PhiHppine Islands) 5,820,054"

Molasses Production^
United States

(Source: Stat. Abs. 1919, p. 231. All figures of molasses
production prior to 1915-1916 are those of A. Bouchereau, New
Orleans, except that for census years and 1898-1899, which are
those of the Census Bureau. Subsequent figures are those of the
Department of Agriculture.)





Louisiana
Gallons


Other Southern States
Gallons


Total
Gallons


1852-18602


20,032,717


1,065,213


21,097,930


1861-18702


8,048,261


951,954


9,000,215


1871-18802


11,096,738


1,213,302


12,310,040


1881-18902


14,737,034


3,800,728


18,537,762


1891-18952


21,277,179


6,124,752


27,401,930


1896-1900'


20,661,216


6,431,452


27,092,662


1901-19052


26,953,377


7,718,527


34,671,902


1906-19102


24,982,244


6,264,496


31,246,748


1911-19152


25,540,900


10,804,632


36,345,535


1915-1916


15,230,000






1916-1917


30,387,000






1917-1918


36,379,000


25,622,811


62^001^811


1918-1919


38,842,000


35,584,000


74,426,000


1919-1920









^All figures for molasses, except those for 1898-99,
for "Other Southern States " relate to sirup only.
2 Average for the period.



include sirup; those for 1918-19



10 MOLASSES

Molasses Production in Louisiana
(Source, Year Book of the Department of Agriculture, 1919.)







Gallons
per ton of




Gallons


Sugar


1911


35,062,525


99


1912


14,302,169


93


1913


24,046,320


82


1914


17,177,143


71


1915


12,743,000


93


1916


26,154,000


86


1917


30,728,000


126


1918


28,049,000


100


1919






1911-1914-


- Louisiana Sugar Planters' Association figures.


1914-date -


- Bureau of Crop Estimates, U.
Exports (United States)


S. Dept. Agr.




Gallons


Value


1910


1,505,355


$216,336


1915


1,148,741


145,274


1916


4,387,369


524,861


1917


2,889,991


442,967


1918


3,811,341


847,692


1919


6,123,765


1,277,980




Imports (United States)






Gallons


Value


1910


31,292,165


$1,367,362


1915


70,839,623


1,963,505


1916


85,716,673


3,775,894


1917


110,237,888


10,946,571


1918


130,730,861


9,177,833


1919


130,074,717


7,471,060



BIBLIOGRAPHY

General

Action of final molasses on iron and steel. La. Planter 52, 414;
CAS 2635

Andrews, Frank. Sugar supply of the U. S. Dept. Agr. Year-
book, 1917, 447-460; C. A. 12, 1708.

Andrlik, K., Urban, Kr., and Stanek, V. Molasses and analagous
waste sugar products. Z. Zuckerind. Bohmen. 25, 247-272
(1901); J. S. C. I. 20, 374.

Aulard, A. Estimation of the commercial value of molasses.
Chem.-Ztg. 18, 1279-1280 (1894); J. S. C. I. 14, 46.

Barbados and Porto Rico Molasses. Imp. Dept. of Agr. for the
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Bass, W. L. Cane Sugar. New Orleans. La. Planter.

Bauer, Emil. Sources of loss in production of potassium car-
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(1909);C. A. 4, 685. .

Besson and Rosset. Neutralization of syrups and molasses with
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and Blouin, R. E. Chemistry of the sugar cane and its



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Caullet, Paul. La Question des Melasses. Paris, 1902. 143 pp.

Chamber of Commerce, New York. Trade in Agricultural Prod-
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Claassen , H. Electrolytic treatment of molasses. Z. Ver. Zuck-
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Coates, C. E. Some notes on present conditions m Louisiana
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C. A. 13, 668.

Comparison of sundry methods for expelling the molasses and
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11, 55-60 (1831).



12 MOLASSES

Crawley, J. T. Incipient carbonization or combustion of molasses.

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therefrom to obtain ammonia products, amino-acids and

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C. A. 13, 1950.
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3179.



GENERAL 13

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Theories of the formation of molasses from the stand-



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14 MOLASSES

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GENERAL 15

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Tremann, F. Sugar from molasses. Ger. Pat. 288,411. Aug.
30, 1913. C. A. 10, 2316.

Urban, K. Vessels to remove foam from molasses and syrup. Z.
Zuckerind. Bohmen. 35, 239-243; C. A. 5, 2753.

Vermehren, A. Brief observations on molasses. Deut. Zuck-
erind. 36, 679; C. A. 6, 1073.

Walker, H. S. The sugar industry in the Island of Negros.
Bureau of Science, Manila. 145 pp.

Wasselenks. Purity of the final molasses. Zapiski, 3, 86 (1907) ;
Centr. Zuckerind. 15, 950; C. A. 1, 2036.

Weisberg. J. Exact comparison between the apparent purities
of all sugar house products during manufacture from diffu-
sion juice to molasses. Bull, assoc. chim. sucr. dist. 27,
1145-1158 (1909); C. A. 4, 2391; Bull, assoc. chim. sucr.
dist. 28, 132-136 (1910); C. A. 4, 3020; Centr. Zuckerind.
18, 1400-1401, 1454-1455; C. A. 4, 3307.

Real and apparent purity. Bull, assoc. chim. sucr.

dist. 25, 944-946 (1907); C. A. 2, 2739.

Wiley, H. W. Adulteration of molasses. Division of Chemistry.

Bull. 13, part VI, pp. 242.
Yield of molasses in Louisiana this season. La. Planter 48, 380

C. A. 6, 2860.

Composition

Andrlik, K. Guanine pentoside from molasses waste liquor.
Proc. 7th Intern. Cong. Appl. Chem. 1909; C. A. 5, 2006;


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