CONCLUSIONS AND RECOMMENDATIONS
Much more progress has been made in finding technically feasible ways of converting agricultural raw materials t o useful end products than in finding economically feasible ways to do so. Many research results must be held in abeyance until price or cost conditions change sufficiently t o permit their profitable application. Such research results are not failures, because they may be regarded as constituting a cushion t o fall back on if agricultural surplus conditions should become still worse, or if our dependence on renewable resources should become greater. They also provide leads for other more successful developments applicable t o current economic situations. T h e quest in technological research should be directed toward
1. Finding less costly methods for converting known ingredients of surplus products t o known industrially useful forms 2. Discovering or identifying unknown components of the products having value to industry 3. Devising new end products t h a t can utilize the components of agricultural surpluses more advant,ageously than alternative sources of the same ingredients The success that has already been attained i n these directions suggests t h a t more such research is entirely warranted. Greater supplementation of the technological research with marketing research designed to solve economic problems associated with assembly or purchase of the raw materials and with distribution or sale of the end products also is warranted. The full fruits of technological research cannot be realized until industry is shown how adoption of the results can yield profits and industrial management is induced t o undertake the operations. It is probably too much to expect that the expediency or profitability of most technological discoveries will be so selfevident that industry will immediately adopt them. Further facts are usually necessary before a board of directors or a manager can afford t o incur the expenses of contracting for raw materials, tooling up for processing, and advertising for distribution of a new or different product. Types of supplementary research t h a t could effectively be in-
tegrated with laboratory research for the purpose of speeding u p or attaining more complete adoption of utilization research results or agricultural surpluses include 1. I n uiry into locations offering continuity of supply, acceptabaity of quality, and stability of price 2 . Inquiry into possibilities for lower buying prices or procurement costs through adjustments in harvesting or assembly methods t h a t may no6 involve the same care of handling required for food markets 3. Inquiry into pricing schemes comparable with the differentiated price methods used in milk markets where greater values are attached to first priority food uses, with attendant lower prices for alternative surplus uses 4. Study of the impact production and sale of the new product will have on other phases of a firm’s operations in order to help judge probable net change in profitability from the new operation 5. Study of economies of scale, work simplification methods, or mechanization techniques that, may be applicable t o the handling and processing of agricultural produce for industrial purposes 6. Market testing of end products to ascertain location and volume of probable potential markets a t varying prices as well as probable colors, forms, sizes, and other attributes of end products, or their packages receiving best acceptance 7 . Estimation of probable cost of launching distribution of the new product and probable time and nature of competition to be anticipated
I
These considerations are probably more applicable to agricultural surpluses as sources of carbohydrates than as sources of protein, fat, or mineral elements. Certainly this is true with respect to plant materials which constitute most agricultural surpluses. Carbohydrates from animal sources such as milk sugar are usually so high priced t h a t a slight excess becomes a serious price depressing surplus; however, these animal source surpluses are not likely t o be of great magnitude. On the other hand, plant sources of carbohydrates must be considered of a n entirely different order of magnitude, purity, and cost. They offer important carbohydrate sources for food as well as nonfood uses and merit serious consideration. RECEIVED for review October 22, 1954.
ACCEPTEDMay 10, 1955.
Economics of Sucrose H. B. HASS Sugar Research Foundation, Inc., 52 Wall S t . , New York 5, N . Y .
ODY H. LAMBORN Lamborn & Co., Inc., 99 Wall S t . , New York 5 , N . Y .
T
HE purpose of this paper is t o call attention t o the opportunities in sugar as a cheap and abundant raw material for industrial organic syntheses. This ifi far from being a new idea, b u t some of us are old enough t o remember when the concept that a major organic industry could be built on petroleum and natural gas was also mostly a matter of conversation on the part of a few enthusiasts. For years the tangible accomplishments were few and of relatively small importance. As one success followed another, chemists succeeded in conveying the spark of imagination to management. As a result, research appropriations became mo?e nearly adjusted to the opportunities implicit in t h e potentialities of petroleum as a storehouse of future chemicals. Now petrochemicals are familiar not only to chemists but also to intelligent laymen. A similar potential exists in carbohydrates, but before it can be realized certain changes must occur in our way of thinking. I n t h e past, and with ample justification, carbohydrate chemists 1392
’
have concerned themselves largely with problems of structure and configuration. This work was absolutely necessary to lay a firm foundation for the future. For the most part, this foundation is now completed for the carbohydrates t h a t eeem destined t o serve aR raw material for a synthetic organic chemical industry of the future. Wow it is necessary t o think of carbohydrates a s organic starting materials. With starch, this forward step has been taken; with sucrose, it is only beginning. T h e curious mental block which prevents organic chemistswith a few notable exceptions-from even investigating the standard reactions of hydroxyl groups with carbohydrate starting materials is almost beyond explanation. About a dozen years ago H. A. Bruson studied the cyanoethylation of about 400 compounds. h’ot until recently was t h e reaction tried on cotton (IO). T h e paradoxical thing is t h a t the cyanoethylation of cotton seems likely t o be far more important economically than the rest of the cyanoethylations put together. This reaction has
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 1
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Carbohydrate Raw Materials Sucrochemistry is the new industrial organic chemistry based on sucrose and its by-products. Although sucrose is the most abundant pure organic compound, it has been relatively neglected as a chemical starting material. Work initiated by Sugar Research Foundation, Inc., has resulted in a new unit process called reductive aminolysis. This yields diamines leading to high polymers, solvents, and water-softening agents. Nonionic surfactants in which sucrose furnishes the hydrophilic moiety are edible and show excellent detergent and emulsifying characteristics. Sucrose by-products yield Celotex, hard board, paper, nylon, cane wax, monosodium glutamate (condiment), aconitic acid, its esters (plasticizers), and ester bisulfite addition products (wetting agents). The manufacture of mannitol, sorbitol and derivatives, and the newest glycerol process are mentioned. Opportunities are available to use sucrose for a host of other interesting syntheses.
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not previously been reported for sucrose, although i t has been carried out at Herstein Laboratories, Inc., without the slightest difficulty. Before a chemist plans a n industrial research program he should have a clear picture of the economics of his starting materials. This is an attempt t o give a bird’s-eye view of the economics of sucrose. I n photosynthesis, the first free carbohydrate t o be formed is sucrose (3). It is not surprising then t h a t sucrose is a component of every green plant that has been carefully examined for its presence. Sucrose is the source of all plant energy and, hence, indirectly of the energy of animals, coal, oil, natural gas, tar, asphalt, and oil shale. Sugar is consumed in all countries and is produced throughout t h e world. I n 1953, world production was 43,625,000 tons or 32.9 lb. of raw sugar per person ( 6 ) . Except for wars, world sugar production has climbed steadily during the years for which statistics are available. Production capacity has outstripped consumption. Cuba in 1952 produced nearly 5,000,000 tons of raw sugar. This year the crop is restricted to 5,000,000 tons because of limited demand. It would not be difficult to double world sugar production if the demand existed. The most important fact about sugar is t h a t more food energ?; can be obtained per acre-year growing sugar cane than by producing any other commercial crop. Last year in Hawaii, for example, the average yield of crystallized raw sugar was more than 10 tons per acre, harvested. With a growing Season averaging 22 months, this was over 5 tons of refined sugar per acre-year ( 1 4 ) . T h e dry weight of bagasse is equal to t h a t of sugar. Including t h e leaves, tops, and molasses, this amounts t o about 12 tons of vegetation per acre-year, dry basis. Crop rotation is not necessary. I n Cuba, sugar has been grown continuously since Christopher Columbus’ second trip in 1493. As many as 35 t o 50 crops have been taken off the same field on successive years without replanting although the average figure is 6 t o 7 years. There is no apparent limit t o the number of successive sugar cane crops which can be taken off the same field with occasional replanting. About 40% of the world supply of commercial sucrose comes from beets, which in Xorth America are grown from Southern California to southern Canada. Europe is t h e big beet sugar source; last year i t produced over 13,000,000 tons. Last year, t h e United States averaged 2.3 tons of beet sugar per acre-year This compares with a national average of slightly over 0.5 ton of wheat per acre-year, 1.1 tons for corn, and 1.75 for potatoes (dry basis) ( 1 1 ) . If the tops, molasses, and extracted pulp of beets are used as cattle feed, more feed per acre can be produced growing beets than alfalfa hay, barley, or a n y crop other than corn. This is entirely neglecting the sucrose which is also of
July 1955
great value in stock feed but is ordinarily reversed for humans. I n addition t o the 2.3 tons of beet sugar per acre-year there are 1.07 tons of beet tops (dry basis), 0.64 ton of dry beet pulp, and 0.25 ton of molasses, totaling 1.96 tons (16). T h e average man requires about 1,000,000 calories of food energy per year. T o raise this in the form of sucrose requires 0.053 acre (Hawaii) or 0.12 acre (beet sugar average, U. S.); as wheat flour, 0.59 acre; as steers, 17.0 acres. I n a world where more than half the people do not have enough t o eat, these facts are important. I n the Western World such productivity makes i t difficult to avoid surpluses. Of course, more than sugar is necessary for complete nutrition; protein, vitamins, and minerals are needed, but it is calories t h a t maintain life. When they fail, the spark of life goes out. Mankind evolved eating sugar. Examination of the natural diets of our closest anthropoid relatives reveals t h a t they are predominantly vegetarian, eating a variety of fruits, stalks, roots, and nuts which contain sucrose. It is, therefore, not surprising t h a t our digestive systems are equipped t o assimilate sucrose, which is inverted as it passes through the intestinal wall and enters the blood stream as glucose and fructose. The efficiency of this process is greater than 99%, and i t is so rapid t h a t a noticeable rise in blood sugar level occurs within minutes after eating sucrose (9). Sucrose is more quickly assimilated than any other food although the difference between t h e rates for sucrose and glucose is only 3% ( 7 ) . The ready assimilation of sugar suggests the desirability of producing pesticides consisting of sucrose attached t o a toxiphoric group. The world consumption of sugar in 1952 by countries is shown on Figure 1. T h e amount ranges from 1.6 pounds per capita for Ethiopia t o 117.7 for Australia. I n general, the more advanced and highly civilized countries are a t or near the top of the list. This may be attributed to three facts. 1. More highly developed countries have the technology and purchasing power t o obtain t h e sugar which their citizens desire. 2. Mental activity on which science and technology ultimately depend is made possible by blood sugar. This can come from a n y food but most readily from sucrose. 3. Excessive taxation limits sugar consumption in many countries with primitive economies.
Figure 2 shows how U. S. sugar consumption has varied over the years. T h e most remarkable thing about this graph is the high degree of constancy in the use of sugar per capita for the past 40 years except for periods of World War I and I1 when the supply was inadequate. For t h e 32 years 1922 t o 1953 inclusive, excepting shortages caused by World War I1 and t h e “scare buying’’ of 1941, the maximum figure is 109.69 for 1926 and the minimum is 93.61 for 1945. This is a fluctuation of &S%. There is no other major commodity of which this can be said.
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COUNTRY
I
the duty of estimating, late in each year, the probable demand for sugar in the United States for the following year. Allocations, based on this estimate, are then made t o the various areas which have historically supplied the U. S. with its sugar requirements-Cuba, Puerto Rico, Hawaii, Philippines, and the U. S. -_ mainland cane and beet areas. Modest amounts are also allocated to certain full-duty producing countries such as Peru and Santo Domingo. This legislation has the effect of supporting and stabilizing, sugar prices in the United States. Ordinarily sugar prices in the rest of the world are high or low, depending upon trading areas and tariffs. There is a trading area involving about 5,000,000 t o 6,000,000 tons of sugar which is spoken of as the world market. The world market involves that sugar which does not have a regular “home.” For example sugar produced in the British Empire has a regular home just as sugar produced in certain areas is usually sold in the United States. Where such preferred homes do not exist, sugar from various countries meets in the world market and generally is sold a t a considerable discount under the price of sugar in protected markets. Measured by how long the average man must work t o earn enough money t o buy a pound of sugar, sugar in the United States is the cheapest sugar in the world. It is usually not realized by chemists, who are considering various raw materials for processes, t h a t the wholesale price of re-
PER CAPITA SUGAR CONSUMPTION - IN POUNDS REFINED SUGAR
11,,
Table I. MOZAMBIOUE
Food
MAPAGASCAR
CHINA ITH’OFIA
COURTESY LAMBORN & CO., INC.
Figure 1. Per capita sugar consumption for selected countries for 12 months, 1951 to 1952, ending August 31, 1952
The oft-repeated statement that per capita consumption of sugar is rapidly increasing in the U. S. is not confirmed by the facts. A remarkable trend of the past two decades is the increase in the consumption of soft drinks, baked foods, confectionery, canned fruit, ice cream, and other manufactured products containing sugar. It is now estimated that in the United States more sugar reaches the home in such forms than in sugar bags. This is shown in Figure 3. It is all part of the broad picture of the emancipation of woman from the drudgery of housework. The tobacco industry is estimated to consume 70,000,000 pounds of sugar annually in the United States. It serves as a flavor, and, after inversion, as a humectant. Figure 4 shows the relation between the retail price of sugar and the purchasing power of the dollar as measured by the Consumers Price Index, For nearly 30 years the corrected pricc of sugar has been uniform to a degree unmatched by any otJher major commodity. As shown in Table I, a dollar in the grocery store buys more food energy when it is spent for sugar than for anything else. Owing to the provisions of the Jones-Costigan Sugar Act of 1934 and similar succeeding laws, sugar prices have remained relatively stable in the United States. Limitation of space prevents a complete treatment of this legislation, b u t the broad principle is t h a t the Secretary of Agriculture is charged with 1394
Sugar-Cheapest
Sugar Wheat flour Lard Corn meal Rolled oats Margarine Navy beans Rice Bread-white Soda crackers Potatoes Corn flakes Peanut butter Butter Hamburger Prunes Bacon Onions Chuck roast Rib roast Salmon-canned Bananas Apples Lamb-leg Carrots Cabbage Round steak Veal cutlets Beans-green Celery
Caloriesa, Pound 1748 1654 4095 1642 1770 3269 1537 1644 1254 1909 318 1748 2615 3251 1457 1036 2857 193 1019 1275 9 22 269 232 885 166 80 829 748 143 52
Energy Food
Retail Priceb Cents/Pound
CaloriesC/ Cent
10.5 10.0 28.0 12.5 14.8 29.8 17.4 19.7 17.0 27.1 4.9 29.2 49.0 69.6 40.9 30.3 89.5 7.8 51.7 70.0 52.3 16 0 16 8 74.4 13.4 7.6 89 9 110.9 23.8 12.7
166 165 146 131 120 110 88 83 74 70 65 60 53 47 36 34 32 25 20 18 18 17 14 12 12 11 9 7 6 4
a Source: U. S. Dept. Agr. Handbook No. 8. b Retail,F?od Prices City Average (U. S.), May 1954. U. 8 . Bureau of Labor Statistics. C Figures rounded to eliminate fractions.
Table 11. Price of Various Forms of Sugar, July 1954 Price, Dollars 0 10 lb.
1+6/ton 107/ton f.0.b. Cuba 61 t o 64)ton, f.0.b. Cuba
33/ton New Orleans 25/ton’ f.0.b. Cuba 163/,/tbn. f.0.b. Cuba
Form of Sugar Retail price of granulated sugar East C o a s t i n d u s t r i a l price-refined sugar Quota-raw sugar-96’ Unrestricted-raw sugar, world price As blackstrap molasses, 50% As high test molasses, 80 to 85% As unrestricted blackstrap molasses, 50%
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 7
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Carbohydrate Raw Materials organic compounds. T h e exhaustion of the petroleum deposits seems t o recede like the rainbow as time advances, but there is now much evidence that the age of sucrochemistry is not waiting for this unhappy event. T h e majority of all organic starting materials are much more Bagasse, tlie fibrous residue from sugar cane, is now usually expensive t h a n sugar. B y way of comparison, burned under the boilers a t the sugar mill, but the Celotex Raw Material Cost, Dollars/Ton industry uses it t o produce insulation against sound and heat. Coal 4 t o 10 The expanding market for paper has emphasized bagasse as a Benzene 115 source of cellulose. Plants in the Philippines, Peru, India, Petroleum 10 Butane 12 Brazil, Taiwan, Columbia, and Argentina are producing pulp and paper from bagasse. I n this country a $3,000,000 mill in More than 97% of t h e organic compounds listed in the Chem. Louisiana is being put in operation by Valentine Pulp and Eng. News Quarterly Report on Current Prices are more exPaper Co. (4). Newsprint, fine writing paper, dissolving pulp, pensive than sucrose, which is 99.96% pure. Almost every grocery and cement bags, corrugated board, and cardboard are material is more expensive than the sugar contained in blackstrap some of the items for which bagasse pulp has been used. Here molasses. 1.9 tons of bagasse worth $6 to $10 as fuel will produce a ton of newsprint currently worth over $125; 21/., tons of bagasse wilt SUCROCH EMISTRY produce a ton of fine writing paper worth $300 to $400. If these Sometime ago the term "sucrochemistry" was coined t o desigdevelopments meet t h e test of economic competition, this market nate t h e branch of organic chemistry in which sucrose and its byfor bagasse will consume increasing quantities; less will b e products constitute the starting materials. T o a chemist familiar burned. with petrochemicals the meaning is obvious. T h e South Porto Rico Sugar Co. has just put into operation a For many years the prediction has been made t h a t as petroleum $7,000,000 plant in Santo Doming0 to manufacture furfural from and natural gas become scarcer and coal more expensive, vegethe xylan in bagasse. D u Pont has contracted t o absorb t h e tation would inevitably become more important as a source of bulk of the 30,000,000 pounds annual output for use in nylon manufacture (IS). Other areas are exploring this development. The Valite bNSUMPn0N Corp. heats bagasse with aromatic deSHORT IONS ~,500,000 rivatives t o produce a resin stock of value in phonograph records. a.Om.m Sugar cane filter muds contain cane 7.mm wax. It has been estimated t h a t about TOTAL SUGAR CONSUMPTION (IN woni ~ONI. R A W VALUE) 30,000 tons are available annually from .. 7.m.m) Cuban sugar cane mills alone ( 5 ) . This 6.5W.m) wax has some of the desirable qualities of carnauba. T h e Cuban-American ....... - . . .8.Om.wo Sugar Co. offers cane wax t o the Amer........... 5,500.080 ican market. I n addition, t h e muds contain untapped supplies of steroids, 5.m.Mo -~ fats, and other compounds. . . . 4.500.oM Molasses contains the nonsugar comu 5. ponents of cane juice. Salts prevent DPULATION 4.000,ow the crystallization of some of the sugar ........... 3.MO.m) I5.oM.W so t h a t the final molasses is about half 3.w0.000 total sugars. These sugars are availi0.mam able for the nutrition of fermentive 2.5W Om !5 o00,aa organisms, cattle, and other animals. 2.wo.Wo Traditionally, t h e major consumer of mYnm molasses has been the alcohol industry. 1.500 ow r5.m.m R u m continues t o be produced by this 1.w0,wo i0.wa.m method, but production of industrial alcohol from ethylene has been ex5oc.Om !5.Wm, panded until there is now only one A 0 major producer of fermentation alcohol POUNDS POUMOS in this country. Similarly, producers 120 120 of butanol and acetone are meeting IO0 100 competition from petroleum chemical processes. However, for more complex 80 80 molecules-such as lactic acid, citric 60 60 acid, or most of the antibiotics-chem40 ical methods of synthesis so far have 40 not competed with fermentation. 20 20 With the loss of much of the fer2 0 mentation business to the petrochemicals industry, much of the slack has 5 YEAR INTERVALS YEARLY INTERVALS COURTESY LAMBORN CO.. INC. been taken up b y the cattle feeders (16) (Table 111). Many of the high Figure 2. U. S. sugar consumption and population, 1853-1953 roughage foods, such as corn cobs, Aotual deliveries for consumption including deliveries for U. S. military forces at home and are made more palatable by mixing abroad fined sugar in the United States is not necessarily the correct one
t o be used in their calculations. Table I1 gives the price of sugar in various forms and of different origins as of July 1954.
r
.
July 1955
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them with molasses. There is a n additional benefit. T h e sugar in t h e molasses so stimulates t h e rumen microorganisms t h a t they make a more complete utilization of the roughage. I n addition t o these benefits, molasses contains nutritionally valuable amounts of copper, iron, potassium, phosphate, and sulfate.
Table 111. Utilization of Molasses, 1952-1954 (Million gallons) Use 1854 Molasses used for Ethyl alcohol& 65 27 Butyl alcohol and acetone Spirits and rum 3 Feed 381 Yeast, vinegar, and citric acid 60 Edible and miscellaneous 10 546 Total utilization Includes high test molasses.
-
1953
1952
180 25 3 354 56
159
8 625
8 3
300 53 7 529
-
5
Y K W
a
1935
1940
194s
and marketed in this country each year from the concentrated Steffen filtrate. A new $3,000,000 plant t o manufacture monosodium glutamate went into operation in November 1054 a t t h e Johnstown Refinery of T h e Great Western Sugar Co. Monosodium glutamate has the unique property of stimulating the taste buds, thereby enhancing or accenting the natural flavor of foods, except those of low pH. It is used in large quantities in both institutional and family kitchens, and in canneries for canned soups and meats. The Stcffen process is one in which beet molasses is treated with lime t o precipitate calcium sucrate which, after filtration, is treated with carbon dioxide t o release the sugar. When t h e Steffen process is operated in connection with a beet sugar factory, as is usually the case, the calcium sucrate is suspended in t h e beet juice before treatment with carbon dioxide. The precipitated calcium carbonate flocculates impurities in t h e beet juice, permitting their easy removal by filtration. Additional sugar is recoverable from the molasses produced b y a factory using the Steffen process if barium hydroxide is used to precipitate the sucrose. The molasses residue after removal of sugar, either as calcium sucrate or barium sucrate, is the raw material for monosodium glutamate. These molasses residues contain a similarly recoverable amount of betaine which is useful as a dietary extender of choline. Markets for this product await development. Beet pulp also is fed t o cattle. To increase storage time and decrease shipping costs, much of the pulp is dried. An increasing amount is being pelletized, which decreases storage volume. ‘The product is a nutritious feed extender. Ammonia will react readily with dried beet pnlp t o increase t h e protein equivalence. Some of the beet molasses is fed to cattle either mixed with pulp or added t o other forage. .However, for this use there is strong competition from the antibiotics and fermentation industries.
1950
YEARS COURTESY LAMBORN & CO., I N C .
Figure 3.
Per cent sugar used in home, United States, 1935-1953 U. S . Dept. of Agriculture
Such feeds, however, have required protein concentrates for good nutrition. Part of t h e nitrogen fortification can be done economically b y adding urea or reacting the molasses with ammonia ( I d ) . These developments are contributing t o the steadily expanding market for molasses in cattle feeding. I n the beet sugar industry, important by-products are beet tops, pulp, molasses, and monosodium glutamate. Beet tops are prized as cattle feed and are valuable green or ensiled. The late James E. Larrowe pioneered the production of monosodium glutamate and eventually sold out t o t h e International Minerals and Chemical Corp. H e financed a research fellowship at Mellon Institute for the purpose of thoroughly exploring the economic possibilities of processing the steffen filtrate, After a long, drawn out, costly, and often discouraging investigation, i t apof monosodium glutamate from the peared t h a t the filtrate might be economically feasible. Venture money then provided the necessary sums t o build a plant for the commercial production of monosodium glutamate by the newly developed process. Although the first few years of operation of this plant proved very disappointing and resulted in financial losses, now millions of pounds of monosodium glutamate are produced
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YEARS
Figure 4. Relation between retail sugar price and dollar purchasing power based on Consumers Price Index
Molasses from immature cane, such as t h a t produced during in contains as much as the limited growing 6% of aconitic acid. Annual production in Louisiana could be 5 ~pounds;~ total production ~ ~might be, ten times ~ as much. ~ Aconitate esters are useful as plasticizers for vinylidene polymers where the activated double bond reacts with traces of hydrogen chloride and exerts a stabilizing effect. The 2-ethylbutyl ester adds sodium bisulfite t o form General Aniline’s Nekal NS, a powerful wetting agent. At present, Godchaux Sugars, Inc., is marketing the calcium-magnesium salt of aconitic acid. In the laboratory and factory, sugar can be converted t o many
1NDUST.RIAL AND E N G I N E E R I N G CHEMISTRY
Vol. 47, No. 7
~
Carbohydrate Raw Materials useful products. The manufacture of Dextran from sucrose is now a familiar story. The manufacture of cyclic acetals of sucrose, glucose, and fructose by treating sugar with aldehydes in the presence of sulfuric acid was developed in the laboratories of the Xational Sugar Refining Co. ( 2 ) . Olin Mathieson Chemical Co. is a t present in pilot plant production of these agricultural sticking agents which cause insecticides and herbicide8 to adhere to the leaves of plants. A paper by Skell, Crist, and Micich (8) describes a new general method of going from soluble carbohydrates t o diamines by catalytic hydrogenation in the presence of ammonia or an amine. At the recent Meeting-in-Miniature of the New York Section, York (17) of Foster D. Snell, Inc., reported the excellent surface active properties of sucrose monoesters of fatty acids. These discoveries are representative of what Can be done with Rugar as a n organic starting material. A question frequently asked by nonchemical friends is why chemists never seem to think of using sugar as a starting material for organic synthesis. I t is cheap and plentiful, and will remain so while the sun shines and fields are fertile. The principal functional groups-primary and secondary hydroxyls-have been thoroughly studied and their reactions are well known. Sometimes all that is necessary to start a new but obviously logical trend is for some one company to break the ice and show that it can be done. But although Atlas Powder Co. has made an outstanding commercial success of mannitol and sorbitol and their derivatives and their proposed $I 0,000,000 plant t o go from sorbitol to glycerol has been announced, sucrose ii: still being neglected. There is no simple answer. Part of the reason is t h e failure of most sugar companies t o carry out the type of use research which any chemical company would automatically do on a product so little explored as sugar. The recognition of t h e potentials in sucrochemistry was one of the reasons for the establishment of Sugar Research Foundation, Inc., by the leaders of the sucrose industry. There is evidence t h a t research moves in surges almost analagous t o fashions. I n industrial organic chemistry first there was the chemistry of coal t a r constituents culminating in Worltl War 11, which can be oversimplified as a struggle between picric wid and T N T . Beginning about 1920 the petrochemicals age began. This has not yet reached its zenith but a recent survey by Ayres indicates that not many decades hence petroleum and natural gas will be x declining source of raw materials ( I ) . Then there is the complexity of the Nucro6e molecule and the
ease with which it comes apart in the presence of a trace of acid. There is one cyanoethylation product obtainable with ethanol and acrylonitrile. Sugar can yield 255 or 28 - 1. Of these, there are 8 each of mono- and hepta-substitution products, 2s each of di- and hexa-, 56 each of tri- and penta-, 70 tetra-, and 1 octa-substitution product. Therefore, a chemist studying a new reaction will use a simple alcoh.ol and avoid the complexities of a highly intricate reaction mixture whose separation to pure products other than the completely substituted one would be difficult. The advent of chromatography has minimized this problem but has not eliminated it. It is high time that, the energy applied t o the fascinating industrial chemistry of sucrosc is brought more nearly in line with its possibilities. T h e movement of sucrochemistry from imagination to laboratory to manufacturing plant should be accelerated. It is safe t o predict t h a t this will happen. LITERATURE CITED (1) byres, E., Chem. Eng. News., 32,,2876 (1954). (2) Bray, D. F., Agr. Exp. Sta., Univ. of Delaware, Bull. 304 (June 1954) (3) Calvin, M., and Benson, A. A., Science, 109, 140 (1949). (4) Chem. Eng., 60, No. 7, 136 (1953). (5) Chem. Week, 69, No. 25, 23 (1951). (6) Foreign Crops and Markets, 69, No. 22, U. S. Dept. Agr. (Nov. 29,1954). (7) Rabinowitch, I. M., Am. J . Digest. Diseases, 14,315 (1947). (8) Skell, P. S., Crist, I. G., and Micich, T. J., Division of Industrial
.
and Engineering Chemistry, 126th Meeting ACS, New York, September 1964. (9) Snyder, H., Agr. Expt. Sta., Univ. Minn., 12th AnnualRept., p. 225 (1904).
(IO) Stallings, J. W., U. 9. Patent 2,473,308(June 14, 1949). (11) “Statistical Abstract of the United States,” pp. 650-2, U. S. Department of Commerce, Washington 25, D. C., 1953. (12) Stiles, H. R., Ibid.,2,603,567 (July 15, 1952). (13) Sugar, 49,No. 1 , 2 8 (1954). (14) “Sugar Manual,” p. 16, Hawaiian Sugar Planters’ Association, Honolulu, 1954. (15) Through the Leaves, Great Western Sugar Co., Denver, Colo., 42, No. 1 and 2 , l O (Spring 1954). (16) Walker, G. L., “Industrial Molasses-An Annual Market Review,” p. 9, U. S. Department of Agriculture, Washington 25, D. C., November 1954. (17) York, W. C., New York Meeting-in-Miniature, ACS, February 1954. RECEIVED for review October 22, 1954.
ACCEPTED April 21, 1955.
Wood Industries as a Source of Carbohydrates AVERILL J. W-ILEY Sulfite Pulp Manufacturers Research League, Appleton, Wis.
JOHN F. HARRIS, JEROME F. SAEMAN, AND EDWARD G. LOCKE Forest Products Laboratory, Forest Service, U . S . Department of Agriculture, Madison, Wis.
W
one of the most important sources of carbomaterial t h a t is actually or potentially available ::a $: on a world-wide basis. Most woods and wood residues average about 50% cellulose and about 20% hemicellulose, The carbohydrate products t h a t are or can be derived from the cellulose or from the hemicelluloses of wood are the principal subject of this paper. Cellulose itself, as used by the structural wood, the July 1955
fiber, the paper, and the chemical cellulose industries, is a polymer beyond the scope of this paper. Much research has been directed toward utilization of wood wastes. The more fruitful of those wood utilization methods finding actual commercial application today use the structural and fibrous properties of the wood. Apart from cellulose and fiber products, the utilization of individual wood components such
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