May 10, 1929
INDUSTRIAL
AND ENGINEERING
CHEMISTRY
5
T h e Florida Tung-Oil Project B Y B. F. WILLIAMSON Gainesville, Fla.
In starting the first scientific mechanical pressing plant the first cycle of t h e Florida tung-oil project is completed, covering t h e actual planting of seed and growing of t h e trees and the production of a very high grade of oil. This represents intensive, practical, scientific efforts of various groups a n d individuals over a period of t e n years. Tung oil w a s first imported into this country about one hundred years a g o in a very small shipment. Twenty-five years ago the United States Department of Agriculture through Doctor Fairchild, chief of t h e Bureau of Foreign Seed and Plant Introduction, brought the first seed and plants into the United States from their native country, China. There are four species. A leurites montana is grown i n southern China. This tree is not prolific, however, a n d furnishes a small amount of t u n g oil, the quality of which is satisfactory. Aleurites trisperma, which grows i n the Philippine Islands, produces a small amount of oil, not so good in quality. A leurites cordata, which g r o w s i n Japan, i s also a shy bearer, producing an inferior oil. A leurites fordi, which is the most hardy a n d m o s t prolific bearing tree, produces more t h a n 9 0 per c e n t of the entire supply. This tree grows best in the provinces lying adjacent t o t h e Yangtze River. The o i l from the fordi i s the c o m m e r c i a l tung oil or T h e F i r s t M o d e r n Scientific Chinawood oil. T H E INDUSTRY IN CHINA
In China t h i s oil i s used i n many places where we use rubber in t h i s country. It produces the high finish on the Chinese junks a n d other river boats. I t is applied to all forms of wood structures, i s used for waterproofing paper for Chinese parasols, silks, a l l kinds of cloth materials and masonry, and i n the back country i t is sometimes used for lighting in lamps a n d for soap. The residue, on being highly heated, is converted into a n indelible ink, so-called India ink. A large proportion of t h i s oil comes from t h e interior of China, where i t is produced by m a n y small units, transported on human backs from twenty-five t o one hundred miles to river boats, brought down the river several hundred miles to Hankow, there settled and transported t o lighters and carried six hundred miles further t o tank steamers, which bring it to the Pacific Coast. It is then transferred t o storage tanks and from there drawn into barrels, drums, and tank cars and distributed throughout the United States. Owing to t h e crude methods of pressing, the yield of oil in China i s small and the quality is inferior. T h e final oil passes through many hands and suffers from poor handling, and is often subjected to considerable adulteration. W e were told a t the first t h a t the production of the oil was a deep oriental secret, carefully guarded for hundreds of years. We pressed from American-grown tung-oil fruit, a n d found that we could produce a lightcolored, neutral oil in comparison with the dark Chinese oil showing 5 to 8 per cent free acid. The conclusion w a s that the Chinaman's secret w a s adulteration and not production. H e was leaving 18 to 2 0 per cent of oil in the pressed cake, whereas our American press reduced t h e oil content to around 5 per cent. T h e Chinese methods a r e entirely b y hand. The American methods are entirely by machinery. Julean Arnold, the commercial attaché in China, states t h a t one American press will do t h e work of ninety t o one hundred Chinamen. EXTRACTION OF On,
Three methods of removing the oil from the fruit were tried— extraction by solvents, pressing with hydraulic press, and pressing with a continuous expeller. The first t w o were impractical. The expeller has been adopted. A picture of the first plant is here introduced. T h e complete unit of this plant is a continuous operation requiring only three t o four men t o operate, and will d o the same work t h a t is done in China by seven hundred t o one thousand Chinamen. W e reduce the oil content t o δ to 6 per cent, whereas the Chinaman pressing b y hand leaves 18 t o 20 per cent of t h e oil in the cake. The extra oil that we obtain
would pay all pressing charges. Mechanical power is also used in cultivation. Four small tractors do the work on 18O0 acres and are half the time under the shed. The residue from the pressing runs 6 to 6.5"per cerat ammonia. This residue reported on by a fertilizer concern is said t o be worth $35 t o $40 per ton, and has about the same availability as cotton seed meal. The hulls have a fertilizing value of $ 4 - 5 0 to $6.00 per ton, and both hulls a n d residue are ground and returned t o the soil for fertilizing the trees. The inner n u t r e m o v e s from the soil, where there is a crop of whole fruit of 5000 p o u n d s per acre, about 108 pounds of ammonia, 70 pounds of phospfciate, a n d 30 p o u n d s of jpotash. B y growing c o v e r crops and returning t h e s e by-prod ucts t o the g r o v e , t h e amount of fertilizer neces sary for the t r e e is greatly reduced. CULTIVATION" INVESTIGA TIONS
After gathering informa tion for four o r five years we found t h a t the reports from Chinese sources were so conflicting -that n o one knew what t i m e of t h e year to plant the seed o r the trees from the nursery. In cooperation w i t h o u r ex periment s t a t i o n , plantings were made e v e r y month in the year for f o u r years t o determine t h e o p t i m u m t i m e of planting. The same procedure was followed in transplanting T u n g - O i l C r u s h i n g Plant the trees from the nursery to t h e grove. Tests were made to determine the best method of propagation a n d whether it would be better to bud and graft t h e trees or d e p e n d on seed ling trees from selected prolific parents. The Government h a v i n g started the planting of these trees some twenty-five y e a r s ago, we were able t o trace from a very prolific tree four generations of bearing trees, which showed general characteristics of the parent up t o 98 per cent. Plantings were made on all types of soil—group plantings of twenty-five to fifty trees in t h e wild, in cleared l a n d without cultivation, in high dry land, and in low wet land. S o m e groups were planted and given cultivation; other groups w e r e planted and given cultivation and careful fertilization. It w a s found that the trees d o best when planted on well-drained l a n d s and given proper cultivation and fertilization. A t this stage a survey was made of the trees that "the Govern ment had planted through their experiment stations a n d collabo rators as far north as the Carolinas a n d as far west a s California. This survey indicated t h a t the best growth a n d yield a f ter t w e n t y years was i n north central Florida i n the vicinity of Oainesville. A close study of the trees in five different groups—one in a group planted near a stable lot, one in another place in a garden, and three in chicken yards—showed that the trees w h i c h received fertilizer produced good crops of fruit eve*/ year. "Where there was no fertilization the growth was very much slower a n d the yield of fruit much smaller, there was a tendency to produce fruit only i n alternate years, and t h e fruit not o n l y showed a smaller yield but contained a lower content of oil. W e undertook the problem of determining the t i n x e of year t o apply the fertilizer, the most economical fertilizer t o u s e , a n d the amount t h a t could be used profitably. T h e study o f the trees showed t h a t the terminal buds bursting o u t in the spring pro duce flowers and fruit and from these terminal b u d s come -. the shoot growth that will produce the terminal buds o f the next season. S o that while t h e fruit is being formed and m a t u r e d the shoot and t h e bud that will produce t h e fruit the following season are in process of formation. Just a t this period t h e trees are under their greatest strain. The terminal bud is either a fruit bud o r a leaf oud, a n d it was necessary to find o u t when these terminal buds "were formed and what effect feeding the tree would h a v e in increasing the number of fruit buds over the leaf buds. I n this w o r k we were successful i n obtaining the assistance of Chas. E . A-bbott, who took buds from trees of various ages under various conditions of fertilization, during t w o complete growing seasons, preserved them and took them for study to Lansing, Mich., wiiere h e had the advantage of a splendid research laboratory working under
6
NEWS EDITION
V. R. Gardner, perhaps the most outstanding man on fruit-bud production in the United States. I t was found that in order to affect the frait buds i t is necessary to apply the fertilizer early in February before t h e buds commence to swell. Applications a t this time will affect the formation of t h e shoot growth and the terminal buds t h a t start thendevelopment in late March. The second application of fertilizer is best applied in July, and the fruit i s mature and begins t o drop in October. T h e fertilizer applied one season materially affects the growth of the tree and Mie development of .the fruit of t h a t
C l u s t e r Type T u n é - O i l T r e e
season, b u t does n o t increase the quantity of fruit that same season, but if t h e proper fertilizer is used a n d applied at t h e right time it m a y greatly increase t h e number o f fruit t h e following season. Eighteen months after the fertilizer is applied t h e fruit affected b y that fertilizer will be mature. If t h e tree is n o t properly fertilized, t h e effect will be shown eighteen months later and i t will take an additional eighteen months t o bring t h e tree back t o its full bearing capacity. Failure to fertilize at t h e proper time may cause loss from which it will take three years t o recover. It is reported that most of the Chinese trees bear a single n u t at t h e terminal. Sometimes, however, t h e fruit appears i n clusters. W e have developed t h e second "type and in our first year's bearing w e obtained a little over 100 per cent greater yield than with the single type, using practically the same cultivation and fertilization. FUTURE OP INDUSTRY-
T h e industry is now on a commercial basis. We are gradually eliminating guesswork, and are able t o judge the profitableness of t h e growing of these trees. Since some $75,000,000 i s being sent out of the country each year for all kdnds of paint oils, o f which $12,000,000 t o $15,000,000 is for tiuag oil, a n d since this is t h e most durable and waterproof of all paint and varnish oils, it is reasonable t o expect that this will develop into a very large industry of economic value to the entire country. W e are constantly reminded of the increased uses of t h e oil— brake bands for automobiles, sheet packing for various purposes, insulation for all kinds of electrical apparatus and -wiring. U n doubtedly producers of linoleum and oilcloth will use more o f this oil when it is available. T h e demand i s constantly increasing. We are told it is impossible to increase the production or improve the quality i n China, which indicates that the increase must come from the production in t h e United States. T h e d e mand today is far i n excess of available supply, a n d it will b e many years before production catches up with the demand.
B r a u n - K n e c l i t - H e i m a n n Co. Anniversary Booklet T h e Braun-Knecht-Heimann Co. of Sao. Francisco, i n commemoration of the seventy-fifth anniversary of the founding o f the business, has issued an attractive illustrated brochure, which, has just come t o our desk. T h e engraving which reaches t h e eye upon opening this booklet is particularly interesting and other sketches in the same style are to b e foixnd within the covers. T h e Braun-Knecht-Heimann Co. began in 1852 with t h e e s tablishment of John Taylor & Co. ; this became F. W , Braun Co. ; and was expanded under its present name in 1908. T h e company is t h e largest of those engaged in the laboratory a n d chemical supply business in t h e West, and h a s continually shaped i t s policies with a view t o obtaining high-quality standardized stocks from reliable manufacturers and selections of materials which, comply with the recommendations of the AMERICAN CHBMICAI*
SOCIBTY, t h e Bureau of Standards, the Ajmerican Society for Testing Materials, and others.
Vol. 7, No. 9
Rayon—The Chemical Yarn B Y ISMAR GINSBERG 113 West Forty-second St., N e w York. Ν. Υ .
Rayon, the newest of textiles, is called chemical yarn. This is only o n e of t h e many names which have been applied t o it, b u t from t h e standpoint of t h e chemical industry it is unquestionably t h e one of prime significance, for it is rayon that h a s changed t h e entire aspect of the textile industry so far a s the manufacturer of chemicals is concerned. True enough, t h e textile industry h a s always consumed quantities of certain chemicals i n carrying o u t various operations on textile fibers, but the consumption of chemicals in t h e dyeing, finishing, bleaching, and chemical treatment o f yarns and fabrics has been comparatively small w h e n compared with other industries. Only within the past five or six years, during which rayon production has increased s o rapidly i n this country, has our chemical industry begun t o consider t h i s n e w textile industry as one of its principal customers. Never before in t h e history of textiles, n o t only i n this country b u t in Europe as well, h a s there been such progress a n d growth a s has taken place since rayon became popular. I t has provided t h e slow-moving, rather unprogressive textile industry with a t least o n e branch full of life and activity, whose expected growth c a n merely be estimated and whose ultimate end c a n only be c o n jectured. A n d in doing so, it has h a d a very important effect upon t h e chemical industry. While i t is b y no means easy t o find t h e reasons for steadiness of markets and t h e difficulty in meeting the demand for most chemicals, as they enter into m a n y different industries, nevertheless the very strong present position of the market for alkali and mineral acid, a s well a s certain other chemicals, such as carbon disulfide, alcohol, and acetone, is u n doubtedly d.ui in n o small part to t h e great demand for these products that has arisen from t h e rayon industry. And, what is perhaps of greater significance, this demand is increasing. T h e rayon producers are building new plants a n d enlarging old o n e s a n d plan an average increase of 25 to 3 0 per cent during 1929. R a y o n P r o d u c t i o n i n the U n i t e d S t a t e s YEAR
β
1919 1920 1921 1922 1923 1924 Estimated.
POUNDS
9,000,000 9,000,000 20,000,000 26,000,000 35,000,000 37,720,000
YEAR
1925 1920 1927 1928 1929
POUNDS
52,200,000 62,575,000 75,050,000 96,531,000 125,000,000 e
Of this 1929 production, over 100,000,000 pounds will be v i s cose yarn. T h e chemical manufacturer m a y not appreciate j u s t what t h i s means to him. To make this amount of viscose rayon alone, there will be required 200,000,000 pounds o f sulfite wood, in addition to normal paper requirements, a n d the accompanying consumption of large amounts of chemicals. For processing t h i s pulp there will be required 200,000,000 pounds of caustic soda, 150,000,000 pounds of sulfuric acid, a n d 60,000,000 pounds of carbon disulfide. These are substantial amounts of chemicals, even for the great industries that supply them. Furthermore, the remaining 25,000,000 pounds of rayon will necessitate the consumption of large amounts of other chemicals. Nitro rayon, which, with 10,000,000 pounds estimated for 1929, is second in production i n this country, will require 6,000,000 gallons gross of alcohol, 10,000,000 gallons gross of ether, a n d 310,000,000 pounds of mixed acid. There is of course an appreci able recovery both of spent acid and of spent alcohol a n d ether. I t is estimated that 40,000,000 pounds of calcium monosulfide a n d 20,000,000 pounds of ammonium sulfate are also required for t h i s production. T o make t h e 4,000,000 pounds of cuprammonium rayon esti mated for 1929, 1,600,000 pounds of copper and 6,000,000 pounds of ammonia will be required. The production of acetate rayon is expected to increase from 4,000,000 pounds in 1928 to 8,000,000 pounds i n 1929, requiring 16,000,000 pounds gross of acetic a n hydride and t h e same amount of glacial acetic acid. I t is esti mated t h a t 80 per cent of the total amount of acid is recovered, leaving a consumption of 6,400,000 pounds. The gross consump t i o n of acetone will b e 32,000,000 pounds, of which 95 t o 97 p e r cent is said to b e average recovery, making a net consumption of 1,600,000 pounds. I n addition to these chemicals, others are used in smaller amounts in the various processes as ingredients of t h e coagulating baths or for special purposes, a s in the production of delustered rayon where both zinc sulfate and magnesium sulfate a r e used, while a large number of other chemicals have also been advocated for this purpose. Caustic soda or sulfuric acid is employed in t h e manufacture of cuprammonium rayon, and glucose is consumed in large amounts as a n ingredient of the precipitating bath in t h e manufacture of viscose rayon. Furthermore, much rayon i s bleached. The debt of the chemical industry t o rayon, as a consumer o f quantities of chemicals is t o a certain degree repaid by services
