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basis of understanding which every true partnership must find in order to be successful and lasting. And let us of industry strive and so conduct ourselves that it will no longer be doubted, but completely accepted, that there are workers in industry who are genuinely inspired by the ideals of advancement of medical science, and of service to humanity. These workers are worthy of the privilegeindeed it is their right-to stand shoulder to shoulder with those in the universities and research institutions. Let them go forward, together, to greater achievement.
has been welcomed by universities in recent years is not measured by their desire for the endowment of fellowships. For example, Merck & Company do not look upon a fellowship so much for what results may come out of it, or what claim they have on that result, as they do upon the value of the contact it engenders between their research group and the workers in the university or medical school departments. Here is cooperation; here is partnership, concrete and practical. From such contact can grow a wider and deeper relationship, so that in the end the leaders in industrial advancement and the leaders in medical advancement will meet on the common ground of research. Clearly the job needs both, and each needs the other. Let them devote themselves to finding a
RECEIVED May 10,1935. Presented before the Division of Medicinal Chemistry a t the 89th Meeting of the American Chemical Society, New York, N. Y., April 22 t o 26, 1935.
OLD-TIMETURPENTIXE AND ROSINSTILL
N
Naval
Stores Courtesy,
U.S. Bureau of Chemistry and Soils
ROBERT C. PALMER Newport Industries, Inc., Pensacola, Fla.
EARLY every industrial history of America records that the production of naval stores was among the earliest chemical processes employed by the first settlers. Williamson’s “History of Maine” states that in 1606 turpentine was being made there which may be considered as the first recorded date when American pine trees were worked for this product. In 1608 a small company of Dutch and Polish workmen were sent to the newly established Virginia settlement a t Jamestown to manufacture among other things “Hard Pitche, Tare, Turpentine and Rozins.” A cargo under the command of Captain Newport which went back to England that same year contained probably the first export of naval stores from American shores. The value of the extensive pine forest for these products was well recognized as early as 1586 by Sir Walter Raleigh, and England was desirous of making use of this new source of supply of naval stores to replace their importations from the Scandinavian countries and Russia. Tar-making was hardly an established industry nor can it be said to have flourished in the Virginias, for the early immigrants found it a poor substitute for the gold they sought. The manufacture of pine tar became, however, one of the first industries of the settlers on the New England coast and was so extensive that by 1650 towns along the Connecticut River were prohibiting the use of “candle wood” for purposes
other than light and fuel within six miles of the river. In 1716, because of the rapid destruction of the pine, hlassachusetts passed laws to conserve the forests, putting an end to the tar as well as the turpentine industry in that colony. In the meantime the Carolinas were being permanently settled and the industry was being established in the new region with its much more resinous pine. By the time Massachusetts was passing its first conservation laws, the coast country farther south was supplying England with a considerable quantity of pitch, tar, and other naval stores and thus North Carolina’s later reputation as the “Tar Heel State” was born. It is well known that naval stores products were among the important “commodity dollars” of commerce in that period. A record of exports of Korth Carolina in 1750 shows about 60,000 barrels of tar, 12,000 barrels of pitch, and 10,000 barrels of turpentine (crude gum), which had increased to 88,000 barrels of tar, 21,000 of pitch, and 88,000 of turpentine by 1770. During the Revolutionary days the industry declined rapidly but with equal rapidity regained its position in the early 1800’s. While tar- and pitch-making continued during this period, crude turpentine which was by then being distilled for the recovery of the spirits became the important naval stores product. The rosin residue of the distillation was worth very little and for many years tremendous quantities were discarded into the river beds as an
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VOL. 27, NO. a
NIGHTVIEWOF STEAM AND SOLVENT NAVAL STORES PLANT, NEWPORT INDUSTRIES, INC., PENS.4COL.4, FLI.
period 1900-1930 and many thousands of cords of pine W O Q ~ , undesirable by-product, to be actually “mined” later in the chiefly f a t stumps and light wood, were distilled for pine tar, century when rosin became a more important product. pitch, pine tar oil, turpentine, charcoal, and obher products. North Carolina was the main source of naval stores until Large plants were built in Fayetteville, N. C., Jacksonville, after the Civil War with Wilmington the principal port, although by 1860 it was furnishing only 70 per cent of the Pensacola, and Xew Orleans which are still. in existence. A number of smaller plants were scattered through the Carocrude turpentine gum produced in the United States. South Carolina, Georgia, and Florida had begun production. Belinas, Georgia, and Alabama which have ceased operations tween I880 and 1890 South Carolina became the center of the and for the most part have been dismantled. The developindustry, Charleston being the important port, and by 1900 ment of flotation processes for recovering copper, silver, and Georgia became the chief producing state. Ten years later lead from low-grade ores and the use of pine tar in the automobile tire industry played a large part in the success of the Florida was producing more than 50 per cent of the total. plants, Such names as Hansen, Clark, Bilfinger, Mayiner, At the end of the World Was Florida continued as the largest producer, but more than 40 per cent of the country’s naval Wernicke, and Merrlwether have been prominently associated stores was then coming from Alabama, Mississippi, Louisana, with the development of the destructive-distillation industry. and Texas. North and South Carolina combined, once the A large number of precess and equipment patents were taken center of the industry, were then producing less than f per out, indicating the wide variety of technical thought given to this industry. Probably the first chemically tral’ned men cent of the total. Within the last few years the supremacy employed by any part of the naval stores industry were has shifted back to Georgia largely because of the rapidgrowing second-growth slash pine areas coming into producengaged in this oldest of all branches. There has been no expansion of the destruct~ve-distillation tion. I n 1932-33 Georgia and Florida combined were furnaval stores industry in recent years; in fact, unfortunately nishing 85 per cent of the gum turpentine and rosin produced the opposite has been the case. The sharp recession in ore in the United States. For many years Savannah, Ga., has flotation and the increasing use of chemical antioxidants in been the world’s largest naval stores port, although Brunswick, Ga., Jacksonville and Pensacola, Fla., and Mobile, the rubber industry instead of pine tar have been important factors working against this industry. Plants located near Ala., are also large and important storage centers.l (The distribution of naval stores plants by states is shown on a large centers of population have found the demand for She charcoal to be of material economic assistance in maintaining map on page 529 of the May, 1935, issue of IXBUSTRTAL operations. Cordage manufacturers still demand pine tars AND ENGINEERING CHEMISTRY.) of various sorts and disinfectants consume pine tar creosotes. Destructive Distillation The destructive distillation of pine wood has a large chemical potentiality, and it is B safe prediction that only by a greater It has been suggested that up t o the year 1800 the so-called application of chemical research than in the past will the naval stores industry may more properly have been named industry progress as it should. pine tar industry, between 1800 and 1900 the turpentine industry, and a t present the rosin industry. The production Turpentine and Rosin from Crude Gum of pine tar and pitch has continued, however, through the years. I n the early days the wood was burned in kilns made The refining of crude gum yielding, upon separation by of sod. Later iron vessels or retorts were employed. The simple steam distillation, spirits of turpentine and rosin has plant which may be considered the inception of the modern always been conducted in comparatively small establishments. branch of the naval stores industry known as destructive Early in the nineteenth century crude gum was not only distillation is believed to have been built by James Stanley refined relatively close to the production but was also shipped in 1872 a t Wilmington, If. C. The destructive-distillation to Philadelphia and New York where the spirits were repine industry assumed considerable importance during the covered. Jn the census of 1850 North Carolina reported 785 plants producing 13,000barrels of turpentine and 300,000 1 Gamble,‘Navai.Stores Year Book, 1921 and subsequent editions.
INDUSTRIAL AND ENGINEERING CHEMISTRY
JULY, 1935
barrels (500 pounds gross) of rosin. I n 1900 the United States census showed a total of 1500 establishments in eight southern states of which about 500 were in Georgia, then the largest producing state; the total yield for the entire country was 600,000 barrels of turpentine and 2,000,000 round barrels of rosin. Production was maintained a t approximately this high rate for nearly ten years, reaching an all-time peak in 1908 of 750,000 barrels of turpentine and 2,500,000 round barrels of rosin. The total production gradually declined to a low of 340,000 turpentine and 1,100,000 rosin in 1918-19 largely because of the World War. A second peak but lower than in 1908 was reached in 1927, the production then gradually declining to a present figure of around 500,000 barrels of turpentine and 1,750,000 barrels of rosin. The United States has for many years produced about twothirds of the world’s supply of turpentine and rosin. France is the only other large producing country, supplying about 20 per cent of the total. Probably not over half of our own production is consumed domestically. With the industry thus dependent on world economic conditions it has been periodically faced with overproduction and wide fluctuations in prices. These conditions together with the large number of comparatively small producing establishments have been determining obstacles in the way of technical advances in the gum turpentine and rosin industry.
Need for Scientific Research Repeated efforts have been made to consolidate and promote scientific investigations within the industry, the most noteworthy being the formation about ten years ago of the Pine Institute of America and the establishment of industrial fellowships a t the Mellon Institute financed by contributing assessments according to production. A year or two of poor hancial returns and the lack of education as to the rapidity with which chemical research can obtain visible cash results brought about a withdrawal of the support. Like many pioneering enterprises the effort was apparently premature, but many a turpentine operator had his thoughts directed to the chemistry of his products for the first time and from that viewpoint alone the results were not lost. There is no implication that technical advances have been lacking in gum turpentine and rosin production, but they have come to a considerable extent from influences outside the industry. For many years the U. S. Department of Agriculture through both the Bureau of Chemistry and Soils and the Forest Service has maintained an active, scientific naval stores program resulting in greatly improved methods in the woods operations and also in distilling the gum.
Experimental field stations have been established to study methods of chipping the pine tree and conditions affecting the flow of the gum as well as fundamental information on the gum formation in the tree. New types of stills have been designed and many technical improvements in their operation have been discovered and demonstrated to large groups of operators. All this has resulted in the increasing use of pine forests for naval stores production along the best conservation principles, with higher quality and better standardized products. At the present time by an Act of Congress the working of the pine forests for naval stores comes under the jurisdiction of the A. A. A., and gum turpentine and rosin are classified as agricultural products. The object of this change of status from a chemical industry is to permit effective regulation of production and to receive the benefits of government loans on surplus products until such time as the world consumption of naval stores resumes a more normal status. Efforts are being made at present by some of the larger operators to stimulate chemical research on naval stores in the state universities of the principal producing states, induced by the obvious necessity for new markets and new uses.
Naval Stores from Wood Waste Between 1900 and 1910 a new influence was created which was destined to have an important bearing on the chemise1 development of the turpentine and rosin industry. It was during this period that the greatest production in the history of naval stores was accomplished. Markets for the products seemed insatiable. I n the same period sawmills cutting turpentine pine lumber were enjoying their greatest prosperity; and with mill waste available in large quantities, this waste in the forms of slabs, edgings, and sawdust was conceived as another profitable source of turpentine. A half dozen or so plants were built to extract turpentine from sawmill waste enjoying several methods, but all used some form of low-temperature distillation. Steam a t high or low pressure was the most common method, and steam-distilled wood turpentine was produced for the first time. Incidentally, a new naval stores product was also introduced which is not present in the turpentine gum which flows from the living pine tree-vie., steam-distilled pine oil. This infant industry was encouraged on all sides by government and other conservationists who saw in the rapid conversion of the forests into lumber an actual end of the gum naval stores industry within a few years. It was soon apparent, however, that the yield of turpentine
NODERN GLMRosrs ALD
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TCRPENTINE PLAAT
Courtesy, U 8.Bureau of Chemistry and Bock
744
INDUSTRIAL AKD ENGINEERING CHElllISTRY
from mill waste was too low for profitable recovery except in periods of high prices; besides, the steam turpentine plants were too dependent on the sawmill for their raw material. Attention was then given to the logging waste, such as stumps, limbs, etc., which contained several times as much turpentine as the mill waste. But even this richer supply x a s not enough for continued profitable operation, as the fattest stumps contained not more than 6 per cent by weight of oil, and by 1910 hardly a plant was still attempting to operate.
Steam and Solvent Industry In 1908 Homer T. Yaryan began experimenting with the recovery of not only the turpentine and pine oil of the logging waste but also the rosin which constituted 20 per cent or more of the raw material. After steaming out the oils he extracted the rosin with gasoline. Yaryan built his first commercial plant at Gulfport, Miss., in 1909, and a second at Brunsvvick, Ga., in 1912. The completion of his first plant marks the beginning of the steam and solvent naval stores industry. In 1913 the Sewport Company erected its first plant at Bay ilfinette, Ala., and its second plant a t Pensacola, Fla., in 1916. In 1922 the plant of the Acme Products Company was completed at DeQuincy, La., and was acquired by the Newport Company in 1928. In this same year the General Naval Stores Company, an organization devoted exclusively to the sales of steam and solvent naval stores and handling only Kewport and Acme products was also acquired by the Kewport Company. In 1918 the Mackie Pine Products Company began operating their plant at Covington, La. The Hercules Powder Company in 1920 purchased the two Yaryan plants and also erected another at Hattiesburg, Miss. The Continental Turpentine and Rosin Company began operations a t Laurel, Miss., in 1921, the Dixie Pine Products Corporation at Hattiesburg in 1928, and the Phoenix Naval Stores Company at Gulfport in 1933. A11 of these plants are in operation a t present, although the original Gulfport operation is no longer a part of the Hercules organization. I n the twenty-five years since the inception of this industry only three small plants were built and abandoned. From the small beginning by Yaryan the steam and solvent industry has become an important factor in the naval stores world. With a combined capacity for treating around 750,000 tons of pine stumps and other resinous wood waste per year, these plants are producing from 20 to 25 per cent of the total turpentine and rosin made in the United States. Engineering skill and chemical research have played no small part in the success of this branch of the naval stores industry. To a considerable extent the chemical developments were forced upon these plants for their continued existence, since the products were a t the outset not as well adapted in naval stores consuming industries as were the gum turpentine and rosin. Centralized production made much of this possible in contrast with the many widely scattered gum-producing units that could hardly afford technically trained employees. Gum naval stores production also has the disadvantage of being seasonal compared to the 24-hour-day, year-round manufacturing operations of the steam and solvent plants. The steam and solvent naval stores industry is on a sound chemical basis and is pointing the way chemically to the entire industry. Many new chemical products have been offered to the consuming industries by the steam and solvent plants in recent years, together with many specially treated rosins of all grades adapted to consumers’ processes and problems.
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Much of the same thing could be done by the gum rosin and turpentine producers with large centralized refineries. One such plant has recently been installed in eastern Florida with a chemical staff. This is a start in the right direction.
Future
of the
Industrq
Khen turpentine was first distilled from the crude gum in about 1800, it soon found a steady demand and n a s used extensively for lighting and as a solvent. Its use for lampi liah long since been abandoned, but it is still used as a solvent for gums and resins, principally in paint and varnish, and for waxes in shoe polishes. Turpentine has found in all the years but two strictly chemical uses. One of these is the conversion to terpin hydrate and terpineol; this use, hoiTever, has been largely supplanted by pine oil which is 60 per cent or more terpineol and contains other valuable materials as nell. The other chemical use is for synthetic camphor which at preqent is well established and is consuming perhaps 10 per cent or more of the present United States production here and abroad, largely from pinene produced from steam-distilled wood turpentine. At one time turpentine was considered the only suitable varnish solvent; but if this were still accepted practice, rarnish production would be but a small part of its present total. Petroleum substitutes for turpentine have by necessity largely replaced it in paints and varnishes, and yet the protective coating field is still by far the largest use for turpentine. Kill the petroleums eventually replace turpentine entirely as a solvent? Can important new chemical uses be found for turpentine? These are questions which the naval stores industry must seriously consider. If the answer to tlie first question is “yess” the answer to the second must also be affirmative; otherwise, the industry must be able to qell its turpentine profitably in lowpriced competitive petroleum markets by providing other more valuable products from rosin, Rosin has enjoyed a much wider diversification of uSe5 in chemical industry. However, probably 70 per cent is consumed in soap, papers and protective coatings, Rosin is rarely used as such, as is turpentine, but as a chemical ram material. It is frequently pointed out that rosin is the cheapest available organic acid, and it is in many cases used as such by neutralizing the acid with alkali or combining with metals or esterification with alcohols. A large past of the chemical developments for uses of rosin has come from without the naval stores industry as is often the case. The industry has been particularly forlunate in recent years in the demand for rosin from the rapidly growing synthetic resin and plastics industries. Most of the developments within the industry, particularly in the steam and solvent branch, have been in new methods in refining and special processing, although as previously mentioned a number of new chemical naval stores products have been discovered. Rosin is a much more adaptable material than turpentine to chemical treatment because of its much greater stability, The future will undoubtedly see entirely new chemical products with rosin used as a starting raw material, and research programs will devote considerable time to such purely speculative fields. At the same time the study of the suitability 01’ rosin in its natural form or by special treatment to new chemical industrial materials is likely to be productive of the quickest returns from research. RECEIVED M a y 3, 1935,
