FIGURE1. RIGHT:WOODSHED IN THE FOREGROUND' MILL IN TEE BACKGROUND. LEFT:STILLHOUSE IN THE BACKGROUND; BOILERk o o IN ~ THE FOREGROUND
H. B. HUDDLE LTHOUGH there distill the oil there twenty years State Teachers College, Johnson City, Tenn. a r e numerous ago. Red cedar oil is also a byreferences to the product of the Musgrave PenciI early use of red cedar wood in the American Colonies, none Company of the same city. The George C. Brown Company, could be found on the distillation of the oil. The following Greensboro, N. C., began the distillation of the oil in a small facts concerning the history and present state of the indusway in 1915. Now it is among the largest producers. B. G. try were obtained through a questionnaire and by personal Rhodes has a still for producing red cedar oil a t Cedar Park, visits to producers. Texas. He is not manufacturing the oil a t present but has a stock of oil on hand, and his still is ready for operation History when the price justifies it. According to the information Apparently red cedar oil has always been a by-product of available, the companies that are in business today are: the cedar wood industry. More than forty years ago the Eagle Pencil Company began the distillation of red cedar oil Geor e C. Brown Company Greensboro N. C. Closet lining erland Cedar Works Sheleyville,' Tenn. Pencil slats cum% a t Cedar Keys, Fla. The total production probably amounted Homisassa, Fla. Pencil slats F. and 0. Cedar Works Lebanon Tenn. to 75 or 100 pounds a week. This oil was exported to GerPencil slats Gulf Red Cedar Company Pencil slats { Monticeilo K y . many for use in soap and perfumes. Lewisburg,' Tenn. Houston and Liggett Closet lining Shelbyville, Tenn. Pencils Musgrave Pencil Company About this time the American Pencil Company was also a TennesseeRedCedar Woodenware Murfreesboro, Tenn. Cedar buokets Company producer of the oil. Beyond the fact that wood and iron Cedar Park, Texas Red cedar oil B. G. Rhodes were used in the construction of the stills, no further information was available. The Gulf Red Cedar Company, which now operates pencil-slat mills a t Lebanon, Tenn., and MontiDistillation of Red Cedar Oil cello, Ky., began the production of the oil in 1896. Some Red cedar oil is obtained by steam distillation of the sawthirty years ago George M. Stiegler, working for the F. and dust. With one exception, all the producers a t the present 0. Cedar Works, Ltd., was in charge of the distillation plant time use only waste wood from mills making pencil slats, a t Nashville, Tenn. This company also has a plant at pencils, cedar lining for clothes closets, cedar chests, cedar Homisassa, Pla. Their plant at Murfreesboro, Tenn., was churns, wine coolers, etc. Some oil is produced from roots acquired by the Tennessee Red Cedar Wooden Ware Comand stumps, old fence rails, timbers from old houses, or any pany, which began to distill the oil after 1909. In 1912 other types of old virgin cedar. The virgin cedar, which Houston and Liggett Manufacturing Company, Lewisburg contains more heartwood than second-growth cedar, is and Walterhill, Tenn., began to utilize its waste wood to becoming very scarce. All of the oil of red cedar comes from produce red cedar oil. Two distilling plants are located in the red heartwood; the sapwood is devoid of oil. It is for Shelbyville, Tenn. H. L. Woosley of the Cumberland Cedar this reason that roots and stumps of virgin cedars and old Works and also of the National Pencil Company began to 18
JANUARY, 1936
INDUSTRIAL AND ENGINEERING CHEMISTRY
19
of the company on the death of their father in 1926. The fence rails or house timbers that were made from them are mill produces pencil slats, cedar buckets, churns, wine coolers, used for the production of the oil. and ice tubs. The waste from the manufacture of these The term “virgin cedar” as used in the trade refers to the products, along with the roots, stumps, rails, and timbers cedar in the virgin forests. This cedar was straight and free mentioned previously, is used for the production of the oil. from knots. I n these old tall straight trees the proportion So far as could be determined, this is th‘e only company of sapwood was small. There seems to be some confusion buying cedar for distillation only at the present time. as to the use of the terms “sap cedar” and (‘second growth.” The roots, stumps, etc., are chopped into suitable sizes in Some distillers consider the terms synonymous. However, the wood yard (Figure 1). This wood and the waste from others call the large trees which have grown since the virgin the mill (Figure 1) is fed into the hogging machine (Figure 2) forests were cut “second growth” and designate the small which consists of a cylinder with twenty knives. This matrees of recent growth as “sap cedar.” One tree of virgin chine reduces the wood to pieces to 3/4 inch in diameter and cedar is reported which was 5 feet in diameter and more than 8 to 10 inches in length. In an underground room directly 100 feet tall. A possible example of second-growth cedar beneath the hogging machine is the hammer mill. The wood might be found in a tree which the writer knows to be seventyfive years old. It is 19 inches in diameter and about 50 feet falls from the hogging machine to the hammer mill which reduces it to dust. This dust is then blown through a pipe high. Small cedars of recent growth have a relatively high percentage of white sapwood which contains no oil. One from the hammer mill into the loft of the stillhouse (backproducer classifies as sap cedar all logs that have from 2.5 to ground at left Figure 1). The six stills (Figure 3) extend through the floor of the 3 inches of white sapwood. loft of the stillhouse. The cedar dust is shoveled by hand There is also some disagreement as to the yields of oil from virgin and sap cedar. However, the virgin cedar yields about into the tops of the stills. The still heads are then replaced 3.5 per cent and the sap cedar less than 1 per cent. Some and steam is blowii into the bottom of the still through a producers place the estimate even lower. The heartwood perforated pipe. The stills are cylindrical steel tanks and from either sap cedar or virgin cedar contains approximately are of two sizes. The larger ones are 5 X 8 feet and the smaller 4 X 16 feet. They take charges of 5200 and 3500 the same amount of oil. The higher the percentage of sapwood, the lower the percentage of oil, provided the whole log pounds of dust, respectively. After about 8 hours the spent is distilled. sawdust is removed from the bottom of the still and shoveled The characteristics of the oil obtained from virgin cedar into a pile in front of the boilers which produce steam for and sap cedar are different also. It is believed that virgin the stills and for power. The sawdust, which is practically cedar yields an oil containing more of the high-boiling comdry by the time it reaches the pile, is the only fuel used. ponents that make the odor of the oil more permanent. It The steam and oil leave the still head and pass downward is also thought that sap cedar produces an oil rich in cedar through a coiled condenser cooled in a tank of running water. camphor or cedrol. This oil is sometimes called “camphor The condenser pipe projects through the side of the cooling oil,” and entire drums of it have been known to congeal. I n tank and allows the oil and water to flow into the receiver. 1916 Gildemeister and Hoffmann (6) advanced the theory The receiver is a 5-gallon cylindrical tank with a gooseneck that cedrol may be formed when cedar sawdust or shavings spout that makes it resemble a coffeepot. The water sepaare exposed to moist atmosphere for a long time. The rates and goes to the bottom whence it passes put through experience of the producers has not the gooseneck spout verified this conjecture. They have into a pipe line that The production of red cedar oil is c o l l e c t s the water noticed that long exposure of the dependent upon the supply of virgin red s a w d u s t to moist atmosphere ref r o m a l l of the six cedar (Juniperus virginiana) which is receivers, The oil duces the yield of the oil by half but being depleted rapidly. The history of that collects a b o v e does not increase the cedrol content. They a r e , f u r t h e r m o r e , of the the water is removed the production of the oil is reviewed from time to time by opinion that long exposure to the sun briefly and a list of the present distillers decreases the yield of the oil. an a t t e n d a n t who is included. The equipment used by the differdips it from the reThe method of production is presented ent producers varies little except in ceiver into a 2-gallon by a detailed description of a typical still. dimensions and in the kind of metal bucket. The bucket .used. The dimensions of the cylinis then emptied into The physical properties and proximate drical tanks which hold the sawdust the filter. The water analyses of three samples of oil distilled vary from 4 X 10 feet, to 5 X 18 f r o m t h e p i p e line in 1932, 1933, and 1935 are given. The feet. Wood, steel, galvanized iron, flows into a n o t h e r varied uses of the oil are discussed at copper, and monel metal have been receiver from which ’ length. used. There is much comolaint as to some oil is recovered. the corrosive action of the oil on the and is redistilled in an old whisky doubler giving a clear oil stills. Since the process used in all the plants is practically known as water-white or double-distilled. the same, the distillery of the Tennessee Red Cedar Wooden Ware Company a t Murfreesboro, Tenn., will be described as The filter (the small tank,at the left of Figure 3) into which the oil is poured is 3 feet in diameter and contains a false an example. bottom on which rests two bolts of cotton batting for reRed Cedar Oil Distillery moving foreign particles. The oil from the filter is light I n 1866 William Doughtery installed a mill a t blurfreesgolden yellow in color and is known as oil of cedar wood. boro for the manufacture of red cedar wood products. He Physical Constants and Proximate Analysis was succeeded by Prewitt Spurr Manufacturing Company. In 1909 W. L. Patterson, who had been employed by the The range of values for the physical constants of cedar oil Prewitt Spurr Company, bought the mill and changed the as found in the literature is as follows: dl, = 0.943 to 0.961; name to the Tennessee Red Cedar Wooden Ware Company. CY’: = -25” to -42”; = about 1.504; acidvalue, up to The present operators, Patterson and Patterson, took charge 1.0; ester value, up to 6.5; ester value after acetylation,
’
1
INDUSTRIAL AND ENGINEERING CHEMISTRY
20
26 to 42. The solubility is 1 volume of oil in 6.5 volumes of 95 per cent alcohol (6). Three samples of oil from Murfreeshoro gave the following values: SeDt., 1932 0.9539
.
n
g
saponifiostion No.
Aord No. Aoetyl value Ester No. (onlod.) Iodine No. Moisture, %
-500
1.5042 8.71 2.63 43.85 6.08 60.96 0.3
Sept.. 1938 0.9581 -44.75’ 1.5058 5.93 2.50
....
3.43 64.30 Trnoe
March. 1985 0.9441
-39-
1.3038 6.76
0.XO 27.66 5.96 61.79
Trace
Cedar oil appears on the market under the names: Cedernholzoel, Essence de Bois de Cedre, Huile de Cedre, Olio di Cedro, Oleum Idgni Cedri, Oleum Juniperi Virginianae, and Zedernorl.
Soap and Perfume Industries On account of its pleasant fragrance and cheapness the oil is extensively used in the soap industry for making fine ‘soaps where a sweet odor is not required. It also finds use as a basis for perfumes and eold cream. Poucher (21) gives the following formula for R typical perfume containing cedar oil:
Cedar oil, OC. clove Oil 0 0 Casnin ec. Bemarnot oil,
VOL. 28, NO. 1 300 120 SO
cc.
400
Densaldehyde, ce. Phenyl ethyl alcohol, 00. Musk xylene, grams
30 50
20
According to the U. S. Dispensatory (16) red cedar oil was one of the principal ingredients of the once popular extract of white rose. The popularity of cedar, which is said to be the seventh odor in order of preference, is attested by the fact that it is used to mask the odors of chlorine disinfectants, furniture polish, insecticides, and naphthalene and pdichlorobenzene moth cakes. It is also used in compounding an oriental perfume oil for deodorizing theaters. In connection with the use of cedar oil in perfumes, Gildemeister and IIoffmann (6) observe that tho oil obtained from drying kilns does not contain the high-boiiing constituents that have been left in the wood. They add tliat the oil thus obtained is limpid and its odor is less delicate and permanent. No infomiation concerning such drying-kdn oil could be obtained from the present producers. It might be possible that this was redistilled red oil. Parry (IO) states that the oil is improved by keeping.
Immersion Oil for Microscopes Students are familiar with the use of red cedar oil as an immersion oil for microscopes. Such an oil should be clear, t r a n s p a r e n t , and colorless, and should have an index of refraction close to 1.52. If the oil is too thin, i t allows bubbles to appear between the cover glass and the microscope objective. On the other hand, oil wliich is too viscous is u n p l e a s a n t to handle. Furthermore, the desired index of refraction places an upper limit on the viscosity. Deussen (9) investigated a sample of oil-immersion cedar wood oil from B u t t n e r and Company, Leipeig. He concluded that some kind of a resinous substance had been added to tho “thickened” oil to make the refractive index the same as that of glass-namely, 1.515. Apparently such additions are unnecessary, for samples of cedar oil with indices of refraction falling between 1.515 and 1.525 have been prepared in this laboratory by fractional distillation alone. Because of its clieapness red cedar oil is not often adulterated. There has appeared on the market, however, a commercial red cedar oil which is a mixture of the oil and turpentine. Another instance of adulteration is reported by Morosov (9)in an article on the “Detection of the Adulteration of Cedar Oil with Manchurian Bean Oil.” The pure oil is easily identified b y i t s high specific gravity, high levorotatory power, and saponification numbers before and after acetylation.
Adulteration with Red Cedar Oil
JANUARY, 1936
INDUSTRIAL AND ENGINEERING CHEMISTRY
and Risse (18) oxidized the oil by means of ozone and also by means of potassium permanganate to the ketonic acid. This product was then oxidized to the dicarboxylic acid by alkaline bromine solution or by nitric acid. A simplified technic for the oxidation of the oil to the glycol was described in 1925 (5). Red cedar oil is the principal adulterant of sandalwood oil. Its addition increases the optical rotation and decreases the specific gravity and also the solubility of the sandalwood oil in 70 per cent alcohol. A liquid or semi-liquid orris oil occasionally found in commerce is prepared by distilling orris roots with cedar oil or with other oils. More often a little orris oil is mixed with such oils to prepare the commercial product. Cedar oil was formerly the principal adulterant of oil of lavender. The adulterated oil was detected by its changed solubility and ester content. Of the two adulterants of camomile oil-milfoil oil and red cedar-wood oil-the latter is used more frequently. The adulteration with red cedar oil can he detected by comparing the odor with that of a genuine sample. Furthermore, the addition of red cedar oil lowers the congealing point. Red cedar oil, as well as turpentine and gurjun balsam, is used to adulterate geranium oil. Such addition lowers the ester value and the solubility of the oil in alcohol. The presence of cedar oil has been reported in palmarova oil, anise oil, peppermint oil, ionone, and occasionally in eau de Botot.
Insecticides Red cedar oil finds wide use as an insecticide in dusting compounds, moth repellents, and sprays. Patents have been granted for a variety of products containing red cedar oil: carbon remover containing also acetone, benzene, camphorated oil, denatured alcohol, and turpentine (4);cleansing and polishing liquid (7); furniture polish (14); and sweeping compound (9). The volatile oil present in cedar wood has given it a lasting reputation as an efficient insecticide and moth repellent. The popular belief in its efficacy goes hack to colonial days; the earliest mention was made of it in 1682 ( I ) . Because of tho popular belief in the efficacy of cedar chests as protectors against moth damage, the U. S. Department of Agriculture has conducted two series of experiments to determine their value (1, 12). In brief, the results were that cedar chests exerted no noticeable effect on the adult moth, the eggs, half-grown iarvae, or pupae. However, thecedar chests did kill young larvae. Since the moth, eggs, and pupae are incapable of injuring garments, it is necessary to make sure only that the garments going into tight cedar chests are free from the older larvae or worms. Clothes closets may be lined with cedar wood or may he plastered with a cedar plaster, among the ingredientsof which are Tennessee red cedar wood and red cedar oil. There are on the market cedarized garment bags and storage cabinets which are impregnated with cedar-wood oil and cedar-leaf oil. Recently a patent was issued to Kinnell (8) for incorporating ground cedar and cedar oil into a paper product for making garment bags. Although cedar products are widely used for protecting garments, apparently the oil itself has not heen tested as a mothdestroying agent. Ce&r shavings are also sold for kennel bedding to drive fleas from dogs and for nests to free hens from mites.
Medicinal Properties Cedar oil resembles oil of savin in its medicinal properties and is used as an abortifacient in this country more often than oil of savin or turpentine. However, of eighteen cases reported by Witthaus (17), no abortions were produced and three deaths resulted. The symptoms are a burning h the stomach, vomiting, convulsions, coma, and a slow pulse,
21
with evidence of gastroinflammation after death. A honreopathic tincture of Jzrniperus virginiana can he found on the market. Though rarely used, it is sometimes prescribed for nausea and vomiting, swollen abdomen, and difficulty in passing urine. Drnggists sell small quantities of the oil for preparing homemade liniment. The oil mixed with alcohol, ammonia, and camphor is used as a liniment for horses. Volhner (16) includes cedar oil in a list of substances which are photoactive and hyperglycemic. Gddenieister and Hoffmann (6)state that inhalation of the vapor of the oil imparts a violet odor to the urine. The present price (June, 1934) of the oil at the still in 55gallon drums (approximately 420 pounds of oil) is 20 cents a pound. The oil has brought as much as 80 cents. Although the oil is obtained from waste wood, the present price does not justify production. The demand for the oil is relatively small and a t least three plants have not operated for 2 years. The annual production is estimated a t 150,000 pounds.
Literature Cited (1) Back. E. A., nnd Rabak, F.,U. S.Dopt. Agr.. Bull. 1051 (1922) (2) Conrad, E., U. S. Patent 1,758,735 (NOT. 25, 1927). (3) Doussen, E., J. prakl. Chon.. 117, 303 (1927). (4) Esaiok. J. H.. U. 6. Patent 1.869.310 (Aoril 4. 1931). (5) Etablisseme&s A. Chiris. Parfums $&ce, No. 28, 168 (June, 1925). (6) Gildemeiater, E., and Hoffmann, F. R.,"Volatile Oile." 2nd ed., Vol. 11, p. 165, New York, John Wiley and Sons, 1916. (7) Iierdy,S.,TJ. S.Patent 1,758,317 (May 24, 1928). ( 8 ) Kinnell, D. C., Ibid., 1,927,798 (Sept. 19, 1933). (9) Mornsov. N. T., J. Tram. Rues. Chinme. Poiglech. In& Horbin., 4, 1 2 1 3 3 (1925). (IO) Parry. E.,"Chemistry of Essential Oils," 4th ed., Yol. I, p. 2, New York, D. Van Nostrand Co., 1921. (11) Pouoher, W. A., "Periumea. Cosmetics and Soaps," Vol. I. p. 92, New York, D. Van Nostrand Co., 1930. (12) Soott. E. W., Ahbott. U'. S.,and Dudley. J. E.. U. S.Dept. A n . . BuU. 707 (191Xj. (13) Senunlcr. F. W., and Risse, F.,Ber.. 45, 355-60 (1912). (14) Sturm, E. E., U. S.Patent 1,739,332 (Nov. 25. 1927). (15) U. S. Dispensatory, 19th ed., Part 11, p. 1537, Philadelphia, J. B. Lippineott Co., 1907. (16) Vollmer, H., Biochem. Z., 174, 143-5 (1926). (17) Witthaus, R. A., "Manual of Toxicology.)' 2nd ed., p. 1095, Wm. Wood and CO.,1911. R e c ~ r v mFebruary 14. 1935.
