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bleaching operations be conducted in solutions. The piling of the goods, either saturated with chemick or saturated with acid, cannot be as efficient as allowing .
the goods to lie in solutions. A simple test to determine whether the bleached fabric is permanent in color consists in steaming the cloth for one hour at a pressure of 5 pounds per square inch. If the color be permanent there is no change in shade, or yellowing, as it is termed; but if the bleaching be not well done orthorough, the white turns yellowish. The change of shade toward yellow, or toward the original color, serves as an index of the quality of the bleach.
J. Ind. Eng. Chem. 1914.6:720-723. Downloaded from pubs.acs.org by UNIVERSITE DE SHERBROOKE on 01/15/19. For personal use only.
FAILURE
OF
WETTING
OUT
TEST
The six samples analyzed, when tested by the wettingout method described above to determine the efficiency of the boil, and by the steaming method to determine
the permanence of the bleached goods, give the following results: The gray goods and the sample taken from the steep did not sink in water, while all the other samples sank instantly. No difference in the time required for the pieces to reach the bottom of the beaker could be noted in the pieces taken from the second boil, the chemick or the sour. The piece, however, taken from the first boil required a perceptibly longer time to reach the bottom. No better illustration could be given of the failure of tests of this character to give positive knowledge. There is, in the sample taken from the first boil, 79.6 per cent of the total fats and waxes, and in the sample taken from the second boil 36 per cent, or a difference of 43.6 per cent; yet the wetting out tests show no corresponding difference. But we must, however, note that the sample taken from the first boil showed that 91.7 per cent of the We must also note that, proteins are eliminated. after the removal of the proteins, more than twice as much of the fats and waxes are eliminated by one boil as are removed by the steep and the first boil. This raises the question, do the colloidal proteins serve as a more efficient waterproofing than the fats and waxes? When steamed, of the samples not bleached, the sample from the gray and the sample from the steep showed the same yellowing, becoming decidedly browner. The samples from the first and second boil showed the same slight yellowing, and the samples from the chemick and the sour hardly changed in tone or shade. CONCLUSION
From these results we must conclude that the proteins are the cause of the yellowing of cloth in steaming, rather than the fats and waxes. Until we have positive proof that the amounts of the pectin substances present are the cause of yellowing in steaming, I think the above statement is a safe inference from the analytical results. This investigation has been made in an effort to determine what constitutes a good bleach from a chemical standpoint. It appears from the results that such a definition is possible. It now remains to compare, by the sanie methods, goods not well bleached with those that are well bleached, and thus determine the definite factors. Providence,
R. I.
AND
ENGINEERING
CHEMISTRY
Vol. 6, No. 9
THE CHEMISTRY OF PINE OIL1 By Maximilian
Toch
One of the industries, which has developed as a result of the policy of conservation in the United States, is the manufacture of useful products from resinous woods. Enormous quantities of the latter, which in previous years were considered of little or no use and were deliberately burned in huge burners, especially constructed for the purpose, or were simply allowed to go to waste, .are now being economically and profitably manipulated for the recovery of turpentine, pine oil, and rosin, or the production of tar oils,
pine pitch and charcoal. The two commercially important methods in vogue are, (1) the steam and solvent or extraction process and (2) the destructive distillation process. Mr. . T. Yaryan has taken out letters patent on a process for extracting turpentine and rosin from resinous woods, which very well illustrates the extraction method as practiced today. Resinous wood, reduced to fine chips by passing through a wood chipper, is charged into an iron vessel through a charging door at the top. The wood rests upon a false bottom over a coil supplied with superheated steam for producing and maintaining the proper temperature within the iron chamber. The door at the top and the discharge door at the bottom are closed, and the current of is steam driven into the mass of superheated chips. This is continued until the more volatile turpentine has been vaporized and driven over into the condensers. The wood in the extraction vessel is left charged with a small percentage of heavy turpentine, together with pine oil and rosin. Steam is shut off, the excess moisture in the hot wood is removed by connecting the vessel with a vacuum pump, and finally, a liquid hydrocarbon (b. p. 240-270° F.) is sprayed over the top and allowed to percolate down through the pores of the wood. The resinous materials are thus thoroughly and completely extracted, and passed into a storage tank, from which they are pumped into a still used for separating the component parts of the solution. From the still the hydrocarbon solvent is readily separated from the heavier pine oils by distillation under reduced pressure, on account of the great difference in the boiling point between the pine oils and the hydrocarbon solvent, the former boiling between 350—370o F. The pine oils are in turn separated from the rosin by distillation with superheated steam. This process has been operated on an enormous scale by the Yaryan Naval Stores Company,2 with plants at Brunswick, Ga., and Gulfort, Miss. This Company’s Brunswick, Ga., plant alone utilizes from 500—600 tons of wood each 24 hours—probably a larger consumption than the combined pine wood destructive distillation plants of the country. Other so-called “low temperature” processes deserve mention as possessing features of merit, although to 1
Presented before the New York Section of the Society of Chemical
Industry, The Chemists’ Club, April 24, 1914. 2 The following is a list of the Yaryan U. S. patents: No. 915,400, March 16, 1909 915.401, March 16, 1909 915.402, March 16, 1909 922,369, May 18, 1909
934,257, September 14, 1909 964,728, July 19, 1910 992,325, May 16, 1911
Sept., 1914
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date sufficient data do not appear to be available to show their true value when operated on a large commercial scale. The Hough process, for example, is in to be considered essentially a preliminary treatment the manufacture of paper pulp from resinous woods. Chipped wood is placed in a retort and subjected to The rosins are saponified the action of a dilute alkali. and the soap separated from the alkaline liquor by cooling and increasing the alkali concentration to the desired degree. The rosin soap may be sold as such, The or treated with acids for recovery of the rosin. turpentine and pine oils are recovered either by preliminary treatment with steam or during; the early stages of the cooking process. It will be noted that in the low temperature processes the only products recovered are turpentines, pine oils and rosins, the first two removed through the .action of steam, either saturated or superheated, and
the latter through extraction by use of a neutral volatile solvent or a saponifying agent. The so-called “spent wood” may be used either for the manufacture of paper pulp or as a fuel to generate the power necessary to carry out the process. In the destructive distillation process, the wood, in the form of cordwood 4' to 6' in length and 4" to 8" in diameter, is placed in a horizontal retort and the temperature gradually raised until the wood is thoroughly carbonized. The factor of greatest importance in the successful operation of this process is temperature control, as it is essential that the turpentine and pine oils be removed in so far as is possible before the temperature at which the resins and wood fiber begin to decompose is reached. The total volume of distillate as well as the percentage volume of each of the several fractions thereof, is largely dependent on the degree of temperature control. Destructive distillation of resinous wood was first carried out in earthen trenches, the combustion being controlled by partially covering the wood with earth. Tar and charcoal were the only products recovered. Then came the beehive oven, operated in much the ..same crude manner, but recovering the more volatile
ENGINEERING
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721
distillates, in addition to tar and charcoal. This was in turn superseded by the horizontal retort, externally heated, hot gases being circulated either through an Next outer shell or through pipes within the retort. came the bath process, wherein the cordwood was immersed in a bath of hot pitch or rosin, thereby volatilizing the turpentine and lighter pine oils and dissolving the heavier oils and rosins. After this the bath was withdrawn and preliminary treatment the wood subjected to straight destructive distillation. More recently1 a retort has been devised utilizing the basic principle of the laboratory oil bath. The retort is heated by means of a layer of hot petroleum oil which is kept continually circulating between the retorts and an outer cylindrical shell that completely surrounds the retort proper. In this way it is claimed the temperature of distillation can be accurately controlled. The turpentine and pine oil obtained are fractionated and rectified by subsequent steam distillation. In running the retort the temperature of the oil bath is so regulated that the heat inside does not exceed 450° F., before all the turpentine and pine oil have been distilled. The products of destructive distillation by the several processes are in each case of very much the same general nature, namely—turpentine, pine oils, tar oils, pine tar, pitch and charcoal. In some instances low grade rosin oils are also produced. “Light Wood” does not refer to woody fiber which has a light specific gravity. The name originated from the fact that this particular wood is so rich in oil and resinous material that it is readily used for lighting fires. In the southern portion of the United States little bundles of “light wood” are for sale in strips about 1/4 in. in diameter and 1 ft. long. When a fire is applied to one of these strips of wood it becomes useful for lighting fires, hence the name “light wood.” I have seen “light wood” so rich in rosins and oily material that by transmitted light a thin section looked like translucent ruby glass. It is this particular wood which is most used for the distillation of wood turpentine, pine oil and rosin. The product from that type of pine tree from which turpentine is obtained has always been regarded as producing two materials when the sap has been collected and distilled. The one material is turpentine, and the other rosin. About ten years ago, when destructive and steam distillation of pine wood became a practical industry, a third substance was recovered. This material, intermediate between turpentine and rosin, is now known as “Pine Oil.” As far as I know, no one has yet determined the chemical constitution of this intermediate product of the pine tree, which has been designated as “Pine Oil.” Two years ago I started this investigation, which is practically finished, and it is my privilege to show you to-night the raw material from which pine oil is made and the various processes by which it is refined. The chemical composition of this material and the work which led to its determination will be published, and therefore I shall not dwell at any great length on this 1
T. W. Pritchard, This Journal,
4 (1912), 338.
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phase of the subject. There is as yet no standard of purity for pine oil, but that it has a definite chemical composition is now fairly well established. The only original investigation of the chemical composition of pine oil was carried out by Dr. J. E. Teeple1 on “Long Leaf Pine Oil.” Dr. Teeple says: “The commercial long leaf oil, on the market, is either clear and water as it comes white, containing 3 or 4 per cent of dissolved water, of it may have a very faint yellow color and be free The specific gravity ranges from dissolved water. from 0.935 to 0.947, depending on freedom from lower boiling terpenes. A good commercial product will begin distilling at about 206o to 210°; 75 per cent of it will distil between the limits 2110—218° and 50 per cent of it between 213-217°. A sample having a ° density of 0.945 at 15.5 showed a specific rotation of about [a]^° —11°, and an index of refraction of of the oil the n 1.4830. In fractional distillation specific gravity of the various distillates rises regularly with increasing temperature, becoming steady at about 0.947 at 217 °. “If the oil consists essentially of terpineol, CioHisO, it should be easy to convert it into terpin hydrate, C10H20O2 + H20, by the method of Tiemann, and Schmidt.2 The conversion was found to proceed easily when the oil was treated with 5 per cent sulfuric acid,
Sample
S-12,200 S-12,201 S-12,496 S-14,499 S-14,500 S-14,501 S-14,560 S-14,561 S-14,562
Acid
Color
Faintly yellow
Not quite water Water white
white
Straw color Pale amber Straw color Water white Straw color Water white
0.68 0.29 0.51 0.59 0.49 0.70 0.17 0.73 0.27
Flash(0)
^afue point eF 142.5 118.4 125.4 161.5
173.9 143.2 129.8
142.7 124.4
170 175 145 160 148 168 175 160 176
of
o'
9 hrs.
10.4 10.7 11.9 7.6 8.5
93.4 96.3 97,3 93.8 85.7 92.7
11.2
10.4
78.3
11.5 11. 1
8.9
10.6
79.0
11.2
9.8
79.6
or
without
admixture
with
benzine.
If
agitated continuously, the reaction is complete within If, on the other hand, the mixture is 3 or 4 days. allowed to stand quietly, the formation of terpin hydrate extends over several months and produces most beautiful large crystals, which, without recrystallizing, melt at 117—118°. When recrystallized from ethyl acetate they melt at 118°. Yield, about 60 per This forms such a simple, cent of the theoretical. of making terpin hydrate method and convenient cheap
that it will doubtless supersede the usual manufacture from turpentine, alcohol and nitric acid, and instead of terpin hydrate serving as raw material for the manuwill be facture of terpineol, as heretofore, the reverse the case.” “Pine oil,” as now understood, is the heavy oil obtained from the fractionation of crude steam distilled wood turpentine. When the sap of the pine tree is subjected to distillation in a current of steam the volatile liquid—turpentine—consists almost entirely of the hydrocarbon, pinene, CmHie. When, however, 1
3
J. Am. Chem. Soc., 30, p. 412. Ber., 28, p. 1781.
On steam bath (b) Per cent loss
H 11.5 11.4 11.1 10,6 10.6 11.4
C 78.1 77.9 77.0 81.8 80.9 79.0
(o) Open cup (Tagliabue tester). (6) After evaporation a small, hard residue, similar in appearance to pale rosin dark, almost black in color, due probably to impurities in the pine oils.
either with
Evaporation
Pine Oils
Ultimate Analyses
78.4
Averages
CHEMISTRY
Vol. 6, No.
9
the trunk, stumps and roots Of the same tree have been allowed to remain on the ground for a number of years and are then steam distilled, there is obtained, in addition to the turpentine and rosin, certain heavier oils formed by hydrolysis and oxidation as a result of exposure to the atmosphere. To the heavier oils thus formed and yielded up in the process of steam distillation the term “pine oil” is properly applied. Pure pine oil has a very pleasant odor, an aromatic odor similar at times to the oil of caraway seed or the oil of juniper seed. When pine oil is impure it is very difficult to use it for interior work on account of pernicious odor of empyreumatic compounds. It has been used to a considerable extent for making paints which should dry without a gloss, and as a “flatting” material it has been very successful. It has the excellent quality of flowing out well under the brush and of not showing brush marks, the latter because it evaporates so very slowly. It is a very powerful solvent, and many of the acid resins which have a tendency to separate when they are insufficiently cooked with drying oils will remain together when pine oil is added. Pine oil can be used to a considerable extent as a diluent in nitrocellulose solutions, and as a cooling agent for the reduction of varnishes it also has excellent qualities. The author takes this opportunity of stating that on previous occasions his recom-
Table I—Analyses Sp. gr. at 15‘A° C. 0.9423 0.9427 0.9338 0.9330 0.9291 0.9355 0.9382 0.9350 0.9383
ENGINEERING
AND
was
left.
9.6
In the
98.6
95.1 98.7
case
room
Tests
temperature
4 Ers.
6 hrs.
43.8 31 .8 46.9
52.2 41.8 58.6
36.8 39.5 46.4
56.6 58.9 68.0
24.6
35.3
—
Per cent loss after
27.8 20.3 30.4
2
hrs.
At
69.8
70.5 81.0 46.0
8
hrs. 67.2 50.8 70.0 80.4 82.5 88.7 53.2
65° F.
24 hrs. 32 hrs.
96.7 92.4
97.5 95.5
96.5 94.0 88.8
of S-14,999 and S-14,500, the residue
was
96.7 92.7 97.5 95.5 96.5 94.0 90.4
very
mendations concerning new and useful materials for the paint and varnish industry have been misunderstood in some instances, and it is to be hoped that this treatise will not be misinterpreted. Pine oil is a new and useful material, but it is by no means a substitute for linseed oil or turpentine or any of the other materials now on the market. It has properties peculiar to itself, and when intelligently used is of considerable value. Practically all of the pine oil obtainable contains a small percentage of water in solution, to which it clings a simple rather tenaciously, and it is by no means A rather complex matter to dehydrate this material. apparatus for dehydrating the material is necessary with temperature control, but the test which the author of water is quite has devised for the determination simple. If 5 cc. of pine oil are mixed with 1 cc. of a neutral mineral oil, like benzine, kerosene or benzol, and a perfectly clear solution is obtained on shaking, no water is present; but if there is any water present in the pine oil the water appears as a colloid, and a milky solution is obtained which does not separate after long standing. The fact that pine oil will take
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THE
Sept., 1914
a considerable quantity of water and still remain clear makes it useful for emulsion paints such as are very much in vogue at the present time for the interior of buildings, and it has been suggested that the addition of water up to 5 per cent for such a purpose is beneficial on new walls. The United States Bureau of Chemistry1 has developed a method for the determination of moisture by the use of calcium carbide;
up
Table
II—Ultimate
-Terpineol (theoretical)............ French turp. (a).................... American turp.(a).................. Wood turp. (a)..................... Pine oil—first running.............. Distillate—pine oil, 345-380° F., 174-
Analyses C 77.85 87.7 87.7 85.7 84.3
H 11 11
.77
.9 12. 1 12. 1
11.8
195° C.......................... 82.6 11.4 (a) M. Toch, “The Chemistry and Technology of Mixed D. Van Nostrand Company, publishers, New York.
O 10.38 2.2 3.9
6,0
Paints,” by
this is being investigated at our laboratories, but on account of being a gas-volumetric method it is not
quite feasible for general
use in technical laboratories. of commercial samples of pine oil were dehydrated and analyzed. Tables I, II and III indicate the results obtained.
A number
of Table III—Fractional Commercial Pine Oil Distillation Fraction in % Total distillate Temperature Sp. gr., 15. 2 2 Water, 100°
174-194 194-205' 205-208 208-2.10
.
210-213
213-216 216-218
218-
5 11
10
25 35 6 1
4
7
18
28 53 88 94 95 99
0882 0.920 0.933 0.939 0.941 0.942 0.942
The author is glad to acknowledge here the assistance which was given him by Mr. C. A. Lunn in furnishing the samples of raw materials. .320
Fífth
Ave., New York
OILS OF THE CONIFERAE. I—THE LEAF AND TWIG OILS OF CUBAN AND LONGLEAF PINES AND THE CONE OIL OF LONGLEAF PINE By A. W. ScHORGER Received July 6, 1914
The annual consumption of leaf oils of certain native conifers amounts to about $50,000. The principal species distilled for oil are the black spruce (Picea mariana, Mill.), white spruce (Picea canadensis, Mill.), hemlock (Tsuga canadensis, Linn.), red juniper (Juniperus virginiana, Linn.), and arborvitae (Thuja occidenialis, Linn.). No attempt appears to have been made to distinguish between the two spruce oils and it is doubtful if much genuine hemlock oil is to be found on the market, since the oils of the three species are quite similar and for practical purposes no distinction seems Fritzsche Brothers of New York necessary. City estimate the annual consumption of spruce oil at 40,000—50,000 pounds. It is extensively employed as a perfume in greases and shoe-blackings and is quoted at $0.45—$0.60 per pound. The leaf oil of the red juniper is sold at about the same price as spruce oil. and is largely used in insecticides. The annual consumption is 15,000—20,000 pounds. The annual cut of lumber from conifers far exceeds that of the hardwoods. The tops are left in the woods and, in addition to being a total loss, are the most fruitful source of forest fires. Several states have 1
U. S. Dept. Agrie., Bur. Chem., Circ. 97.
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723
attempted to cope with the fire problem by passing laws compelling either the “lopping” or burning of the tops. The Forest Service in leasing timber rights stipulates that the tops must be burned or lopped and scattered. If only sufficient oil could be obtained to for the cost of handling the material, there would pay be an economic gain to the lumberman, since lopping or burning entails an expense with no return whatever for the labor involved. This investigation was undertaken with a view to determining the yield and composition of the leaf oils of the more utilization.
important conifers with
a
view to their
Several western species were distilled by Mr. G. M. Hunt of the Forest Service. The yields obtained for these oils and their composition will be published later. In most cases the yields from the western species were low. The odor of the oils from both the western and southern species was peculiar and less pleasant than the This may be accounted for spruce oil of commerce. by their low alcohol and ester content compared with spruce oil. From the yields of oil obtained from the southern and western species it was thought that an approximate idea of the probable yield of a species could be obtained from the cross section of the needles. The inference is logical that the yield should depend on the number and size of the resin ducts per unit of cross sectional area. Cross sections of the needles of several species were made and the above inference was verified in a striking manner, as will be noted by reference to Figs, i, 2, and 3. apparatus—The still proper was constructed in three parts (Fig. 4). The cylindrical body of the still for holding the needles was 3 feet 6 inches in height by 2 feet 3 inches in diameter, made of No. 16 B. W. G.1 The ends were flanged out and attached to copper. iron rings i3/4 inches wide. The covers of the still and of the heating vessel were similarly flanged and provided with rings. The top and base were clamped to the cylinder by 21/2 inch malleable iron clamps. Asbestos wire tape was used in these make and break joints. The inner base of the cylinder was furnished with lugs upon which rested a frame covered with 20 mesh No. 25 B. W. G. brass wire to support the needles. To reduce radiation and resultant condensation of the vapors the cylinder was covered with asbestos. The heating vessel was 3 feet in diameter by 2 feet 1 inch high and constructed of No. 16 B. W. G. copper except the bottom, which was No. xr B. W. G. copper. The heating vessel was supplied with a 4V2 inch funnel provided with a lever handle stop, and a l/2 inch water gauge.
An 8 foot copper pipe, in two sections, two inches in diameter, connected the cover with the condenser. The latter consisted of 20 feet of 1V4 inch copper tubing wound in a coil of 1 y2 feet internal diameter. The coil was placed in a galvanized iron tank 2 feet in diameter by 21 /1 feet deep. The receiver (Fig. 5) consisted of a 2 gallon aspirator bottle furnished with a brass siphon. During distillation the receiver was 1
Birmingham wire
gauge.
