INDUSTRIAL AND ENGINEERING CHEiMISTRY
February, 1925
19.1
Composition of the Oleoresin of Douglas Fir' By H. K. Benson and D. v N 1 V E F S I T Y OF
WASHINGTON, SEATTLE, WASH.
T
HE oleoresin of the Douglas fir occurs in seams or cracks due to internal injury of the tree from wind-shake. Experienced timber cruisers are able, in many cases, to spot the resin-bearing trees, but in general there is no reliable method for determining whether or not a tree contains a shake. It has been found advisable, by those engaged in the business of gathering the resin, to tap all large trees in areas of plentiful shakes and to let the extent of their tapping operations in the various areas be governed by the immediate success obtained. The resin is obtained by boring the tree near the ground with an augur at an angle slightly inclined to horizontal until the resin pocket is struck. It is frequently necessary to tap a tree in as many as six places. The yield per tree varies from a few pints to as much as 15 gallons at the first tapping. If the trees are properly plugged, the boring does not injure them and they will yield varying quantities of resin each year for an indefinite length of time. Good resin trees will yield an average of 2 gallons per year after the first tapping. Description of Samples Two samples were obtained, one from western Oregon in a region where considerable oleoresin is collected and sold under the name of fir balsam. The other sample was obtained by the authors from a single tree near Seattle. The Oregon sample may be regarded as a composite of oleoresin from numerous trees. It constituted the material for this investigation. Methods of Examination and Results The sample of Oregon oleoresin was distilled with superheated steam a t a temperature of 150" C., for the purpose of separating the volatile oil and rosin. The residue was then heated to this same temperature until all water had been expelled. To the sample of Washington oleoresin water was added and the mass heated until all the water had been expelled.
SAMPLE Oregon Washington
T a b l e I-Crude Oleoresins Specific Viscosity gravity (Saybolt) (Westphal) 99' C. 15' C. (210' F.) 1.105 97 0.970 b9
Refractive index 15. c. 1 4930 1 5145
Volatile oil Per cent 36.0 26.0
VOLATILE OIL-The volatile oil was fractionally distilled using a Galinsky column, and t'he specific gravit'y, refractive index, and polarity were determined for each fraction. T a b l e 11-Volatile Distillation temperature Fraction
O
c.
Per cent of total 6.65 6.65 6.65 6.65 6.65 6.65 6.65 6.65
154 0 1 5 4 . 0 to 1 5 6 . 5 166.5 to 157.0 157.0 to 1 5 7 . 5 157.5 to 1 5 8 . 0 158.0 158.0 8 158.0 9 158.0 to 159.5 6.65 10 159.5 6.65 11 160.0 6.65 12 1 6 0 . 0 to 1 6 1 . 5 6.65 1 6 2 . 0 t o 165.0 13 6.65 14 165.5 3.33 15 166.0 t o 178.5 5.00 16 188.0 3.33 Total 154.0 to 188 0 Residue and loss on distillation
' Received July 24, 1924.
Oil
Refractive index 1 4689 1.4689 1.4689 1.4689 1,4689 1.4700 1.4701 1.4693 1.4702 1,4695 1.4696 1.4702 1.4709 1.4727 1.4766 1.4840 1.4704 = 1.84 per cent.
Specific gravity (Westphal) 15' C . 0.8679 0.6700 0.8696 0.6690 0.8700 0.8670 0.6745 0.6661 0.8760 0.8665 0.8655 0.8670 0.8690 0.8690 0,8748 0.9261 0.8700
F. McCarthy
Specific rotation 2 , 5 O C. Degrees -25.80 -26.00 -24.75 - 25.85 -25.70 -25.90 -25.70 -26.10 -24,90 -26.60
-26.90 -27 00 -28.50 -29.90 -33.30 -29.30 -27 . 00
ROSIN-Samples of the rosin were given 10- and 20-minute treatments with excess of calcium carbonate at 288" C. (550" F.) for the purpose of determining the hardening effect. The specific gravity, saponification number, acid number, ester value, and softening point of the three rosin samples were determined by methods suggested by Griffin.* T a b l e 111-Rosin Specific Softengravity SaponificaAcid Ester ing point Sample 20' C. tion number number value Color C. 1 1.051 153.0 147.7 5.3 Darkbrown 74 2 1.062 148.0 143.8 4.2 Dark brown 72 3 1.076 146.5 142.0 4.5 Darkbrown 73 Sample I-Crude (residue after removal of volatile oil). Sample 2-Crude rosin treated with excess of calcium carbonate f o r 10 minutes a t 268' C. (550.O F.). Sample 3-Crude rosin treated with exress of calcium carbonate for 20 minutes a t 268' C. (550O FJ.
ROSIXOILS-A quantity of crude rosin was heated in a flask until decomposition was complete and the product's of decomposition had distilled off. The crude rosin oil was then fractionally distilled, using a Galinsky column, and the constants of the various fractions were determined. Discussion of Results Examination of Table I1 shows that about 90 per cent of the volatile oil distils between 154" and 165" C. This fact and the similarity in physical properties, as shown by the constants listed below, indicate that the volatile oil contains approximately 90 per cent 1-0-pinene and @-pinene in about' equal proportions. NAME Volatile oil Z-a-pinene I-@-pinene
Boiling point
= c.
154 to 188 155 to 156 162 to 163
Specific gravity 150 c. 0.8700 0.6630 0.8740
Refractive index 15' C. 1.4704 1,4678 1.4724
Specific rotation 25' C Deerees -27.0 -27.6 -26.2 Y~
~
~
S ~ h o r g e r in , ~ a careful chemical study of the volatile oil obtained from the oleoresin from heartwood, showed the presence of I-n-pinene with small amounts of I-limonene and I-terpineol. p-pinene was not detected. In the oleoresin from sapwood, obtained by scarification, he showed the presence of I-0-pinene, I-p-pinene, and I-limonene. The constants obtained from the rosin indicate that it is similar to commercial rosin in composition. Specific gravity NAME 200 c. Fir rosin 1.051 Commercial rosin 1.011 t o 1 . 1 2 2
Saponification number 153.0
Acid number 147.7
168.2to222.0 146.5to164.4
Ester value 5.3 15.7to30.0
Comparison of the softening points of the samples treated with calcium carbonate indicates no marked change in this property. The soft and tacky character of the crude rosin at room temperature is not found in Samples 2 and 3. These samples also show a rather sudden and abrupt change of state, whereas the crude rosin softens more gradually. The rosin oils are, of course, subject to variat'ions in methods of production, but in general they approximate the properties of commercial rosin oils of the same range of boiling points. Uses of Oleoresin The crude oleoresin is marketed at present by the individual collectors to a firm of chemical exporters who filt'er and clarify it. The larger portion is exported for use in the preparation. 2 3
"Technical Methods of Analysis," pp. 327 and 542. J . A m . Chem. Soc., 39, 1040 (1917).
INDUSTRIAL A N D ENGINEERING CHEMISTRY
194
Table IV-Rosin
Fraction
1 2 3 4 5 6 7
8 9 10
Distillation tempoerstwe C. 170 to 190 190 t o 335 235 t o 336
336 336 336 t o 350 t o 358 t o 365 366 to 170 to
350 358 365
370 370
Per cent of total
Refractive index 15O C.
15.1 9.3 9.3 9.3 9.3 9.3 9.3 9.3 9.3 7.0
1.4924 1.4910 1.4920 1.4918 1.4919 1.4922 1.4920 1 ,4920 1.4920 1.4920 1.4930
Total Residue and loss on distillation = 3.5 per cent.
Oils
Specific gravity (Westphal)
160 c.
Viscosity (Saybolt) 99' C. (210"F.)
Saponification number
38.5 57.3 58.3 79.2 120.0 141.5 94.6 123.2 130.0 138.0 63.5
of chemicaliand medicinal products. One local concern, however, uses it in the manufacture of paint by combining it with a solution of rubber and the requisite amount of thinner. Conclusions
oleoresin from different localities is subject to variation in composition.
Vol. 17, No. 2
Acid number
77.2 79.3 69.1 69.7 73.2 84.8 69.8 61.2 21.9 29.9
..
..
Ester value
4.5 7.1 4.9 3.8 2.3 15.9 3.3 0.2 . I
..
2-The volatile oil contained in the oleoresin varies from 26 to 38 per cent. 3-Crude rosin from the fir oleoresin is soft and tacky, which property can be overcome by treatment with calcium carbonate without appreciable alteration in composition. 4-The rosin oils are similar to those obtained from pine.
Sugar Formation in a Sulfite Digester' Quick-Cook Process By E. C . Sherrard and C. F. Suhm FOREST PRODUCTS LABORATORY. MADISOX, WIS
I
N A previous paper2 the writers dealt with the rate of
sugar formation and the quantity of sugar produced in a sulfite digester using the Mitscherlich process. In order to obtain similar information regarding a quick-cook process a series of determinations was made on liquors obtained by the use of the same apparatus but by a modified quick-cook process.8 The modification consisted in heating by means of indirect steam and with varying excesses of free sulfur dioxide. The use of indirect steam was necessary in order to avoid dilution by condensation, which would cause a variation in concentration of sugars per unit volume. Table I-Sugar
Cook 676
Length of cook Hours
3 5
GONDITIONOF WOOD
Shredded
6.5
677
3 4.5
Shredded twice
6
678
3 4.5
Shredded
9
680 682 683
3 4.5 8.5 5 6.5 3 5.75 6.5
Shredded twice Shredded twice Shredded twice
One series of cooks was run on white spruce and a second on jack pine. The cooks in the first series were made with indirect steam by means of a heating coil. No relief was permitted, the pressure being allowed to go as high as it would. I n this series the temperature was raised rapidly to 100" C. and held until the third hour; from that point the temperature was raised a t the rate of 20' C. per hour until the desired maximum temperature was reached and then held a t that point until the end of the cook. It was found that the rate a t which it was possible to heat the digester depended in part upon the
Formation i n Pulping White Spruce by Quick-Cook Process
--DIGESTERLiquqr Temperremaining ature Pressure Gallons OC. Pounds
60.98 59.60 60.27 61.03 61.85 62.21 61.01 61.81 64.42 59.89 60.61 62.73 61.69 63.04
100 140 140 100 129 130 130 131 100 130 130 140 140
61.04
100
62.54 62.64
150 150
100
54 114 131 50 94 98 50 90 100
62 80 108 120 128 40 119 126
-LIQUORSpecific gravity
Per cent sugar
Total sugar Per cent dry wood
1,0399 1.0496 1.0599 1.0400 1.0467 1,0537 1.0396 1.0442 1,0579 1.0463 1.0397 1,0660 1.0540 1.0010 1.0314 1.0460 1,0481
0.51 1.81 2.86 0.63 1.54 2.85 0.47 1.07 2.51 0.59 1.49 3.29 1 89 2.70 0.46 2.25 2.83
3.15 11.08 17.97 3.26 9.78 18.40 2.92 6.77 16.82 3.62 9.22 21.60 12.06 17.80 2.77 12.31 18.26
By avoiding dilution accurate determinations of sugar in the liquor were obtained, and the quantity of sugar that was produced was then calculated on the dry weight of the wood. 1 Presented under the title "Sugar Formation in a Sulfite Digester (Ritter-Kellner Process)" before the Division of Cellulose Chemistry a t the 67th Meeting of the American Chemical Society, Washington, D. C., April 21 t o 26, 1924. 2 Sherrard and Suhm, THISJOURNAL, 14, 931 (1922). a The data in this paper in regard to pulp and cooking conditions are taken from a report by Miller and Swanson, Paper Trade J., 7 8 , 178 (1924). For further information with regard to cooking conditions, yields, etc., reference should be made t o this paper.
REMARKS Chips shredded. Pulp yield, 46.1 per cent Prematurely blown.
Pulp yield, 55.00 per cent
Pulp yield, 47.35per cent Pulp yield, 48.8 per cent '
Pulp yield, 46.0 per cent Pulp yield, 45.55 per cent
concentration of excess sulfur dioxide in the acid liquor. An acid with a high excess could be heated much more rapidly than one with low excess without burning an abnormal quantity of chips, the higher concentration of excess sulfur dioxide evidently being favorable to rapid penetration of the chips by the base. So far as the quantity of sugar produced was concerned, little or no difference could be noted when the concentration of excess sulfur dioxide was varied between 2.50 and 3.58 per cent. Doubtless the reason for this is that after the desired pressure is reached an equilibrium is established between
