T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
920
wood a t 70' C. for five hours, nearly complete extraction of rosin occurs. 11-From the general properties of ammonia and its complete recovery in gas works, it is believed that nearly complete extraction of rosin from wood may be made and complete recovery of ammonia obtained. LABORATORY OF-INDUSTRIAL CHEMISTRY UNIV~RSITY OF-WASHINGTOX, SEATTLE
DISCOLORATION OF MAPLE IN THE KILN By ROY C.
JUDD
I n kiln-drying green frozen maple lumber, a brown stain or discoloration occurs unless the most favorable conditions are maintained. An investigation of the causes and of the nature of the discoloration was made. Irving W. Baileylstates that some sap staining is due to an enzyme. To substantiate this view, Mr. Bailey states that the action can be arrested by simply dipping the lumber in hot water. To study the possibility that this action is due to some enzyme, such as an oxydase, several small blocks of maple were given various preliminary treatments, and then placed in an oven where the humidity exceeded 90 per cent. The temperature was maintained a t 90'' C. for from one to three hours. The preliminary treatments were made as follows: I-Dipping in water a t 90' C. a-Soaking in boiling water for I , 2 , 5, 60, and zoo-minute periods. 3-Steaming a t 100' C. for 5 , 60, and 200-minute periods. 4-Heating in a drying oven a t 105' C. for I O rnin., 30 min., I hr., z hrs., I O hrs., and 20 hours. 5-Previous treatment with solutions of germicides : a-Zinc chloride b-Mercuric chloride c-Sodium fluoride d-Phenol e-Arsenious oxide +Hydrogen peroxide g-Sodium carbonate
Discoloration appeared in every case when these samples were finally subjected to the unfavorable conditions of a warm humid atmosphere. The stain was formed on the surface first, but, on remaining for a longer period in the moist air, the stain appeared throughout the specimen. The possibility of the discoloration being caused by an enzyme was disproven because a t least some of the above treatments would have destroyed the enzyme. If dipping maple in hot water prevents subsequent staining in the kiln, i t is not because the enzymes are destroyed but because the heated wood dries more readily. A series of experiments were carried on in an autoclave. Pieces of fresh green maple were given the following treatments: I-Enough of a 3 per cent solution of hydrogen peroxide was added to cover the sample. The air was pumped out and the temperature of 75 C. maintained. 2-An atmosphere of sulfur dioxide was supplied and the temperature kept a t 80' C. 3-An atmosphere of carbon dioxide was added and the temperature maintained a t 80 O C. 4-The air was removed and live steam passed through continuously. 5-An NHsOH solution was placed in the autoclave and the air exhausted. The temperature was kept a t 75 C. 6-A little water was added and air was left in. A temperature of 80' C. was maintained. The duration of the above experiments was from two to four hours. The results of these experiments showed that discoloration did not appear in the presence of hydrogen peroxide, carbon dioxide, sulfur dioxide, nor with steam in the absence of air. In a n atmosphere of air saturated with moisture and also 1
Botanical Gazette, 60, 142-147. S o . 2, August, 1910
Vol. 7 , No.
II
in the experiment with ammonium hydroxide, discoloration was very appreciable. Three sets of experiments were carried on simultaneously. Pieces of maple were placed in flasks containing distilled water. Air was continuously bubbled through one and carbon dioxide and sulfur dioxide, respectively, through the other two. The initial temperature of 40' C. was maintained for one hour. Then the temperature was raised 10' a t one-hour intervals till the temperature of boiling water was obtained. At the end of the process the pieces of maple in the flasks through which carbon dioxide or sulfur dioxide had been passed were even lighter colored than the original, while the maple in the flasks through which air had been passed was very badly discolored. The first evidence of discoloration appeared a t about 60" C. and became more pronounced as the temperature was raised. Several experiments indicated that weak solutions of organic or mineral acids prevent discoloration. Some experiments were carried out on a small scale in laboratory drying ovens. It was found that no staining took place when the humidity of the air in immediate contact with the drying wood was kept low. The investigation seems to indicate that the staining is probably of a physical chemical nature and is independent of enzymes. This paper is not intended t o cover the subject of kiln-drying but is written for the purpose of showing that it is possible with conditions well under control to dry green maple lumber artificially and still retain its natural color. The conditions that prevail in a commercial kiln for drying lumber are not as easily controlled as those in a small laboratory apparatus. The section of timber physics in the Forest Products Laboratory has worked out its application in a dry kiln. The only available means of overcoming this difficulty in commercial practice is by the use of a low temperature (120' to 130' F.) and a low humidity (60 per cent or less) in the dry kilns. Fortunately, maple is a wood which does not check easily and hence these low humidities are quite practicable on a commercial scale. I wish to express my appreciation of the suggestions and interest contributed by Mr. H. D. Tiemann, in Charge, Section of Timber Physics, and a specialist in kiln-drying, and Dr. S. F. Acree, Chief of the Section of Derived Products, who suggested the studies of the chemical and enzymic phases of this problem. FOREST PRODUCTS LABORATORY hI.4DISON. W I S C O N S I N
MANUFACTURE OF ETHYL ALCOHOL FROM WOOD WASTE-11. THE HYDROLYSIS OF WHITE SPRUCE By F. W. KRESSMANN
A paper' presented a t the Forty-Ninth Meeting of this Society a t Cincinnati, described ( I ) the scope of the work, ( 2 ) the apparatus used, (3) the method of procedure, and in addition gave the results obtained from a series of preliminary experiments on white spruce. Since the above work was done the yeasting operations and fermentation conditions have been standardized so that duplicate and comparable data have been made possible. The yeast used is a pure culture strain of Saccharomyces cerevisiae, isolated from a yeast used in a Hungarian distillery, producing alcohol from beet sugar molasses. It is well adapted to the fermentation of sugar solutions obtained from the hydrolysis of wood, although the addition of nitrogenous food is necessary. This yeast nutrient is a mixture of ammonium sulfate and malt sprouts. The details of yeast propagation and the preparation of the mashes for fermentation along with other details of the present work will be given later in the form of a professional paper of the United States Department of Agriculture. In all cases, 7 , 5 0 0 cc. of a solution having a gravity 1
THIS JOURNAL 6 (1914). 625.
Nov.,
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
1915
921
from four different cooks, give an indication of the method of fermentation, the average results and degree of accuracy t h a t are being obtained at present. In the former paper the influence of temperature and pressure and time of cooking were discussed. The ratio of water to dry
around 12.5 O Brix were used for fermentation. The fermentations were carried out in a constant temperature room, maintained a t 30' C. * 0 , s ', which could be kept in a sterile condition. The beers were distilled after 96 hours (distilleries operating on this type of materials are classed as sour mash distilleries
TABLE I-FERMENTATION RECORD F O R WHITESPRUCE Fermenter set a t 9.15
A.M.
Distillations begun a t 9.15
--
YEAST
MASHBEFORE FERMENTATIOX
BEER
7
c
7
96 Hour yeast
c
Seed yeast
.7
k
E
.8.8d
--
-
,Ea
itcv: o
g,u9
8:
PU
11.4 11.4 13.9 13.9 11.4 13.9 13.9 11.4 11.4 11.4 13.1 13.1 11.4 11.4 11.4 11.4 12.9 12.9 11.4 11.4 12.9 12.9 13.1
18.5 18.5 18.5 18.5
'L :: 1.0216 5 . 9 2 2 1 . 0 2 1 6 5.922 1.0223 6 . 1 6 7 1.0223 6 . 1 6 7 1.0210 6 . 0 0 9 1.0223 6 . 1 6 7 1 ,0223 6 . 1 6 7 1.0216 5.922 1.0216 5,922 1.0210 6.009 1,0230 5.650 1.0230 5 . 6 5 0 1.0216 5.922 1.0216 5.922 1.0210 6.009 1.0210 6.009 1.0232 5.541 1,0232 5 . 5 4 1 1.0210 6.009 1.0210 6.009 1.0232 5 . 5 4 1 1.0232 5.541 1.0230 5 . 6 5 0
18.7 18.7 26.2 26.2 22.3 26.2 26.2 18.7 18.7 22.3 18.0 18.0 18.7 18.7 22.3 22.3 16.5 16.5 22.3 22.3 16.5 16.5 18.0
u c
d:: 1.0470 64.48 1.0454 6 2 . 4 4 1.0498 5 8 . 1 2 1,0478 56.40 1.0498 5 9 . 7 4 1.0514 6 5 . 2 0 1,0509 64.60 1 ,0475 5 7 . 3 4 1.0498 6 0 . 1 0 1.0487 6 6 . 5 2 1.0429 26.904 1 ,0542 / 1 . 2 8 8 1 ,0529 7 0 . 2 4 1 ,0509 66.32 1 ,0463 6 2 . 0 2 1 ,0400 5 2 . 2 6 1 ,0474 60.984 1.0472 6 0 . 4 7 6 1 ,0468 7 5 . 8 1 1.0497 8 1 . 4 8 1.0523 8 3 . 1 5 2 1,0540 87.192 1.0553 87.792
