lune 1951
INDUSTRIAL AND ENGINEERING CHEMISTRY
In continuation of these kinetic studies, the influence of catalysts and different pH conditions on the resorcinol-formaldehyde reaction is presently under investigation, and resorcinol may be expected to react basically different from phenol. ACKNOWLEDGMENT
The authors gratefully acknowledge the support of this work by the Koppers Co., Inc., through its multiple fellowship on special resins and its permission to publish this paper. LITERATURE CITED
1
(1) Aero Research, Ltd., Duxford, England, Sci. and Tech. Memo 1-47 (December 1946). (2) Boehm, T., and Parlasca, N., Arch. Pharm., 270,168 (1932). (3) Boutaric, A., and Engeldinger, M., Compt. rend., 206, 1488 (1938). (4) Caro, N.,Ber., 25,939 (1892). (5) Carswell, T.S.,“Phenoplasts,” New York, Interscience PublishBrs, Inc., 1947. (6) D’Alelio, G. F., “ExperimentaI Plastics and Synthetic Resins,” New York, John Wiley & Sons, 1946. (7) Dostal, H., Marks, H., and Raff,R., IND.ENG.CHEM.,29,595 (1937). {8) Dostal, H., and Raff, R., 2.physik. Chem., 32B,117 (1936). (9) Dubrisay, R., and Papault, R., Compt. rend., 215, 348 (1942); Inds. Plastics, 1, 132 (1945). (10) Engeldinger, M., Compt. rend., 202,842,1854 (1936). (11) Euler, H.V.,et ai., 2.physik. Chem., 189A,109 (1941); 2.ang e m Chem., 54,458(1941).
1427
(12) Fineman, M. N.,and Puddington, I. E., Can. J . Research, 258, 101 (1947);IND. ENQ.CHEM.,39,1288 (1947). (13) Finn, S. R., and Rogers, L. R., J . SOC.Chem. Ind., 67,51 (1948). (14) Houwink, R., Ibid., 55, 247 (1936); Trans. Faraday Soc., 32, 122, 131 (1936). (15) Hultsch, K.,“Chemie der Pheolharse,” Berlin, Springer-Verlag, 1950. (16)Jones, T. T.,J . SOC. Chem. Ind., 65,264 (1946). (17) Lomakin, B. A.,and Guseva, V. I., Plastichestic M a s s y , Sbornik. 2, 111, 281 (1937). (18) Megson, N. J. L., J . SOC.Chem. Ind., 57, 189 (1938); 58, 131 (1939). (19) Nordlander, B. W., Oil, Paint Drug Reptr., 130,I, No. 11, 3,27 (1936). (20) Novotny, E.E., and Stokes, J. S., U. S.Patent 1,776,366(Sept. 23,1930). (21) Olson, W. C.,et al., U.S. Dept. Agr. Forest Service, Forest Products Lab. Rept., 1531,1532,1537, 1565,1568 (1946-1948). (22) Rhodes, P. H., Modern Plastics, 24,145,238 (1947). (23)Robitschek, P., “Phenolic Resins,” London, Iliffe and Sons, Ltd., 1950. (24) Shipley, R. L.,Plastics (Chicago),4,No. 1, 58,60,62 (1946). (25) Sprung, M. M., J . Am. Chem. SOC.,63,334(1941). (26) Sprung, M. M., and Gladstone, M. T., J. Am. Chem. SOC.,71, 2907 (1949). (27)Vieweg, R., and Knappe, W., Kunststoffe, 39,279 (1949). (28) Yanagita, M., J . SOC.Chem. I n d . J a p a n , 45,1297 (1942). (29) Zamparo, A.,Boll. chim. farm., 63,161 (1924). RECEIVED September 9, 1950. Presented before the Division of Paint, VarCHIOMnish, and Plastics Chemistry at the 118th Meeting of the AMERICAN ICAL SOCIETY, Chicago, Ill.
Catalytic Hydrogenolvsis of Wood U
EARL G. HALLONQUIST Plywood Research Foundation, Tacoma, Wash.
*
-
Hydrogenation has shown considerable promise as a means of obtaining useful chemical products by the controlled decomposition of wood. The present investigation was carried out to explore the possibilities of hydrogenolysis (concomitant hydrogenation and hydrolysis) in converting wood to distillable liquids. Optimum yields of slightly more than 50% of the weight of the wood were obtained as nonaqueous distillable liquids by this method. Nickel catalysts were the most effective, and yields varied considerably, depending on the amount of catalyst used and the time and temperature of reaction. The quantities of gas and water formed, and the amount of unreacted material remaining, were determined for various conditions. The ultimate feasibility of the conversion of lignocellulose to chemicals and oils is of continuing scientific and industrial interest, and the information contained in this report should indicate the possibilities for wood liquefaction by methods involving hydrogenolysis.
V
ARIOUS investigations into the catalytic hydrogenation of
wood have been carried out in recent years. Some of these have had as their object the production of hydrocarbons and liquid fuels from wood by methods similar to those employed for coal (10-12, 16). I n other cases hydrogenation was effected using a suitable catalyst and a solvent or carrier such as alcohol (S), dioxane ( 1 , 9,IS), or dilute aqueous alkali (7,8, 14). Hydroxyl compounds such as ethylene glycol, glycerol (6),and various cyclohexanols ( 4 , 5 , 9 )have been identified in the reaction products of these hydrogenations of wood. This report gives the results of a study of the hydrogenation of wood in water (here referred to as the hydrogenolysis of wood). The work described was carried on primarily to determine the
effect of type and amount of catalyst on the quantity of distillable products obtained from this reaction. No attempt was made to identify these distillables except by classification into rough boiling point ranges. Water was used as the diluent and carrier in order to avoid any suspicion of products‘being obtained from sources other than the wood. An effort was made to determine also the amounts of gas and water formed during the hydrogenolysis, the unreacted material remaining, and the hydrogen absorbed. APPARATUS AND PROCEDURE
A n American Instrument Co. shaker-type reaction bomb having a capacity of 2500 ml. was used for this work. The quantities of wood or other material was varied from 35 to 150 grams, with the catalyst ranging from 0 to 50 grams. The liquid carrier (water) was maintained generally a t 1200 ml. The maximum temperature range was 250” to 290” C. and the initial hydrogen pressure 1800 pounds per square inch. The time of reaction a t the maximum temperature varied from 0 to 8 hours. After completion of the hydrogenolysis and cooling of the bomb, the contents were removed and filtered to separate the catalyst and unreacted material from the liquids. The catalyst and unreacted material were washed with 100 grams of water. I n some preliminary runs the combined aqueous solutions were subjected to fractional distillation a t atmospheric pressure. Considerable darkening of the solution occurred, and the amount of material boiling lower than water which was recovered was only 1or 2yo of the weight of the original raw material. I n order to expedite the results, and to avoid decomposition, the atmospheric fractionation for low boiling material was eliminated. The water was removed under reduced pressure a t 25” to 28” C., using a nitrogen source for the boiling capillary, and a short packed column. A sharp break always occurred between the last of the water fraction and the next highest boiling material, no distillate being obtained up to about 50” C. a t 17 to 23 mm. The liquid remaining after removal of the water was transferred to a flask of suitable size, and the distillation was continued a t 17 to 23 mm. for material boiling up to 150” C., and a t 2 to 5 mm. for higher
INDUSTRIAL AND ENGINEERING CHEMISTRY
1428
Vol. 43, No. 6
TABLE I. DATAON EXPERIMENTAL I~YDROGENOLYSIS Expt. YO. 121 122 123 124 127 131 132 133 134 135 136 137 139 140 141 142
143 144
145 146 147 148 149 151 154
155
156 158 165 166 168 169 170 171 178 179 180
181 182 183 185 186 187 188 190 193 194 195 196 197 198 199 200 201 203 207 208
Raw Material Grams Douglas firb 35 Douglas fir 70 Douglas fir 100 Douglas fir 150 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douilas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 70C Cotton linters Douglas fir 70 Cotton lintels 70 Cotton linters 70 70 Cotton linters 70 Douglas fir 70 Douglas fir Douglas fir 70 70 Douglas fir 70 Douglas fir Douglas fir 70 Alder 70d 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Douglas fir 70 Dounlas fir 70 70 70 70 70 70 70 70 70 70 70 70 Douglas fir 70 Douglas fir Douglas fir 70 Redwood 70 Douglas fir 70 Douglas fir 70 ~-
_ _ _ _ _ _Catalyst __~
__
Grams 10 10 10 10
Raney nickel Ranev nickel K a n c j nickel Rar.ey nickrl Hancj. nickel None Raney nickel Raney nickel Raney nickel Raney nickel None Raney nickel None Raney nickel Raney nickel Raney nickel Raney nickel Ranev nickel
Copper turnings Zinc acetate Zinc nlpatp
Raney nickel Ferriq oxide (FezO?) Aluminum hydroxide
..
.. ..
10
%2 5
.. ..
0 5
,.
..
20
2.5
.
7
10 10 10 10 40 40 40 *O
. , . .
.. ..
,
.. .,
..
..
Magnesium carbonate
5
.. ..
.......... . . . . . . . . . . . . . . . . . . . . . .
.. , .
..
. . . . . . .
........ . ., ..,. ...........
10
10 10
........
...........
10 10
10
..
.......... . . . . . . . .
10 10
10 10 10
,.
..
...........
10 20 50 10
10
..
. . . . . . . .........
0
10 10
, .
..
. . . . . . . . ........... ..........
2.5 50 0 10
‘0 Raney nickel Harshaw Cu 461 Harshaw Xi 287 Harshaw Xi 79 16.67, Ni on Porocel Harshaw Ni 79, Spec. 104 Raney nickel Raney nickel Raney nickel Raney nickel Ranev nickel I
