UMASS/AMHERST 3iaDbt,00S0fc7'^b4 i i t^/dl-fJ^ LIBRARY OF THE MASSACHUSETTS AGRICULTURAL COLLEGE No L^ a SOURCE v59 mf'cM 0^***4* *J863 DATE DUE 1 UNIYERSITY OF MASSACHUSETTS LIBRARY CAkD LEATHER REFUSE; Its Value in Agriculture. BY J. B. LINDSEYy Ph. D., MASSACHUSETTS STATE EXPERIMENT STATION, AMHERST. W. F. HCMPHRSY, GENBVA, N. V. 1894. L L f Agricultural Science. Vol. VIII. FEBRUARY, 1894. No. 2. LEATHER REFUSE — ITS VALUE IN AGRICUL- TURE. BY J. B. LINDSEY. First Paper. During the past few years, claims have been made at various times that large quantities of leather shavings and the like have found their way into the so-called commercial fertilizers that are so widely used by the farmers of the United States. The writer has no means of knowing whether this claim is true or not. It should be the object of the fertilizer manufacturer to utilize all kinds of waste products that possess distinct manurial value. By so doing he not only benefits himself, but the farmer as well. It was very early assumed from its chemical character, without any exact experiments upon which to base the assumption, that leather refuse would yield its nitrogen as plant food very slowly if at all. Methods Employed to Make the Nitrogen Available to Growing Plants. The first method suggested, so far as the writer has been able to ascertain, was that prescribed by F. O. Ward*, of England, in 1857, for turning to account woolen rags, wool, silk and leather clippings. The process as described was as follows : The refuse was introduced into an ordinary autoclave digester, and there kept for about three hours, surrounded by steam heated to a pres- sure of from three to five atmospheres. Wool required a higher temperature than leather, and silk than wool. The materials condensed a portion of the steam, and absorbed its heat. This joint action converted the animal matter into a friable substance, which, * Report by the Jtiries of the International Exhibition, 1862. Reporter, A. W. Hoffman. Repertory of Patent Inventions, Aug. 1857, page 137. 50 AGRICUI.TURAI, SCIENCE. Vol. VIII. No. 2. however, still retained its original form and aspect. It was then ground fine, sifted, and bagged. " The details of the process, the fuel- and labor-saving arrangements that have been learned, point by point, by costly manufacturing experience cannot, ' ' says Ward, ' ' with propriety be divulged, ' ' The final product is described as a dark colored powder. The nitrogen in the finished product is said to exist to a small extent, as ready formed ammonia, being in combination with ulmic and humic acids developed during the process. It was stated at the time, that this manufacturing process was carried on at large works on the Thames. The ma- terial for the most part was sold to manure manufacturers, who used it as an ingredient of their several fertilizing compounds, and it was ' ' used by many farmers who are not aware of the fact. ' ' Ward says that ' ' while this material is not as active as some other forms of organic nitrogen, it possessed distinct value as a fertilizer."* Kdw. Toynbect in 1858, also described a process whereby leather and wool waste could be cooked in sulfuric acid, and be made more available as a fertilizer. He said " that to one cent- ner of sulfuric acid, four or five centners of wool or leather waste could be added." The writer does not see how such a large amount of leather could be added to the acid, as will be shown further on. L,. MeyerJ speaks of dissolving all such refuse sub- stances in warm sulfuric acid, and neutralizing the moist mass with bone. A Lipowitz§ notes the fact that the Posner fertilizer factory utilizes all such kinds of waste, as have already been referred to. Runge^ speaks of rendering leather and wool more available, by dissolving them in a mixture of Glauber's salt and quicklime. This chemist manufactured a fertilizer upon a large scale from these materials. R eichardt*Mescribes his method of subjecting the leather refuse * The writer does not know whether this process is still in operation in England, for utilizing the leather, wool, and silk wastes. t Repertory of Patent Inventions 1858, p. 389 ; Jahresbericht Agric. Chem., 1859. t Jahresbericht Agric. Chem., 1859, 228. I Allgem. Zeitung fiir deutsche Land, und Forstwirthe, 1859, 153. ^Jahresbericht Agric. Chem., 1865. ** Zeitschrift fiir deutsche Landwirtschaft, 1865, 136. Jahresbericht Agric Chem., 1865. l894- AGRICUI^TURAL SCIENCE. 5 1 to steam pressure, and then drying it quickly. After such a treatment he found 15.75 per cent, of the material to be soluble in boiling water, and that after standing for some time, 20 per cent, could be dissolved. By treating the dry leather that had been sub- jected to steam, with 20 to 40 per cent, sulfuric acid, he was ena- bled to dissolve from 22 to 29 per cent, of the leather in water. With a 5 per cent, solution of crystallized soda, 28.8 per cent, could be brought into solution. He therefore concluded that the best method was to subject the leather to the action of a weak soda solution. Coignet's* method was reported in 1874 by H. Mangon. Briefly stated, it is as follows : The refuse material is placed in a room having a cubic area of 20 meters. Directly outside of the room is a coke oven, connected with a chimney that has an open- ing into the room containing the material to be treated. Into this chimney are conducted jets of steam, so that the room is heated from 150° to 160° C. for several hours by this moist chim- ney air. Under these conditions the leather swells somewhat, and becomes dark, brittle, and can easily be rubbed to a powder. Storerf says, "It is evidently with reference to this process, that the statement has recently been made, that certain manufac- turers of fertilizers at Paris devote themselves particularly to the preparation of torrefied wool, horn, leather, and even bone, the leather having first been steamed strongly to remove oil and gela- tine." I^'Hotet describes a method whereby such waste material as wool, leather, etc., can be converted into sulfate of ammonia. He suggests dissolving the material in a ten per cent, solution of caustic soda in the cold. The substances will be partly dissolved, or their structure more or less destroyed. The jelly-like mass is then mixed with caustic lime till it becomes of a doughy consis- tency. It is then brought into iron retorts, and heated at first at as low a temperature as possible in order to prevent the dissocia- tion of the ammonia, which is caught in sulfuric acid. After the gas has been nearly driven off, the retorts are subjected to red * Organ der Verein f. Riibenz. Industrie in CEster-Ungarn, 1874, 32. Jahresbericht Agric. Chem. 1873-1874, 37. ^ Agriculture 1., 382. X Centralblatt fiir Agric. Chem. 5, 258. lUustrirte landw. Zeitung, 1874, No. 2. 18. 52 AgricuIvTurai, Science. Vol. viii. No. 2. heat. At the end of the operation, a white powdery substance is left behind, consisting of carbonate of soda and caustic lime. By cooking this substance with water, caustic soda is formed and can be again utilized. By this method all the nitrogen is obtained. The resulting sulfate of ammonia is somewhat colored. For utilizing leather Riimpler* suggests the following method : In lead or iron jacketed kettles, sulfuric acid of 50° B. is heated very hot, and leather stirred in till a dark brown fluid is obtained. This fluid is then used to dissolve the phosphate of lime. He re- marks that ' ' the nitrogen is saved, and without doubt is much more available from the fact that the tannin is destroyed." Brhardt t suggests that such refuse material be slowly burned in closed ovens, and the gas collected in moist muck, till the lat- ter becomes saturated. This muck mixed with superphosphate gave, he says, a quick acting manure. DeherainJ says that this leather refuse can be dissolved in sul- furic acid, and the excess of acid neutralized with phosphate of lime. In this way he claims a very active fertilizer can be ob- tained at a low cost. The writer understands that this latter method has been in quite general use for many years by European manufacturers. Not only has leather been thus treated, but also a great variety of nitrogen-containing refuse materials. American manufacturers also subject various waste materials to the action of sulfuric acid, in order to render them more quickly available. From the many methods suggested for the utilization of leather waste, it is evident that, in the older countries, especially Eng- land, France and Germany, this material after having been sub- mitted to some mode of treatment, is quite generally used, to a greater or less degree, in the manufacture of commercial fertilizers. Petermann § says, ' ' that it is well-known that certain Belgian and French manufacturers use leather in their products, but that such goods contain, in addition, nitrogen in other forms, such as blood, horn meal, sulfate of ammonia and nitrate of soda." He further states that the "factories producing this material are numerous, and a considerable q uantity is produced annually." *Kaufliche Diingestoffe. H. Riimpler, 1875 (Thaer Bibliothek). t Jahresbericht Agric. Chem., 1880, 337. tDeherain, Chimie Agricole, [1892], 624. I Recherches de Chimie et Physiologic [1886], 144. i894- Agricultural Scienck. 53 Manurial Value of Prepared Leather Waste. The different experiments made to prove the value of leather have been conducted either with untreated finely ground leather, with torrefied leather, or with leather steamed under pressure. Three different methods have been used, in testing the agri- cultural value of leather: (a) by directly testing its fertilizing effect either in pot or plat experiments ; (b) by artificially digesting it with a pepsin solution ; (c) by noting the length of time required to nitrify it. The first method is by far the most interesting, and leads to direct results. The other two serve at least to confirm the results obtained by the first method. (a) Pot and Plat Experiments. Very early experiments are not to be found in the literature. The first experiment recorded was made by Ladureau,* and lasted but a single season. He found that 2500 kilos, of torrefied leather yielded 30,100 kilos, of sugar beets, testing 8.83 per cent, of sugar, and 2500 kilos, of the same leather plus 200 hectolitres of lime gave 38,600 kilos, of beets, with 10. 10 per cent, sugar. The same area of land without leather, yielded 20,000 kilos, of sugar beets testing 10.93 percent, sugar. Petermann remarks on these results as follows : " In spite of the increased yield obtained by using the leather, the experiment was not a success financially and further, the beets produced with the aid of the leather were poorer in quality than those without it." In 1880, Petermann t carried out a series of experiments with ground, steamed leather, to test its manurial value. It was very dry and brittle, and contained 7.51 per cent, of nitrogen and 0.81 per cent, of phosphoric anhydride soluble in hydrochloric acid. The experiments were carried on in the plant house in pots, with oats ; in the garden, with the horse bean {Vidafaba) ; and in the field, with sugar beets, /. Experiments with Oats in Pots. Kach test was made in duplicate. The soil was what might be called a sandy clay, each pot holding 4,000 grammes. The ferti- lizer was mixed with three-fourths of the soil of each pot. To the soil * Annales Agron., 1878 ; Loc. cit., 146. t Loc. cit., 144, Centralbl. Agrie. Chem. 10, 590. 54 Agricultural Science Vol. viii. No. 2. ineacli pot were added 0,25 gramme of nitrogen, 0.30 gramme of phosphoric acid, and 0.20 gramme of potash. Resui,ts — Average oe the Duplicates, Expressed in Grammes. Entire plant. Straw. ChaflF. Grain. Unmanured 22.34 15.19 0.95 6.20 Series i. Nitrogen (a) Leather 34.85 26.65 1.25 6.95 (b) Dried blood 5i-9i 36.68 1.82 13.41 Series ii. Nitrogen + Phosphoric Acid. (a) Zi?a/A(?r + precipitated phosphate.. 39. 93 31.28 1.15 7.50 (b) Blood + precipitated phosphate 51.97 36.45 1.91 13.61 Series hi. Nitrogen + Phosphoric Acid + Potash. (a) Leather + precipitated phosphate + muriate of potash A30.55 21.90 1.09 7.56 (b) Dried Iblood + precipitated phos- phate + muriate of potash 37.40 29.65 1.82 15.93 In observing the results of the experiments, we notice especially with reference to the grain produced, that the leather did not increase the yield to any appreciable extent over that of the unfertilized pots. When phosphoric acid and potash were applied with the leather, a slight increase in the yield of grain was noticed, while in case of the dried blood plus the phosphoric acid and pot- ash, the yield was twice that of the unfertilized pot. (b) Garden Experiments with Horsebeans. The soil was the same as in the previous experiment, Size of plats, 60 sq. meters. The fertilizer applied was leather and nitrate of soda. Nitrogen was applied at the rate of 58.5 lbs. per acre. Results per Plat. stems and pods Beans in Beans per acre in kilos. kilos. in kilos. Unmanured 9,869 1,131 37.7oo Leather 12,822 1,178 39.268 Nitrate of soda 11,465 2,035 67,832 It will be observed that the leather produced only a slight increase in the yield of beans. 1 894- Agricultural Science. 55 (c) Field Experiments with Sugar-beets. Same soil as in previous experiments. Kach plat measured i ar. The fertilizer was applied at the rate of 42^ pounds of nitrogen, and 528 pounds of phosphoric acid per acre. Resui,ts per Hectare. Percentage Kilos. increase over unmanured. Unmanured 34)830 Soluble phos. acid 34.38o —1.5 Water and citrate sol. phos. acid 34,290 — 1.2 Citrate sol. phos. acid 34,38o — 1.5 Unmanured 33,840 Leather + sol. phos. acid 37,890 ' 11. 9 Leather -\- water sol. + citrate sol. phos. acid 37, 180 10.7 Leather-!- citrate sol. phos. acid 35,9^0 6.0 Unmanured 32,940 Nitrate of soda -f- sol. phos. acid 43,38o 28.1 Nitrate of soda + water -|- citrate sol. phos. acid 42,070 24.2 Nitrate of soda -f- citrate sol. phos. acid 43,830 29.4 While the leather has shown its effect, it runs far behind the nitrate of soda. Petermann says that from a financial standpoint the leather shows a loss and the nitrate of soda a gain. Of his results the experimenter makes the following resume : " With horsebean, the leather shows practically no influence the first year. With oats and sugar beets an increase is noted, but this is slight when compared with that from blood and nitrate of soda." In a later publication, Petermann says that in his experiments from 1 880-1 885, the various forms of nitrogen have shown the following relative worth : i . Nitrate of soda ; 2. blood; 3. dissolved wool ; 4. ground bone ; 5. raw wool ; 6. leather. Deherain* gives the results of the following experiments con- ducted in the field at Grignon with ground leather. The results with wheat in 1880 and 1881, show the residual effect of that applied to potatoes in 1879 : Potatoes. Wheat. Hectolitres. Grain, Straw. Grain. Straw. Qtm.* Otm. Qtm. Qtm. Unfertilized.-. 224 25.0 37.25 164 20.5 Leather, 2000 kilos 295 27.5 40,00 23.4 38.7 Leather, 1000 kilos 277 25,0 38.00 23 37.6 * Qtm. = quintal metrique = 100 kilograms. Deherain remarks that his experiments make it clear that the * Chimie A^ricole ( 1892), 619. (Dry Matter). 1889. Average of Kilos. both years. 47 190 48 178 52 175 61 152 43 102 56 Agriculturai< Science. voi. viii. No. 2. leather yields its nitrogen very slowly. He does not state whether the leather used had been steamed, roasted, or was untreated. Miintz* and Girard, in connection with their experiments on the nitrification of various nitrogen-containing organic sub- stances, carried out also a series of field experiments with various nitrogenous materials. Each plat had an area of one ar. and received 1.25 kilos of nitrogen the first year, together with the necessary quantity of phosphoric acid and potash. No manure was applied the second year. The soil was light and sandy, being quite favorable to nitrification. The plats were planted with fodder com during both years. Fodder Corn Grown Upon One Ar. 1888. Form of nitrogen. Kilos. Nitrate of soda 143 Dried blood 130 Roasted horn 123 Roasted leather 91 No nitrogen 59 The above results show that leather even when roasted is quite inferior in its action to dried blood and nitrate of soda. Marckerf gives the following results obtained by Seyffert, at Halle, with cole-rape : Form of nitrogen. Yield in grammes. No nitrogen 75.5 riveather 469 ,, .. Steamed bone meal 1,572 No nitrogen j ^^^^^ ^;g^^ [^Nitrate soda 2,607.5 In order to control the above experiment another test was car- ried out with oats by Julius Albert-Miinchenhof. YlEl