INDUSTRIAL A N D ENGINEERING CHEiUISTRY
1286
Italian Letter
Paris Letter
By Carlo Padovani
By Charles Lormand
BOLOGNA, ITALY
4 AVENUSDE L’OBSERVATOIRE, PARIS,FRANCE
THEGEOTHERMICLPOWER STATION OF I,ARDERELLO A t the World Power Conference which was held in Wembley, the last of July, by the British Electrical and Allied Manufacturers Association, Prince Ginori-Conti read a very interesting communication on the Geothermic Power Central Station of Larderello. The country of Larderello, in Tuscany, has long been known for its celebrated soBoni-that is, natural hot springs or geysers, from which steam containing a small amount of boric acid issues. The boric acid in the sofioni was first discovered in 1777, and the production of boric acid was begun in 1815. Boric acid was a t that time crystallized from the small natural marshes, or lagoni, by artificial heating, and the fuel con$umption for evaporating purposes was considerable. Under the direction of Counts of Larderel, proprietors of the country and builders of this industry, the boric acid extraction made great progress. Artificial heat was entirely replaced by natural heat, and the boric acid was crystallized by conducting the hot vapors of the sojtoni,which had no other use, under the evaporating pans. At the same time the technic of boring and canalizing vapors was greatly developed, and the properties and constitution of natural gases and the production of several byproducts were carefully studied with the assistance of Prof. R. Nasini, of the University of Pisa. Thus the boric acid extraction industry of Larderello, which was a t first very primitive, became a sort of model industry, a truly self-controlled industry, which burned not one kilogram of coal or wood. But it was not until the beginning of this century that Prince Ginori-Conti, the president of the SocietA Soffioni Boraciferi di Larderello, undertook to study the utilization of natural steam for electrical power production. The solution of this problem offered great difficulties, but now, after twenty years of research, it has been accomplished. The first attempts a t natural power utilization in Larderello were made in 1904. Other successful experiments were made in 1905 (20 horsepower for illuminating purposes) and in 1912 (Fabbrica del Lago, 250 kilowatts, 250 kilowatts with turbines). Finally, in 1914 work at the central station a t Larderello with three turbo-alternators, each furnishing a motor power of 2500 kilowatts, was commenced. The steam as it comes from the earth is not directly available for the turbines, owing to its high gas content (HzS, COZ,He, etc.), and its low pressure (2 atmospheres). The steam producers indirectly he Led with natural hot vapors did not give good results. Now th? steam is freed of the gases in special apparatus invented by P. ,righenti. The pure steam a t a pressure of 1.5 atmospheres goes into the turbines a t 1.25 atmospheres. The turbines are of a modern type, with 3000 turns, and are joined to an alternator of 400 volts, 50 cycles. The steam already atilized is but a small proportion of that available. By increasing the number of borings it has been possible to obtain 150,000 kg. of vapor per hour. New borings gave steam a t higher pressures; a bore a t Serrazzano gives 24,000 kg. of steam per hour at 2 atmospheres, or 13,000 kg. a t 5 atmospheres; another boring a t Castelnuovo gives 60,000 kg. per hour a t 2 atmospheres. At Serrazzano a turbine has recently been tried which makes use of exhaust gases for heating the evaporating pans. The Geothermic Power Central Station of Larderello is capable of large development, and is, perhaps, the only example in the world of a great industrial utilization of volcanic power; and it shows a truly fascinating result of modern collaboration between science and industry. Prince Ginori-Conti believes that the utilization of volcanic vapors for generation of electricity could be successfully extended to the other volcanic regions in Italy, such as Pozzuoli, Etna, Stromboli, Vulcano, as well as in various other parts of the world.
3
October 10, 1924
Regulations Governing the Duty-Free Importation of Industrial Chemicals into the Dutch East Indies-The collector of customs of Java has issued rules of procedure which must be followed in order to obtain benefit of the duty-free admission of chemicals imported into the Dutch East Indies for industrial purposes, provided under the royal decree of March 17, 1923. These regulations have been forwarded to the Bureau of Foreign and Domestic Commerce, Department of Commerce, and information will be furnished upon request to the Division of Foreign Tariffs.
Vol. 16, No. 12
FUEL CONGRESS MEETS
A small congress for the study of fuels was held in Paris the first of October. Few contributions to this field were made which had not already been given to the congress of 1922. Although it is certain that the Maihle process, which consists of hydrogenating vegetable or fish oils, can give a theoretical solution of the fuel problem, it is no less true that this process does not permit obtaining fuel a t a price that can compete with the natural fuel. A ton of oil gives 98 kg. of glycerol and 902 kg. of fatty acids. From these fatty acids 630 kg. of petrol can be obtained. The value of the glycerol is about 500 francs; that of petrol, after fractionation into petrol, heavy oils, and lubricating oils, is about 1200 francs. After adding to this the cost of manufacture, estimated a t about 100 francs, one has a total of about 1800 francs. It would therefore be necessary for a ton of oil to sell a t a price less than 1800 francs-for example, 1500 francs; but actually, a ton of oil is worth about 3000 francs, which renders the process impracticable. The study of yields using chlorophyll is not yet sufficiently advanced for one to judge the economic value of the process. AS for the Bergius process, the problem seems to be advanced to the extent that it is now possible to treat, by berginization, bitumens, tars, asphalts, and in general all the liquid products; but berginization of coal is not yet perfected. In connection with this meeting considerable has been said in the press concerning the Bourgeois and Olivier process. This process uses the water gas furnished by the coke furnaces and, by a series of catalysts, passes successively through the first members of the hydrocarbons series-that is, methane, ethylene, and acetylene-and through successive polymerizations produces a synthetic oil having a calorific power of 11,539 calories per kilogram. Although it was stated that this process is already in the semiindustrial stage, the absence of details concerning its application causes a certain skepticism, inasmuch as, in the scheme of the process, there is nothing which was not already known in 1858, when Berthelot described these reactions. It was announced a t this congress that synthetic methanol is being made on an industrial scale in Germany. Under these conditions the wood carbonization industry, which was quite flourishing in France, will meet with severe competition. The production of wood charcoal will suffer by this, although its use for gas generators should be extended; since these generators have been on the market, wood charcoal has doubled in price. Along the same line, MM. Oswald and Penta have continued their researches on the solution of coal by means of naphthalene. By working a t temperatures around 270’ C., under a slight pressure, they have obtained extracts of coal containing neither sulfur nor ash, and by heating these extracts a t low temperature oils and tars containing considerable oil and little phenol are obtained. On carbonization these extracts give a coke without ash which is suitable for the metallurgical industry and the production of electrolytic carbon. Finally, and this is perhaps the most interesting point, these naphthalene extracts of coal containing no ash can be used directly in combustion engines using either solid pulverized products, or liquids similar to mazout. There are now under way numerous investigations to find an engine with a catalyst-that is, an engine in which a very heavy fuel can be transformed, in the same engine, into a lighter product. The solution of this problem seems to have been realized in the Mikhniof process, which the French navy has just adopted and which we know is already’in use in the United States. PREPARATION O F HYDROCARBONS M. Bourguel has studied a general method for the preparation He starts with true acetylene (C,,-) and passes to the higher product in the following manner: True acetylene is combined with soda in the form of sodium amide, then methylated by the action of dimethyl sulfate on the sodium compound obtained; a disubstituted hydrocarbon (Cs + I), which is isomerized by means of sodium amide is obtained. An identical operation applied to this C, + 1 hydrocarbon produces a Cn+ 2 hydrocarbon. Starting with true cyclohexylpropine, by five successive transformations M. Bourguel obtained the true cyclohexylhexine. This method should give very interesting results when applied, as M. Bourguel hopes to do, in the benzene, toluene, and napthalene series.
of true acetylene hydrocarbons.
December, 1924
INDUSTRIAL A N D ENGINEERING CHEMISTRY
FORMALDEHYDE IN VEGETABLES For a longztime the presence of formaldehyde in vegetables has been conceded, according to the hypothesis of Baeyer who considers i t as the first member of the carbohydrate series, and numerous reactions for showing its presence in plants have been described, especially the reaction of Schryver (red coloration due to its formation in the presence of a reagent formed from phenylhydrazine chlorohydrate, from potassium ferricyanide, and from concentrated hydrochloric acid.) MM. Fosse and Hieulle have recently shown that this reaction is not specific for formaldehyde, but is given also by glyoxylic acid, even in a one-millionth dilution. AMMONIUM CHLORIDE AS
A
FERTILIZER
It is known that in the Claude process for the synthesis of ammonia it is advantageous to obtain ammonium chloride as the final product. Several years ago, I summarized the reasons given by M. Claude, who estimates that it is more economical to obtain ammonium chloride than the sulfate. It was important to know if the ammonium chloride had the same fertilizer properties as the sulfate, for this point was considerably discussed in France. Experiments have been conducted by M. Vilcoq in the department of Loiret. For wheat, under the same conditions of cultivatipn and for the same quantities of fertilizer, the sodium nitrate and ammonium sulfate gave the same yield (NaN08, a yield of‘ 2 0 . 8 kg., (NH&S04, 20.3 kg.). On the other hand, for an identical lot in which ammonium chloride was used, the yield was 24.4 kg. MM. Demolon and Monbrun have made similar but more complete experiments, and have compared ammonium sulfate, ammonium chlorohydrate, urea, and sodium nitrate. Taking as a standard of yield a test crop equal to 100 for the grain figure and 100 for the husk figure, they obtained the following yields: Ammonium chloride Sodium nitrate Ammonium sulfate Urea
Grains 182 175 167 154
Husks 186 174 16; 150
The ammonium chloride was thus a t least equal t o the sodium nitrate and superior to the ammonium sulfate, the urea showing distinctly inferior to the mineral compounds. Independent of Haber’s process which he is operating a t Toulouse, the French Government has just negotiated with the Soci& d’Alias et Camargue to obtain the license and apparatus of the Casale process, which will also be operated a t Toulouse for the production of 120 tons of ammonia per day.
ETHER A SOLVENT FOR VEGETABLE TANNIN In the extraction of vegetable tannin almost always boiling water is used as a solvent. M. Durand has shown that this treatment gith boiling water is insufficient and that it would be of great interest industrially to treat all the plants from which the tannin is extracted, not only with boiling water, but with ether. Treatment of vegetable tannin (grapevine twigs, for example) with ether after extraction with the boiling water gives a second quantity of tannin equal to that already extracted. The method does not offer difficulties from an economical point of view, as the ether is easily recovered. ODORSIN CHLORINATED WATER An incident which may be instructive recently occurred in Paris. The public water supply in a whole quarter had a taste attributed to phenol. A quick investigation was made to find the cause. I n this quarter the water came from the Marne River, upstream from Paris, and before its distribution this water was treated by chlorination in the factory of Parc St. Maur. Above the chlorination plant, a pharmaceutical products plant accidentally emptied with its sewage the contents of a carboy of 50 kg. of guaiacol, used in the manufacture of a sirup for colds. It seems that the action of chlorine on the water containing small quantities of guaiacol, even in very weak dilution, gives chlorine derivatives the taste and odor of which are infinitely more pexceptible than the taste and odor of guaiacol. The most interesting fact is that the trouts which were used in tests, to prove that the quantity of chloride in the water was not too much, were not injured or killed as when a toxic compound or even malodorant is added to the water. This fact has been compared with a previous case where the chlorine-treated water went through pipes which had been freshly tarred and showed a disagreeable odor a t the point of distribution. October 31, 1924
1287
Washington Letter BARBITAL DUTYBASEDON AMERICAN VALUATION On November 14 President Coolidge issued a proclamation changing the basis of computing the duty on barbital from the foreign to the American valuation. This action was in harmony with a report made by the United States Tariff Commission following its investigation of foreign and domestic production, costs of this commodity. The present duty is 25 per cent ad valorem, but the Tariff Commission found that an increase of 50 per cent would not equalize the differences in cost of production, and in such cases the tariff act provides that the President may proclaim that the American selling price of the commodity shall be used in computing duty a t the ad valorem rate provided in the schedule. In other words, the ad valorem rate of 25 per cent will remain unchanged, but will be applied to diethylbarbituric acid on the basis of the American rather than the foreign value. This means an actual increase of about 100 per cent in the duty. The change in duty becomes effective fifteen days after the issuance of the proclamation. Application for an increase in the rate of duty on diethylbarbituric acid was made by the Abbott Laboratories of Chicago some months ago. This is the first time that an American valuation has been recommended under the flexible provisions of the tariff act. CONVENTION OF FEED CONTROL OFFICIALS The Association of Feed Control Officials held its sixteenth annual convention a t the Hotel Raleigh on October 23 and 24. Dr. H. W. Wiley delivered the address of welcome. Papers read during the convention included “Minerals in Animal Nutrition,” by J. 0. Halverson, of North Carolina, president of the association; “The Open Formula,” by E. S. Savage, of New York; “The Value of Coordinated Work by Feed Manufacturers and Feed Control Officials,” by E. W. Elmore, president of the American Feed Manufacturers’ Association; and “The Relative Economy of Feeding Factory-Mixed and Home-Mixed Dairy Rations,” by R. W. Chapin, president of Chapin & Company. A number of definitions and standards for feeds were adopted and several changes were made in existing standards. G. L. Bidwell, in charge of the Cattle Food Laboratory of the Bureau of Chemistry, was elected president for the ensuing year; W. H. Strowd, of Wisconsin, vice president; and A. W. Clark, of New York, secretary-treasurer. The executive committee consists of J. W. Sample, of Tennessee; J. K. Haywood, of the Bureau of Chemistry; H. H . Hanson, of Delaware; and the president and secretary-treasurer as ex-oficio members. MEETINGS OF METALSCOMMITTEES OF A, S. T. M. A series of meetings of the various metals tommittees of the American Society for Testing Materials was he/d in Washington on October 22, 23, and 24. The daytime sessions were held a t the Bureau of Standards, and the reports presented included those on the standardization of corrosion tests, methods of sampling and testing ferrous alloys, and specifications and tests for steel tubes, pipes, plates, fbrgings, etc. Other alloys, such as those of aluminium, were also considered. A special trip was made to Annapolis, Md., t o inspect spqcimens of sheet iron and steel, exposed for a weathering test a t this place seven years ago. These sheets are one of three sets similarly exposed, the one a t Annapolis being subject to sea air, another a t Fort Sheridan, Ill., and a third set a t Pittsburgh, Pa. The test at Pittsburgh is now over, all the sheets having failed. The sheets a t Annapolis and Fort Sheridan are now beginning to fail, and in each case it has been found that copper-bearing sheets stand up better than those free from copper. Plans for a similar series of tests of wire screens were reported to another committee of the society. These tests, which are being undertaken with the aid of the Bureau of Standards, involve the exposure of screens in four locations. A similar investigation is planned to cover galvanized and other coated metals. NEWFUMIGANT FOR CONTROL OF GRAINWEEVILS A new fumigant, which is noninflammable and nonexplosive but effective for the destruction of weevils in wheat in grain cars, has been discovered by specialists of the Bureau of Chemistry collaborating with the Bureaus of Entomology and Agricultural Economics. This new fumigant leaves no objectionable odor in the flour or other products made from the grain. It consists of a mixture of 4 volumes of ethyl acetate with 6 volumes of carbon tetrachloride. The new fumigant was discovered as the result of an extensive research to findsomething to take the place of the highly inflammable and explosive carbon disulfide, which was used extensively
w
