October, 1926
ISDlJSTR/;IL = I S DESGIXEERISG CHE.IIISTR Y
999
The Development of the Chemical Industry in Italy' By Prince Piero Ginori Conti S E S A T O R OF THE
Introduction
Y SUBJECT is a brief review of the actual conditions of the chemical industries in Italy, and my aim is t.0 make better known in America the efforts which are being made in Italy t'o develop her natural resources to their fullest extent'. These efforts are sponsored by our national government, and also by the hIinister of National Economy, H. E. Belluzzo, who was largely instrumental in my selection as the representative of the Italian chemical industry, and who has especially requested me to describe the work now under way to achieve this object.
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Deficiency of Fuel
Although Italy is favored by h'ature with all the most, splendid gifts of beaut,y, Kature appears not to have been so bountiful in the matter of supplying one of the most essential industrial commodities, coal. As yet, no coal has been discovered in Italy; and as for oil, we can only hope that it may be found. Therefore, the national government has given serious cons.ideration to this problem, and has instituted a special research service for exploring the undersoil of our peninsula, .in order to discover any oil beds, vhich we hope may be found in the deeper strata of our undersoil. At Ragusa, in Sicily, some asphaltic rock exists, and a methodical exploitation of such minerals ha:, been begun. The studies that have been made have led to the construction of a special form of retort, wherein very poor materials ( 5 per cent) can be distilled without resorting to ext'ernal fuel. Our only sol.id fuel is lignite, of which there are several beds of some importance in central Italy (Valdarno, Ribolla, Mugello) and in Istria (Arsa). Several plants for the extensive and .rational utilization of this fuel have been constructed or planned. At the same tinie, legislative measures have been introduced t o insure ecclnomical combustion of all kinds of fuel. Utilization of Hydroelectric Power
Notwithstanding, our industries are placed under a formidable handicap by our unfortunate condition with regard to coal and oil. Therefore, the general Italian industry, especially the chemical industry, has directed its efforts to better utilization of hydroelectric power. Although Italy has not very large individual sources of hydroelectric power, she has taken advantage of every opportunity to exploit the smallest sources of hydroelectric power. Her engineering feats in this direction have rightly been greatly admired all over the world. In the native 1a)nd of Galvani and Volta, (2. Ferraris, the electrical engineer, followed the noble national traditions. Nowadays, many of the pupils of Ferraris, scattered throughout It'aly as directors of great electrical enterprises, bring t o their daily work the idealism and enthusiasm of their teacher. So the dream of that pioneer to bring into existence one unified transmission and distribution network throughout Italy, from the Alps to the African Sea., has materialized in a comparatively short time. Hydraulics and electrotechnics have helped to combine their resources to absorb all of the problems of this gigantic 1 Presented a t the 72nd Meeting of the American Chemical Society, Philadelphia, Pa., September 6 to 11, 1926.
KINGDOM OF
ITALY
hydroelectric v-ork, putting in parallel the stations of the Alps with those of the Apennines. The winter water shortage of the first is compensated by the production of the others. Large reservoirs complete the great work, and it will be sufficient to mention the great installation of Sila, from which the power will be distributed through a network a t 200,000 volts, to Kaples from one side a t a distance of 600 kilometers, and to Sicily, the other side, spanning an overhead line through the Messina Narrows. A figure of something like six milliards of kilowatt hours represents the yearly consumption of electric power in Italy a t the present time, but we expect shortly to increase that figure very substantially and in course of time to double it. Compared with America's enormous consumption, these figures may appear insignificant, but the area of Italyand the daculties, both technical and financial, which we have had to face, should be considered. Since the beginning of the century, all of our industries have benefited by the extensive use of electric power, particularly the chemical industries, but at the same time we have been increasing very considerably our imports of coal, which indicates that the progress of work has been very important. Electrochemical Industries
HISTORIC.~L-I~~ the field u i electrochemical industries Italy has aln.ays occupied one of the first places, demonstrating again that, if natural conditions permitted, our country was not lacking in competent men with the right sort of initiative. Our first electrochemical industries date back as far as the close of the last century, when the nianufacture of calcium carbide was begun at the Terni waterfalls, not far froni Rome. These waterfalls, which rank among the finest in Europe, are not the work of Nature; they are remnants left by our great Roman forefathers, who diverted the course of the River Velino, causing it to fall into the River Kera. CALCIUM CYANAMIDE-The first plant in the world for the industrial manufacture of calcium cyanamide was erected at Piano d'0rta. The production soon increased so that the Italian works ranked, in 1909, with the largest in Europe, being second only to those of iiorway. The act'ual trend lies rather in the direction of synthetic ammonia, though calcium cyanamide is still manufactured in very considerable quantities, especially a t Terni. SYXTHESIS OF hlZI,MoNIA-~he contribution of Italy to the synthesis of ammonia has been very great, not only from the technical but also from the industrial side. The great successes of the German industry in the large works of Oppau and Merseburg were followed by the Italian processes of Mr. Casale, which are noted for their extreme simplicity of installation. The synthesis of ammonia could be developed quickly all over the world with units of small and medium capacity. The total world capacity of the Casale installations now amounts to 200 tons of fixed nitrogen per day. The Italian firm, Montecatini, also has developed the Fauser process in many works in Italy. This process alone will soon fix more than 100 tons of nitrogen per day. R e owe this large development to engineer Pauser, who constructed electrolyzers for the cheap production of hydrogen. These electrolysers can be installed at a lorn cost.
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
We now have the following plants: Nera Montoro (Casale processes, 20 tons per day); Agordo (10 tons); Sovara (20 tons); and Merano (50 tons). These plants are in full operation, and in a short time others, which are now in course of construction, will be added, as follows: one at Cotrone (20 tons); and the other on the Coghinas River, in Sardinia (20 tons). Besides nitric acid by oxidation of ammonia, ammonium sulfate is manufactured a t most of the synthetic ammonia works which have adjoining sulfuric acid plants. Ammonium sulfate is also obtained as a by-product a t ordinary gas works and in gasification plants of Torre del Lago and Pietrafitta, which are erected on large fields of peat and lignite to produce electric power. At Torre del Lago, not far from Pisa, the peat is gasified on the Mond system (conveniently modified), thus giving power for the state railways and ammonium sulfate as a by-product. Something along similar lines is done a t Pietrafitta, near Perugia and Lake Trasimeno, where lignite is used instead of peat. The result of all these plants has practically emancipated Italy from importing any nitrogen compounds, with the exception of some Chile saltpeter. The total output of ammonia compounds in Italy, reckoned as nitrogen, amounted to 6800 metric tons in 1925. Of these, about two-thirds were obtained by direct synthesis of atmospheric nitrogen and electrolytic hydrogen, the remainder coming from other sources. For the current year these figures will be more than doubled, and when the new plants are in complete operation the yearly output will be about 35,000 tons of nitrogen. CAUSTICSODA-Another important electrochemical industry is that of electrolytic caustics. About 70 tons of caustic soda per day are produced in five large plants, three of these applying the mercury process, the remaining, diaphragm processes. This great production compelled the Italian chemists to visualize a possible utilization of the large quantities of by-product chlorine. This has been completely worked out, and all the chlorine produced finds useful applications. Besides the production of hypochlorites, chlorates, carbon tetrachloride, and other chlorine derivatives, these are two other methods of utilizing chlorine which are worthy of mention; namely, the extraction of cellulose with chlorine gas and the treatment of leucitic rocks with hydrochloric acid. For the production of cellulose, two Italian plants a t Naples and a t Bussi have succeeded in making industrially possible the old analytical method of Cross and Bevan. This is a very important result for Italy, because by this method, besides utilizing chlorine, cellulose is extracted so as not to require the great quantities of fuel used by the old processes. The chlorine process is very well suited for the treatment of many Italian fibers such as straw and esparto. In fact, Italy has the most convenient geographical location for the utilization of esparto coming from the northern coast of Africa. POTASH SALTS-It is noteworthy that in the last year, especially through the efforts of G. A. Blanc, deputy to the Italian Parliament, the problem of the utilization of leucitic rocks has been completely solved. Leucite is an aluminum and potassium silicate, existing in large quantities in the magmatic rocks belched forth from volcanoes of Latium and Campania. The American scientist, Dr. Washington, in the course of his appreciated studies on the “Roman Comagmatic Region,” has shown that the Italian deposits of leucitic rocks are the greatest in the world, and their total content of K20 is of the same order in both the fields of Stassfurt and Alsace. The first problem to be solved is the separation of pure leucite from the magmatic rocks in which it is contained. The proposed method of magnetic enrichment met with great difficulties in connection
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with the particular magnetic properties of the material. After a very accurate scientific study, Mr. Blanc has been able to explain the phenomenon in all its detail and, in consequence, to construct a special model of magnetic separator, which has given excellent practical results. Almost pure leucite (98 to 99 per cent) so obtained is attacked with hydrochloric acid, so that potassium and aluminum are made to pass into solution, leaving an insoluble residue of silica, which can be obtained hy special devices in such a form as to obviate the well-known filtration difficulties. The second step is the separation of the two chlorides found in solution-i. e., potassium and aluminum chlorides. In order to make the process feasible and adaptable to Italy’s peculiar conditions, costly evaporations must be avoided. This has been accomplished by applying, in a large measure, the known principle of solubility influences. In this particular case, the electrolyte to be added is hydrochloric acid, and favorable results can be secured, provided the gas is in a concentrated and very pure form. Such is the acid obtained by direct synthesis of hydrogen and chlorine by-products during the electrolysis of alkali chlorides. It is not possible in this brief survey to discuss the details of the process, but it gives directly potassium chloride, 99 per cent pure, and makes it possible to recover alumina in a state of purity much superior to that obtained by the Bayer process. The solution of the chlorine problem has had a favorable effect in Italy on the following three leading chemical industries: production of potassium fertilizers, production of aluminum, and production of cellulose as raw material for the manufacture of artificial silk. METALLURGICAL PROCESSES-Electric power has had extended applications also in metallurgical processes. Particularly noteworthy are the plants of Val d’Aosta, where the magnetite coming from Cogne is worked in electric blast furnaces, producing pig iron of high purity, especially suited for the preparation of special steels; and, further, the plants of St. Dalmazzo and Iglesiente (Sardinia) for the electrolytic production of zinc; thus utilizing the minerals that have been exported for many years owing to the impossibility of applying in our own country the old thermic process. Recently, a new firm has started plants in Val d’hosta for electrolytic iron. Heavy Chemicals
.A few words must also be said concerning the normal production of heavy chemicals. SULFURIC AcID-It is a by-word in competent circles that the industrial progress of a country can be measured by its output of sulfuric acid. This product is being manufactured on a steadily increasing scale in Italy, over eighty large works supplying it. The greater part of these works are controlled by one important concern, the Montecatini Company, which owns pyrite and sulfur mines and has plants scattered all over Italy for the manufacture of fertilizers. The Italian demand for sulfuric acid is now completely covered by national production. Sulfuric acid is chiefly used by the following Italian industries: fertilizers, copper sulfate, explosives, artificial silk, organic dyestuffs, and several others. The output in 1925 was 1,100,000 tons of the 55 BC. type, by the chamber process. -4t the Merano works of the Montecatini group, the output can attain 6000 tons of sulfuric acid per annum. Rotatory ovens are used there for burning iron pyrites. This type of oven is prevalently used elsewhere, and some plants have adopted the Cottrell process for the electrical precipitation of pyrite cinders. The actual supply of iron pyrites is more than sufficient for the needs of the chemical trade in Italy, and the surplus is exported. Refuse of pyrite cinders
October, 1926
INDUSTRIAL A N D ENGINEERING CHEMISTRY
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in 1924 amounted to about 350,000 tons. This has compelled the Italian iron industries to find a way to substitute these cinders for iron ores. These studies have led to a very biinple process of roasting, which allows the coniplete elimination of sulfur in a very cheap way without special plants. The Nontecatini Company proposes to erect a large plant a t Porto Marghera, near Venice, for the purpose of purifying and agglomerating pyrite cinders. Coke for the further metallurgical process will be supplied by the neighboring gas works, erected for the large glass factories of the Societsi Italiana Vetri e Cristalli. Handling 300,000 tons of pyrite cinders per annum, with a mean content of 50 per cent of iron, about 150,000 tons of pig iron could be obtained, which would considerably diminish imports of that material. The Italian iron works are obliged to import large amounts of pig iron, and all the efforts to emancipate the country are welcomed. HYDROCHLORIC AND NITRIChcms-The domestic production of hydrochloric and nitric acids and sodium sulfate and bisulfate can meet all the requirements. The plants for direct synthesis of nitric acid from air (arc process) are now closed, being substituted by ammonia oxidation. ALKALIIsDosTRY--The alkali industry, besides the electrochemical plants for caustic soda, is mainly represented by the large works of Solvay a t Rossignano, near Pisa, n-here carbonate of soda and caustic soda are manufactured. The Adria plant ai, Monfalcone, near Trieste, has also been completed and is now in operation. The output of these two plants will be able to cover almost Completely the deinands of the Italian market, which practically doubled between 1922 and 1!324. A large part of the caustic soda is produced in liquid form a t 36" or 50" BE. Over 20,000 tons of solid caustic soda were imported in 1925 to meet the demands of the artificial silk industry. The growing Italian output, as shown byst,atisticsfor 1926, leads us to hope that the national requirements will be covered by home production. All the more important products of chlorine and its derivatives, such as liquid chlorine, calcium and sodium hypochlorites, chlorates of potash and sodium, carbon tetrachloride, are manufactured with by-product chlorine. The Pomilio and Bussi plants, where chlorine is used in the manufacture of cellulose from esparto grass and straw, have already been mentioned.
Sulfur dyes and other types of dyes, including synthetic indigo, are being manufactured in growing quantities and a certain amount of export is also noticeable. ARTIFICIALSILK-The development of the Italian artificial silk industry has been of great importance. This delicate industry requires a large number of skilled hand laborers, while the raw materials represent only a small fraction of the total value, so that it is especially adapted to our conditions. I n fact, notwithstanding the enormous difficulties arising from the high tariff protection of foreign countries, the Italian industry has rapidly grown, until in 1924 Italy occupied second place in world production of artificial silk, following immediately the United States of America. In 1925, the Italian output of artificial silk was approximately 13,500 tons. Eleven large plants were working in 1925, and eleven others are being erected. The total capital invested in the artificial silk industry is about one milliard and a half lire. The viscose process is employed exclusively, but one of the new plants intends to revert to the cuprammonium process, formerly tried a t the Pavia works, and another system, the cellulose acetate process, is about to be applied. About one-half of the total Italian output is exported. The principal raw materials for this industry are cellulose, caustic soda, carbon bisulfide, sodium sulfate and bisulfate. Cellulose has to be imported almost completely, although, as previously mentioned, the Pomilio and the Bussi works are now manufacturing it. The other materials are manufactured in Italy in sufficient quantities and ' only small amounts have to be imported. PLASTICS AND CELLULOID-The manufacture of plastics is amply sufficient for the requirements of the home market. The same can be said of the special branch of cinema films. The Ferrania works can turn out 24 million meters of films per annum. Synthetic camphor, galalite, synthetic resins, Bakelite, etc., are being manufactured with success in several works, and it is hoped to increase the output of these materials, especially synthetic resins obtained by treating casein with formaldehyde (galalite) .
Organic Chemical Industries
Mention only can be inade of the sugar and alcohol industries, which have progressed sufficiently to allow a certain amount of export trade, but a few words must be said about the manufacture of citric acid, tartaric acid, and essences. Citric acid is produced as such and also as citrate of calcium. It is exported in very large quantities, especially from Sicily. Production of tartaric acid is also increasing, and the export trade is growing steadily, notwithstanding competition. The same can be said about essences and extracts.
Let us now turn to the large organic chemical. industries, taking first the manufacture of methylated spirits, which are a t present obtained by the distillation of beech wood; but soon the synthetic methods TTill be applied i n the Terni plant of the Casale Ammonia Company. Formic acid is already being made a t the large Cengio works of the Societli Italiana Prodotti Esplodenti, by reaction between carbon monoxide and caustic soda. Formaldehyde is now produced a t Maccagno on Lake Ilaggiore, in such amounts as to cover domestic requirenients and permit a certain export trade. The manufacture of acetic acid from acetylene has been resumed at T-illadossola in the Province of Kovara. DYESTUFFS-The subject of coal by-products and their consequent industries is far too exhaustive to be dealt with completely. iLluch has been done t o increase the output of coal tar, and legislative action has been introduced to insure the proper treatment of coal in gas and coke works. This will contribute substantially to the further development of our dyestufY industry, which began during the World War and which has been steadily progressing, notwithstanding the very serious post-war crisis which affected all industries but particularly this one.
Citric and Tartaric Acids
Boric Acid Industry
Having reviewed the principal chemical industries in Italy, a few words must be said about another essentially Italian chemical product, the manufacture of which began in Tuscany over one hundred years ago. I allude to the boric acid industry, with which I have been personally concerned for many years and to the perfecting of which I have devoted the best part of my life. Boric acid is contained in the fumaroles or natural steam springs which are situated between Pisa and Siena. The acid can be crystallized from the waters resulting from the condensation of this steam, after proper concentration, x-hich is accomplished without using any fuel but by means of the steam itself. The acid is partly sold in the crude state (82 per cent purity) and
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
partly refined to the required standards up to the C. P. type. It is turned out in crystal, powder, and pellet form, according to demand. The company of which I am the chairman and general manager, the Societh Boracifera di Larderello, owns eight different works, all of which are situated in the volcanic zone of the fumaroles, which are locally called “soffioni,” a word which can be translated as “vents,” from the peculiar hissing noise which they make. Borax is made at our works from boric acid and soda ash. Practically all the boron salts are manufactured, among others sodium perborate, which is used for bleaching purposes. The mother liquors contain ammonia, which is extracted from them and made to react with carbon dioxide. The latter is one of the gases accompanying the steam. Ammonium carbonate is thus obtained. A large plant handles the gases, separating carbon dioxide, which is also turned out in liquid form. Helium and the other rare gases are also present and studies are being made to extract them. The special feature of our plant is that the thermal energy of the natural steam is utilized for generating power.
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Three electric plants, one of which has three units of 2500 kilowatts each, are running by means of natural volcanic steam, the output of which, whether condensate or exhaust steam, is passed on to the chemical department for the boric acid treatment, while special depurators separate the gases which are sent on to the carbon dioxide plant. Steam is given out by drillings, and considerable outputs-up to 60,000 kilograms per hour from one well alone-can be obtained. This industry illustrates the thorough utilization of natural resources to which reference has previously been made. Conclusion
The chemical’industries of Italy not only are gradually providing for a very large part of home requirements, but in some instances their output is such as to allow a considerable export trade. The growing efficiency of Italian industries, and more especially of the chemical industries, can be traced to the advent of the present national government in 1922, which is responsible for the renewed spirit of discipline in the working classes and the consequent collaboration of labor and capital.
The Dyestuffs Industry, Forerunner of What?’ BY &&e E. I. DW
du Pont
P O N T DE NEMOWRS & CO.,WILMINGTON, DEL
ONE seven years ago the AMERICAX C H E m c A L SOCIETY, Progress in the dye industry can be broadly measured by at its meeting in Philadelphia, passed the following a comparison of (I) the volume of manufacture measured in resolution: pounds, (2) the variety of products made, and (3) the selling prices of the dominating items. For this purpose it seems WHEREAS,The establishment of a complete self-sustained coalproper to choose for the comparison the years: tar chemical and dye industry is a national necessity because of
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its well-defined character as a key industry in our economic life; and WHEREAS,This industry has a much deeper significance in t h a t it constitutes a vital reserve both as to personnel and supplies for our Army and Navy in modern warfare; and WHEREAS,This industry is also essential for supplies of synthetic drugs for the health of the Army, Navy, and general public in peace and in war; and WHEREAS,This country possesses a n abundance of raw material for such an industry, ample capital and chemists capable of solving the many scientific and technical questions involved, as evidenced by the splendid progress of the past three years; and WHEREAS,This initial period, with all of its attendant difficulties, has not yet been adequate to admit of the efficient production in domestic plants of all colors needed by American consumers; and WHEREAS,The greatly depreciated rate of exchange in t h a t country which in the past has manufactured the bulk of the world’s supply of dyes preeent a new and threatening factor in all transactions of a n international character: Therefore be it Resolved, First, t h a t we urge all Americans to stand loyally by the young industry which embodies such far-reaching potentialities of service and protection for our country; Second, t h a t every needful safeguard be thrown around this industry by the Congress of the United States, especially through the imposition of effective import duties and the provision of a temporary licensing system along the general lines embodied in H. R. 8078 as the Longworth bill. Correct. CHARLES I,. PARSONS, Secretary
It seems, therefore, appropriate to review, in the light of the years which have elapsed, the progress made in the dye industry, and also the progress made in analogous chemical industries, which progress is dependent on the same character of reactions, apparatus, and personnel as the dye industry. Presented at the 72nd Meeting of the 1 Received August 25, 1926. American Chemical Society, Philadelphia, Pa., September 6 to 11, 1926.
1914-Largely before the World War, when the United States was dependent on Germany for its supplies of dyestuffs. 1919-Immediately after the World War, which had caused a period of five years of substantially complete embargo of the importation of dyes. 1925-The most recent year available after a period of tariff protection.
Table I gives data compiled by the United States Department of Commerce, but takes no cognizance of the improrement in tinctorial power in the products in the later periods. Table I-Comparison Kind of dyes Acid Basic Direct Lake and spirit soluble Mordant and chrome Sulfur Indigo Other vats Unclassified
of Dyestuffs I m p o r t s and Production (Figures are in units of 1000 pounds) 1914 -1919-1926Imports Production Imports Production Imports 10.214 590 93286 12,196 4,122 608 3,002 4,036 14,788 759 10.264 14,445 1.512
1.813
4,450 7,054 8,407 1,945 27
3,985 17,624 8,864
-
TOTAL 45,947
1.606 24 1,051 2,215
63,401 3,290
5s
2,543 20,760 29,122 2,608 581
642 122 2 2,41i 12
86,344
5,210
- _ _
It takes but a cursory examination of these figures to show that the complete embargo for the years 1914 to 1919 resulted in the establishment of a real dyestuffs industry in the United States and that, so far as tonnage is concerned, the dyestuffs industry has not made commensurate progress during the period when tariff protection was relied on for its stimulation. It is quite striking to point out, however, that in the case of indigo and sulfur colors, which have a low selling price and are protected by a prohibitive tariff, satisfactory growth has continued. I n the case of vat colors the tariff protection has not been sufficient to enable American manufacturers to pro-
