Feb.,
1920
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
was attaiped when the contact potential reached * 0.03 volt. This potential was found in the presence of KC1, 51 millimolar AlC11, 0.02 millimolar ThC14, 0.007 millimolar BaC12, I .9 millimolar
McNear and Bowles' have patented an apparatus for electrical treatment of emulsions. Attempts have been made to precipitate emulsified water in linseed oil, etc., by high tension electrical discharge, but so far as can be learned the method has not been perfected. The sparks tend to jump over the surface rather than through the mixture. Pilat and Piotrowskiz favor heat treatment under pressure for breaking of crude petroleum emulsions consisting of oil, salt water and earthy matter. I n closed kettles holding 40,000 kg., the crudes were heated by steam to ~ z o ' t o 130' C. a t 3 to 3.5 atmospheres pressure. A practically quantitative separation took place in 5 hrs. a t 3 atmospheres pressure. The separation was accomplished more quickly a t higher pressures.
A slight increase over these concentrations charges the particles with positive electricity and they become stable again. I n 1914 Ellis1 showed that colloidal ferric hydroxide from 0.0017to 0.0039 per cent final concentration coagulates this type of emulsion. Higher concentration results in reversal in charge of the dispersed phase and stability ensues. Philip2 advised that the emulsification tendencies of a lubricant be tested before using. He found that very slight contamination of a good nonemulsifying mineral oil by Mexican, Trinidad or Persian crude oils greatly increased the tendency to emulsify. He described a test for the purpose. Harris' proposes to break emulsions of water and petroleum oil by passing a heavy electrical current. The electrodes must be close together. Dijxhoom4 removes emulsified lubricating oil from condenser water by passing I Io-volt current through the water as it passes through the feed water pipe. Rogers6 breaks emulsions of mineral oil and water by adding sodium salt of a sulfonated mineral oil (0.25 to 4 lbs. per barrel of mixture) and heating. McK.ibben6 passes emulsion of petroleum and water (heated sufficiently to produce vaporization) through an intensified electrical field. The vapors are condensed and cooled and the water drops out.
Koetschau: claims that by heating Roumanian and Galician petroleums to 1 2 0 ' to 130' C., the emulsions broke within a few hours. He recommends heating acidified distillates with steam a t 3 to 4 atmospheres pressure. Newman' found that emulsions of oil-in-water with soap as emulsifying agent are irreversibly broken by freezing. One could continue indefinitely discussing special means of breaking emulsions, but from a knowledge of the nature of a given emulsion and application of the principles laid down a t the head of this chapter, one ought to be able to deal with each special case. Since foams are closely related to emulsions it is of interest to note here that Fiskes has found isoamyl valerate to be an excellent inhibitor of foaming. He describes methods of preparations of this ester. 1 U. S. Patent 1,297,378 (1919).
Chem., 89 (1914), 145. J . SOC.Chem. Ind., 84 (1915), 697 * U. S. Patent 1,281,952 (1919). 4 Le Pagier, 22 (1919), 53. 6 U. S. Patent 1,299,385 (1919). 12.ghysik.
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8
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Petroleum, 18 (1918). 1045. Z . angew. Chem., 84 (1919), 45. 4 J . ghysik. Chcm., 18 (1914), 34 8 J . B i d . Chem., 86 (1918), 411. 8
8
U. S. Patents 1,299,589 and 1,299,590 (1919).
FOREIGN INDUSTRIAL NEWS By A. MCMILLAN,24 Westend Park S t . , Glasgow, Scotland
FUEL DEPOSITS IN ESTLAND According to an article in Engineering, Estland Seems to be better off than most of her neighbors as regards fuel. Large deposits of shale extend from the coast to Wegenberg Over an area 80 versts long by IO versts wide, containing an amount estimated a t ~ , ~ o o , o otons. o The shale contains so large a percentage of oil that it burns if a light is applied, It is being used for the production of gas and electricity in Reval and also for factories and pr:vate houses. Preparations are also being made for its application in the driving of locomotives. In the powdered state i t is used for firing boilers and is said to give satisfaction. While its calorific value i from 50 to 60 per cent that of coal, its cost is only one-fourth that of coal. The deposits are being worked by the Estnian state and are also attracting attention in England. SULFURIC ACID MANUFACTURE A short account of the effective "Grillo" plant erecied in England by the government for the manufacture of sulfuric acid by the contact process is given in the Journal of the Society of Chemical Industry for October IS. The catalyst employed is platinum, deposited on granules of calcined magnesium sulfate in the proportion of 0 . 3 per cent. The purified gases from the sulfur burners heated to about 350' C. are passed through two converters in parallel, each containing 10,000lbs. of the platinized
.
mass distributed on four trays. For absorbing the trioxide produced, towers packed with quartz are used and practically Perfect absorption can be obtained. The purification of the gases, which is important in preventing deterioration of the Catalyst, is effected by passing the cooled vapors through coke columns and sulfuric acid drying towers; arsenic is thus diminated and less than 0 . 0 2 per cent of other impurities (water and inert dust) retained. Details of efficiency and productioncosts are given.
GROWTH OF FRENCH CHEMICAL INDUSTRY According to Schweiz. Chem. Zeit., September IO, rgig, the French chemical industry has developed greatly during the war. The annual output of sulfuric acid was doubled, increasing from I,OOO,OOO to z,ooo,ooo tons. The output of nitric acid per month is three times greater than the total annual output of pre-war days. The yearly output of cyanamide has increased from 8,000 tons in 1913 to IOO,OOO tons a t the present time. Prospects are favorable for the absorption of the surplus war products for agricultural purposes, and viniculture should benefit in particular. Copper sulfate is indispensable in the vine industry and of the yearly output of 50,000 tons, 40,000 tons are absorbed by viniculture. The necessary copper, which is mined in Spain, is, however, controlled by English interests.
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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 C H E M I S T R Y
Vol.
12,
No.
2
JAPANESE CELLULOID INDUSTRY
NICKEL-IRON ACCUMULATORS
According to the Japanese press, the following developments are taking place in the celluloid industry: Several Japanese business men have been asked to join in promoting a concern for the amalgamation of the 130 small celluloid factories in Tokyo, the new concern to be capitalized a t $I,OOO,OOO. Another proposal by a prominent Japanese factory owner is for the formation of a concern with a capital of about $6,030,000, which is to amalgamate the present factory owned by him and the Sakai and the Abosh factories, the capital to be increased to $7,5oo,ooo when and as necessary. The scheme will be extended to cover all the factories in the country. Another version of the proceeding is that eight large firms are to amalgamate shortly. The joint concern is to be called the Dai, Nippon Seruroido Kubushika Kaisha, and its capital is to be $6,250,000.
Arrangements have been made with Batteries (Ltd.), Redditch, to. manufacture in England the nickel-iron-alkaline electric accumulator for which Dr. V. Jungner, a Swede, took' out his first patent in 1899,and which began to be manufactured on a large scale by a Swedish company about eight years ago. The active material of the positive electrode is nickel hydroxide, mixed with other ingredients, to increase the conductivity. The composition is formed into briquettes which are fed between two inactive perforated nickeled steel strips. The strips are cut up into suitable sizes, folded together and fitted into a steel frame, the complete electrode being then put through a rolling process to ensure perfect contact between the active material and the steel strips. At the same time grooves are formed on the plate to keep the Para rubber insulators in position. The negative electrodes are constructed in the same way, the active material being iron oxide specially prepared and mixed with other materials to prevent self-discharge of the cell. The assembled positive and negative plates are immersed in a solution consisting chiefly of potassium hydroxide, contained in a steel cell with brazed joints. The batteries are made in two types, one {or a normal slow discharge in 8 hrs., and the other for rapid discharge in 4 hrs. The average working voltage is 1 . 2 volts; i t drops slightly during the first 15 min. of discharge and then remains practically constant until the cell is discharged.
ARSENIC COMPOUNDS At a recent meeting of the Chemical Society, London, Prof. F. I,. Pyman described a number of arsenic compounds which had been prepared with the hope that they might be used for direct intravenous injection in simple aqueous solution and so replace the elaborate technique required in the administration of salvarsan. These compounds are arseno-benzenes of a new type obtained by t h e reduction of benzodiazolearsinic acids, which are produced by the action of acetic or formic acid on diaminophenylarsinic acid and its homologs. The new arsenobenzenes form dihydrochlorides which are soluble in water, but, although weaker in acid properties than salvarsan, they still prove too acid for direct intravenous injection, These experiments, says Nature, 104,342, are, however, of considerable value, as they form a starting point for further work on the replacement of amino groups by heterocyclic nuclei in arsenobenzenes.
INDUSTRIAL SYNTHETIC AMMONIA According to an article in Compt. Rend., 168 ( ~ g ~ g )1001, , the chief object for the fixation of nitrogen in peace times is the manufacture of fertilizers. Ammonia itself cannot be assimilated by the soil, while the nitrate is expensive and the sulfate requires the use of sulfuric acid. According to G. Ville, ammonium chloride is a t least equal to the sulfate as a fertilizer and is less heavy than the sulfate. In the Solvay process the ammonia is recovered by the use of lime, but the lime and calcium chloride are wasted. By a new process both the sodium bicarbonate and the ammonium chloride can be precipitated, thus the chlorine and lime are no longer lost and a good transportable fertilizer gained from synthetic ammonia in addition to three tons of sodium carbonate per ton of fixed nitrogen.
MANIHOT SEED AND OIL The manihot, a well-known rubber plant found in Brazil, has not hitherto been considered as a very valuable source of vegetable oil. The Germans in their desperate search for oil from any quarter have turned their attention to this plant. They planted large areas of manihot in German East Africa for the production of rubber and they now propose to consider seriously the possibility of obtaining oil from the plant. Analyses of three varieties of manihot gave the following percentages of shell and oil:
.
M . glaziovii Per cent
Shell: Kernel.. . . . . . . 7 3 . 2 5 ; 26.75 Oil in kernel.. . . . . . . . . 41.34 11.06 Oil in whole seed.. . . . .
M . dichofoma M pianhyensis Per cent Per cent 68.25; 31.75 46.14 14.65
7 4 . 2 5 ; 25.75 48.95 12.60
Technical manihot oil was prepared from a mixture of 67 per cent dichotoma, 30 per cent pianhyensis, and 3 per cent glaziovii unshelled manihot seeds, the yield by extraction being 13 per cent. On the basis of figures given above, the theoretical yield should amount to 14.15 per cent, and an analysis of the residue showed an oil content of I .3 per cent. The fatty acids are hard and of brown color. This technical or unrefined oil is used for the manufacture of varnish and soap. The residual cake is said to be a valuable cattle food.
FREEING FATS AND OILS FROM METALLIC IMPURITIES According to a German patent, the contaminated fats are treated with aqueous solutions of the lower organic acids or their salts which are capable of forming complex salts with the metallic impurities, the fats, etc., being oxidized or reduced by the reaction. For example, contaminated maize oil is dissolved in benzine or hydrocarbons and treated with a 5 per cent oxalic acid solution, and the mixture warmed to goo C. and well mixed by stirring. At the end of 4 hrs. the emulsion is left in the warm until the oil and acid liquors have separated, the latter being then drawn off. The oil, which formerly was dark in color and malodorous and contained 0 . 1 per cent ash is now light brown, of agreeable odor and taste, and free from ash. Lactic, tartaric, citric, glycolic acid, or glycocoll, or their salts, may be used.
MENTHOL AND PEPPERMINT MAFXET IN JAPAN According to a report from Tokyo, the menthol and peppermint market has become very dull and prices are still strikingly high. The amount exported is also decidedly lower. Last season more than 500,000 lbs. of menthol and peppermint were exported, the largest buyer being England, the second the United States, and the third Russia. The average price per pound was $2.30 for menthol crystals and 70 cents fo? peppermint oil. Before the war the exports amounted to 300,000 to gjo,om lbs. Germany was the largest buyer, England the second, and the United States came far down in the list. The pre-war prices were about $2 per lb. for menthol crystals and $ I for peppermint oil. The present prices of $5 and $ I .so per Ib. are too high to tempt foreign customers.
