T H E J O U R N A L OF I N D C S T R I A L A X D ENGI-VEERING C H E M I S T R Y
528
used t h i s a p p a r a t u s for t h e p a s t t w o a n d a half years with entire success in washing large a m o u n t s of gelatinous precipitates, working with as m u c h as t h r e e p o u n d s of precipitate i n one funnel a n d washing with t e n liters of water a t one filling of t h e flask. BUREAUOF PLANT INDUSTRY DEPARTMENT O F AGRICULTURE WASHINGTON. D. C.
u. s.
1’01. 9 , NO. 5
face when breaking t h e c o n t a c t a n d t o prevent deterioration of t h e b a t t e r y . c o m p e n s a t i o n should always be m a d e with a rising m e r c u r y column a t point of contact. I n practice this compensator checks t h e gas volume consistently a n d accurately a n d does i t in less t i m e t h a n t h e old optical m e t h o d of adjusting t h e height
AN IMPROVED COMPENSATOR’ FOR GAS ANALYSIS By
E. T. GREGG
Received February 10, 1917
An i m p r o v e d compensator, described below, has been used with m o s t satisfactory results i n connect i o n with t h e H e m p e l a p p a r a t u s for gas analysis in t h e fuels efficiency l a b o r a t o r y of t h e Federal B u r e a u of Mines. As s h o w n i n t h e a c c o m p a n y i n g drawing, t w o p l a t i n u m wires a r e sealed i n t o t h e compensator side of t h e m e r c u r y m a n o m e t e r . T h e upper wire which is sealed a b o u t 3 / ~ in. a b o v e t h e m e r c u r y when level, is b e n t d o w n w a r d s a t right angle a n d just touches t h e surface of t h e mercury. T h e lower p l a t i n u m wire enters f a r e n o u g h t o m a k e electrical c o n t a c t w i t h t h e mercury. I n series with t h e t w o p l a t i n u m wires a r e a small d r y cell, switch a n d miniature l a m p . To use t h e compensator for adjusting t h e v o l u m e of a gas before m a k i n g a reading, t h e contact between t h e m e r c u r y a n d upper p l a t i n u m wire is broken b y means of t h e leveling bulb containing mercury, t h e switch is t h e n closed a n d t h e compensator a d j u s t e d till t h e break i n t h e circuit a t t h e m e r c u r y p l a t i n u m c o n t a c t is j u s t closed, whereupon t h e l a m p lights a n d t h e compensation is completed. R o u g h a d j u s t m e n t is m a d e b y sliding t h e m e r c u r y bulb a n d i t s s u p p o r t u p o n t h e iron rod b y h a n d . T h e fine a d j u s t m e n t is m a d e b y t a k i n g u p t h e s a g in t h e a r m supporting t h e b u l b b y means of t h e t h u m b screw. T h e switch is t h e n opened t o p r e v e n t sparking a t t h e m e r c u r y s u r 1 Pettersson, “ 0 . Luftanalyse nach einem neuem Princip,” 2. anal. Chem., 2S (1886), 467; also Hempel’s “Gas Analysis,” translated by I,. M. Dennis from 3rd German Edition, 19011, 59.
I
of t h e m e r c u r y t o a m a r k . It removes t h e difficulty of a d j u s t m e n t due t o poor or changing light a n d d e creases t h e s t r a i n u p o n t h e eyes of t h e operator. Where m a n y analyses are m a d e it removes one of t h e chief sources of fatigue. U. s. BUREAUO F MINES EXPERIMENT STATION. PITTSBURGH
ADDRESSES ONE BILLION GALLONS OF SYNTHETIC GASOLINE IN 19181 By WALTERF . RITTMAN Received April 9 , 1917
The market value of synthetic gasoline produced by cracking in the United States during 1917 will be sufficient to supply the navy with ten superdreadnaughts. In other words, one-fifth of the 3,000,000,000 gallons to be produced will be made by cracking. By July I of the present year there will be in operation in the United States 4,000,000 automobiles. Financial men, in considering the investment value of motor stocks, have for several years been dwelling upon the saturation point, but despite this consideration the demand for machines still keeps well ahead of the 40 per cent average yearly increase of past years. When the saturation point will be reached nobody knows. Responsible and successful automobile men maintain that the present increase in rate of production will keep up for years, and that 1 Paper read at the Spring Meeting of the American Chemical Society, Kansas City, April 10-14. 1917.
I
after the present high prices of materials the price of cars can be so reduced that every family having an income over $1,000 may own a car. On this basis, the United States will have in the neighborhood of IO,OOO,OOO automobiles, two and one-half times the present number. Assuming an annual life of five years per machine, IO,OOO,OOO cars means an annual replacement number equal to z,ooo,ooo;i. e., our present rate of production. When one questions the correctness of the opinion of the automobile man who suggests the above figures, one is answered with the statement that every prediction which the automobile man has heretofore made has been too conservative. An important consideration is the greatly increasing number of motor trucks necessary to replace the shortage in horses. As to the influence on this industry of the United States’ entrance into the European war, time will tell. Only the steel, lumber, and clothing industries exceed the automobile business in importance today. Detroit, the center of this new industry, has risen as a manufacturing center from sixteenth place in 1900 to sixth place in 1914. In the United States over 500 factories are to-day engaged in making different
May. 1917
T H E JOCRArAL O F I - V D C S T R I A L AAVD E Y G I N E E R I Y G C H E M I S T R Y
types of automobiles, and new companies of varying stability are announced each week. As a sidelight, it is interesting to observe the approximate annual upkeep involved in America's automobile bill which is as follows: Gasoline ............................. Tires. ............................... Accessories., ......................... Garage hire.. . . . . . . . . . . . . . . . . . . . . . . . . . Repairs.. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
$500 000 000 $500 ' 0 0 0 ' 0 0 0 $300'000 ' 0 0 0 $1 50 ' 0 0 0 ' 0 0 0 $150~000~000
The number of automobiles in use in this country on January 1st over the period of the past fifteen years is as follows: Number of Cars 85,000 400,000 600,000 677,000 ......... 1913 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1,010,483 1914. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1,253,875 1915 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1,754,570 . . . . . . . . 2,225,000 3,250,000 1917 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4,750,000 1918 (estimated). . . . . . . . . . . . . . . . . . . . . . . . .
Year 1905 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1910 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1911 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In addition, gasoline requirements are not limited to the above automobiles, for tremendous quantities are used in motor boats, motor cycles, farm engines, chemical manufacture, cleaning establishments, etc. The requirements per machine per annum vary with different users, some using on an average of less than a gallon a day, whereas, the public vehicle often uses as high as I O gallons a day. Statistics would indicate that the average consumption per car per annum approaches joo gallons. Of the various problems confronting the automobile industry, the motor fuel problem of the future has loomed UI) as the most important, but it would seem that this problem will temporarily a t least be solved. Much discussion and attention is paid to the use of gasoline substitutes, such as alcohol, benzol, gasoline from natural gas, electricity, etc. All of these materials are very valuable sources of power, and the extent of their use is entirely a question of quantity produced, and price. Alcohol is commercial when gasoline exceeds 35 cents per gallon. This price, however, is based on ante-war prices, as every one realizes that the present price of alcohol makes i t prohibitive. Benzol, when mixed with gasoline, makes a superior type of motor fuel, and here again it is entirely a question of the supply available. The figures of the best informed people in this field indicate a supply gallons, of benzol and light oils available equal to ~oo,ooo,ooo which i t is observed will fulfill less than I O per cent of our motor fuel requirements even though none of the benzol and similar materials were used for explosives and other chemical purposes. Casing-head gasoline (gasoline from natural gas) is an item of considerable importance because it is so volatile and has such wide explosive limits that i t can be blended with naphthas and thereby makes available for motor use materials which were not available. The production of this material has been as follows, but this production, it may be remarked, will hardly supply more than one-tenth of our fuel requirements: Year 1911 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1912 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1913. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1914 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1915,. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1916 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1917 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Gallons 7,425,839 12,081,179 24,060,817 42.652.632 65 ;364: 665 125,000,000 200,000,000
iMuch is heard of the kerosene carbureter, and the patent office holds thousands of carbureter patents. Prof. Lucke of Columbia University rightly believes that in the development of a commercial kerosene carbureter it will not be a new invention, but a matter of a design utilizing parts from various patents or designs already developed that will solve the problem. Practically no consideration has been paid to what is perhaps the most important factor militating against the use of kerosene; i. e., the question of explosive limits. This will be discussed later. The carbureters already invented surely embody all possible principles, so it would seem that from this time forward
529
the problem is one of a design wherein ideas from different carbureters are brought together in a new form. A partial way out of the difficulty may be by reversion to the steamer type of automobile in which heavier oil is used to generate steam. The crude oil production and the gasoline production in the United States, during a period corresponding to the automobile figures previously given, is shown as follows in barrels of 42 gallons : Year 1905... . . . . . . . . . 1910...... . . . . . . 1911 . . . . . . . . . . . . 1912.. 1913. . . . . . . . . . . . 1914..... . . . . . . . 1915.. . . . . . . . . . . 1916.. . . . . . . . . . .
..........
Crude Oil Production 134,717,580 2093557,248 220,449,391 222,935,044 248,446,230 265,762,535 281,104,104 292,300,000
Gasoline Year Production 1904 . . . . . . . . . . . . 6,920,000 1909. . . . . . . . . . . . 12,900,000 l 9 l 4 . . . . . . . . . . . . 34~915,000 1915 . . . . . . . . . . . . 41,600,000 1916' . . . . . . . . . . . 1917 (estimated).
54'7602000 70*000,000
From these figures it will be observed that during the period from 1910 to 1917 when the number of automobiles increased eightfold, crude oil production grew but a little over one-third, and gasoline production increased four times, an order of magnitude comparable with the growth in production of automobiles. This increased production of gasoline from a relatively constant quantity of crude oil is obviously the result ( I ) of taking a larger portion of motor fuel from the crude oil and calling it gasoline and ( 2 ) of producing gasoline from heavier oils by cracking. The question naturally arises as to how much further into crude oil the petroleum man can cut in order to increase the supply of motor fuel. We have all observed the Baume gravity of gasoline decrease from the seventies to the fifties, which means an increase in the specific gravity from 0.700 to 0 . 7 7 8 . But practical motor men to-day believe that, with the present automobile carbureter and engine, gasoline containing heavier portions of the crude oil below 50' Be. does not work efficiently. Scientific explanation of the fact can be found in a consideration of the explosive limits of various hydrocarbons. For every mixture of hydrocarbons and air, as produced in the carbureter, there is a proportion below which the mixture contains too small a percentage of hydrocarbons to explode. There is also an upper limit above which the mixture contains too large a percentage of hydrocarbons to explode. Between these two limits is the desired range in which the proper explosive mixture is formed. For instance, a mixture of natural gas and air containing below j pei cent of gas will not explode: also a mixture containing more than 11.5 per cent of gas will not explode. Hence, the explosive limits for mixtures of natural gas and air are between j and I I .5 per cent of gas. Similarly, the explosive limits foi mixtures of gasoline vapor and air lie approximately between 1.4 and 6 per cent of gasoline vapor. When the size and weight of petroleum molecules increase, the boiling point is raised. In other words, the higher the molecular weight, the heavier and less volatile is the material. Furthermore, as the volatility of these hydrocarbons decreases, the limits for their explosive mixtures with air, below which nothing happens and above which there is a burning rather than an explosion, come closer and closer together. Consequently, as we go from lighter petroleum products, such as gasoline to heavier petroleum products, such as kerosene and up to materials boiling above 400' F., the range for explosive mixtures of air and heavy hydrocarbon vapors becomes more and more narrow, until a point is reached where there is great difficulty in adjusting the mechanical parts of the carbureter, so that they deliver the proper explosive mixture. For example, suppose a mixture of 5 per cent hydrocarbon vapor and 95 per cent of air is the only possible explosive mixture for the vapors of a certain substance, how difficult, if not impossible, it would be to adjust a carbureter to deliver accurately and continuously that exact mixture. The result then is that when this heavy material, with narrow
5 30
T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
explosive limits, is used for fuel, there is slow burning rather than explosion, and only a part of the combustion occurs in the cylinder where it can be utilized. Therefore, i t is questionable whether an efficient carbureter for heavy kerosene can be devised. Other suggested solutions of the motor fuel problem involve the use of oil derived from coal, shale, peat, and lignite. These will be immensely important sources of liquid fuel in the more remote future. Passing over the large supply of light oil possible from coal now burned without coking, which may amount to as much as a billion gallons of fuel per annum, there are immense shale deposits in America, containing a volume of oil many times greater than that now known. Here the problem of obtaining motor spirits from the oil will arise again and the solution of it, as of our present problem, will necessitate cracking processes. Then, as now, the demand for motor spirits will run ahead of the supply obtainable by straight distillation; and the logical solution of our present motor fuel problem will be the logical solution in future problems. The fundamental proposition is that when the demand for gasoline doubles or trebles, while the amount of petroleum remains nearly constant, we must make more gasoline from a given volume of crude oil. The best evidence that this proposition furnishes the answer t o our problem, is the fact that cracking processes are now solving the problem. I n other words, since 20 per cent of our gasoline is now being made by cracking, the price of gasoline would of necessity be much higher without this increased supply. The chemical phenomena involved in the cracking of heavy oils into lower boiling oils have been discussed in considerable detail in Bulletin 114, United States Bureau of Mines. Broadly
CURRENT
Vol. 9, No. 5
speaking, and without consideration of relative merits, cracking processes may be classified under the five heads : I-Liquid condition processes wherein oil is cracked as a liquid; z-Gaseous condition processes wherein oil is cracked as a gas; 3-Processes wherein cracking is aided through the use of catalyzers; 4-Processes wherein the oil is mixed with steam, hydrogen, or other materials; combinations of the above four methods. The object of the present paper is not t o discuss the technical nor the research side of cracking, but t o indicate how real is this industrial operation to-day. During the present year, 1917, approximately 600,000,000 gallons of cracked gasoline are being produced in the United States. It is estimated by competent authorities that the production of cracked gasoline in 1918 will be 1,00o,ooo,~ogallons, and that by 1920 more gasoline will be produced by cracking than by all other methods. Many people have been disappointed because cracking processes have not reduced the price of gasoline materially, but fail t o consider their tremendous benefit in keeping the price of gasoline from going IO cents a gallon higher: 7 , 0 0 0 automobiles a day require a cumulative supply of motor fuels. Our crude oil production is not increasing. Kerosene carbureters as yet are not a factor. The entire load is falling on the shoulders of cracked gasoline, and cracked gasoline promises t o make light of its load. PITTSBURGH, PA.
INDUSTRIAL NEWS 1 -
BEET SUGAR INDUSTRY The report of the Incorporated English Beet Sugar Pioneer Association on its second year's experimental culture in Montgomeryshire, England, states that, taking into account the shortage of labor owing t o the war and the consequent inability of growers t o give proper attention, the crops generally as regards shape, size of roots, heads and estimated weight per acre were entirely satisfactory and, in the opinion of experts, in many ' cases equal t o the growing crops in Holland and Germany in 1910. From the one-acre plots, the estimated yield was from 17 t o 18 tons. On analysis, the following results were obtained: 17.75per cent sugar in root, 18.68per cent sugar in juice and 89.70 per cent coefficient of purity. German roots, which are considered a good type, contain 16t o 16.5per cent sugar, while the average of the English roots was 16.48per cent.-A. MACMILLAN.
NEW METHOD OF EXTRACTING VAPOROUS CONSTITUENTS FROM COAL GAS At a recent meeting of the Society of Chemical Industry, London, a paper was read by Dr. R. Lessing on the above subject. The author said that, so far, the method had been used only for research purposes but it was hoped that, before long, it would be available on a commercial scale. The principle of the process is that of a dry scrubber filled with solid absorbent material which will strip the benzole from the gas without the employment of running wash oil and from which the volatile products can be recovered by steam distillation in situ. At first, i t seemed that crushed pitch would serve the purpose of the absorbent matter, but i t was found that its viscosity decreased to such an extent by the absorption of the solvents from the gas, that it began t o run after a while and was liable to consolidate and block the passages of the apparatus. Finally, i t was decided to use a rigid material and broken fire-brick was found t o answer the purpose very well.-M.
ITALIAN CHEMICAL INDUSTRY According t o a report in a contemporary, great activity characterizes the chemical industry in Italy at the present time. The war has caused great changes both in the materials used and in the methods of production. During last year one of the leading companies produced 35,000 tons of sulfate of copper, ~ ~ , o tons o o of superphosphates, 270,000 tons of sulfuric acid and IZ,OOO tons of fine sulfur, and was able to furnish 80,000 tons of sulfuric acid t o France.-M.
MOLYBDENUM Some years ago, says Engineer, 123 (1917),109, molybdenum looked very promising as an alloy in tool steel but, unfortunately, it was found that, while the steel had very often remarkably efficient cutting qualities, it frequently ran with fine hairline seams, and, very peculiarly, the molybdenum seemed t o volatilize out of the surface of the steel on heat treatment. I n the case of magnet-steel, also, it has not proved as satisfactory as tungsten. Metallurgically considered, molybdenum should have about twice the efficiency of tungsten.-M.
BARIUM-RADIUM CARBONATES The Golden, Colorado, Experiment Station of the Bureau of Mines, Department of the Interior, reports that it has been found that, by fusing-radium barium sulfates carrying a considerable proportion of silica with a mixture of caustic soda and sodium carbonate, the whole of the barium and radium are converted into carbonates. The amount of sodium carbonate required is comparatively small, IO to 15 per cent only being required. The reaction goes a t a low temperature, and the difficulties of fusing with carbonate alone are entirely eliminated. The product is also much more easily washed free from sodium silicate.
