888
INDUSTRIAL A N D ENGINEERING CHEMISTRY
Vol. 15, s o . 9
Research for the Petroleum Industry By Raymond F. Bacon 50 EAST41sT ST., NEWYORK,N. Y
HERE is no industry of anything like the magnitude formed are probably ring compounds. Still, so far as the of the petroleum industry which has such a dearth writer’s observation goes, these ring compounds formed in of fundamental chemical knowledge on which to base this way are not of the same character as the naphthenes, as its operations. The reasons for this fact are twofold: One they do not show the same resistance toward chemical agents is that petroleum refining as conducted in the past has been as the true naphthenes. largely -by physical seiarations rather ELECTRICAL WAVESI N CRACKING than by chemical processes. The other PROCESSES is that a study of the structure and reactions of petroleum hydrocarbons inIn the patent literature on cracking volves very great difficulties. The inprocesses claims are made by various industry in the past has separated the ventors of the efficacy of electrical waves, petroleum into certain of its original of the impact of ions, and even of meparts and has marketed these parts as chanical impact itself in causing the gasoline, kerosene, lubricating oil, fuel breaking down of hydrocarbons containoil, paraffin, etc. The time has now ing many carbon atoms into those concome when commercially successful petaining a lesser number. Scientific worktroleum refining means the manufacture ers would find here an interesting and from the oil of substances which do perhaps profitable field of investigation, not exist in the crude petroleum as such, for it is, of course, known that under but are formed by chemical transmutaproper conditions electrical waves of tions from other compounds present as suitable character can cause profound constituents of the petroleum. For examchanges in chemical compounds. It is also ple, the time has come when not all the known that electrons meeting molecules at kerosene hydrocarbons which exist natusufficient velocity can cause the disinterally in crude petroleum can be advangration of those molecules, thus forming Bachraich tageouslv sold as kerosene. Ideal refinRAYMOND F. BACON new compounds. Furthermore, impact ing means production from the crude of sufficiently violent character does cause oil of only those products which can be most profitably the breaking down of many types of compounds-as, for marketed a t a particular time. This means chemical change instance, explosives. The scientific study of reactions of this of many of the compounds contained in petroleum into other type should yield most valuable results which might also chemical individuals. possibly prove to be’ of great practical value. The industry is meeting this situation, as the thousand and LUBRICATION more patents relating to cracking processes for making gasoWhen one considers the subject in all its ramifications, line would indicate. The industry, however, could work out its salvation much faster and on sounder lines if more were there is hardly anything in the world quite so important as known regarding the nature and properties of the individual lubrication. The world’s consumption of lubricants does hydrocarbons constituting petroleum. One can read in not rank with its consumption of many other products, but scientific literature pages and pages describing the properties without the lubricants all machinery stops. There is no and chemical reactions of hydrocarbons of which a t most a doubt that one of the greatest sources of worry of the German few hundred grams may have existed in the whole world, General Staff in the war was as to whether they could mainwhile tons and thousands of tons of hydrocarbons are being tain a sufficient supply of lubricants in a shut-in Germany. produced daily of which we know absolutely nothing regard- Yet, with the subject so important, what do we know about ing their chemical properties, their reactions, and their the scientific nature of lubrication or the chemical or physical structure. There is almost no field of research open to the structure of a substance which makes it a good lubricant? pure scientist which offers such fascination in its difficulty, Our ignorance is really appalling. The writer well remembers nor such promise, if its difficulties are overcome, of opening the fascination with which he heard Dr. Mabery tell about up a whole new field of chemistry, as the study of these how he had fractioned a certain petroleum into various narrow unknown petroleum hydrocarbons. The action of heat alone fractions and had found that one of these fractions made a on these hydrocarbons, under all possible conditions, is an most excellent oil for lubricating watches, while a nearby alluring field of study, and on this heat action (pyrolysis) fraction was of such a character that it stopped the watch. most of the processes of gasoline manufacture are founded, It is well known to all who are conversant with the subject but largely on an empirical basis. As an example of interest- that there are no chemical or physical tests which can be made ing relations of this character, the Burton and other similar on a new product which will prove definitely whether or not pressure distillation processes of cracking give gasoline which, it will serve as a good lubricant for a particular piece of maconsidering its saturated constituents,’ is apparently of much chinery. The only test that is of real value is to try it on the same character as the gasoline hydrocarbons found natu- the machine to be lubricated. I n this connection, there is another subject which offers rally occurring in petroleums. On the other hand, when heavy petroleum oils are cracked under the conditions of the Ramage great promise for investigation, and that is the relation of process, the gasoline hydrocarbons obtained have for similar those hydrocarbons which go to make up what we call “petboiling points a much higher specific gravity and a much rolatum” to other hydrocarbons, possibly with the same higher refractive index, indicating that the hydrocarbons number of carbon atoms, which are either liquid oils or are
T
September, 1923
INDUSTRIAL A,VD ElVGINEERING CHEMISTRY
solid, crystalline compounds of the type which make up paraffin wax. There are indications that in petroleum there may be a t least three classes of hydrocarbons all with the same number of carbon atoms, one class being liquid a t ordinary temperatures, another of the consistency of petroleum jelly, and still another solid and of crystalline structure at ordinary temperatures. A joint attack on a problem of this kind by men with the viewpoint of the colloidal chemist and of the structural organic chemist would seem to promise greatest results. Before leaving the subject of lubricants it should be pointed out that there are many indications that small quantities of other substances mixed with the base lubricant may greatly improve the qualities of that lubricant. In fact, from the viewpoint of those who think in matters colloidal, it may be that a good lubricant is a colloidal dispersion of a substance in a liquid which itself may have only indifferent lubricating qualities. I n this connection, it might be mentioned that it has been well proved that one requisite of a good lubricant is that the lubricant should stick tightly to the metal surface lubricated; it should, in other words, so tightly adhere to the lubrivated surface that it is almost impossible to remove every trace of it. The process of the flotation of ores is based on the fact that certain kinds of substances preferentially wet metallic or metal-like mineral surfaces as compared to gangue surfaces. The quantity of substance required to change the surface sufficiently to permit the flotation of ores is extremely minute, and there is every reason to believe that there is an actual ad5,orption of the flotation agent on the metallic surface. Substances of very diverse chemical and physical properties exhibit this phenomena, such as fatty oils, petroleum oils, phenol arid cresol, and even soluble solids like a-naphthylamine and thiocarbanalide. May it not be that small quantities of properly chosen materials colloidally disbursed in the usual lubricating oils might increase this wetting or adhering power of the lubricating surface and thus make better lubricants? This subject has its fascination not only from the industrial possibilities, but also from the pure science standpoint. The reason why one liquid will wet a certain surface and another will not is one of the very obscure phenomena of physical science, and it is only recently, since Langmuir and others have visualized the actual physical structure of the molecules, that any picture at all has come to us as to why or how these things can be. UTILIZATION OF XATURAL GAS One of the great problems of the petroleum industry is the utilization of natural gas. In almost all new petroleum fields large quantities of natural gas are found in the wells. Wells flowing 10,000,000 feet of natural gas per day are not unusual and those with 60,000,000 feet have been recorded. The petroleum field is usually located so far from industrial centers that this gas cannot be profitably piped for fuel purpose,$. Moreover many structures drilled for oil yield little or no oil, but large quantities of natural gas. If this natural gas contains small quantities of the higher hydrocarbons, it is usually stripped of these hydrocarbons, which form the so-called casinghead gasoline of commerce. The methods in use for obtaining casinghead gasoline from natural gas are fairly satisfactory, but one great need is to so simplify the apparatus that it can be cheaply moved when the gas supply diminishes. The stripped gas is used to a minor extent in drilling operations and in local industries, but the history of most fields is that a great percentage of it escapes and is wasted. Natural gas is utilized in some fields for the making of carbon black, and this is quite justifiable at points where no better use can be made of the gas. Carbon black is an important and necessary commodity, the use of which is rapidly increasing. The attack on the use of natural gas
889
for carbon black manufacture is based on the fact that the gas by present methods only yields 1 or 2 pounds of carbon black per 1000 cubic feet of gas consumed, whereas the gas actually contains upward of 40 pounds of carbon black for each 1000 cubic feet. Researches directed toward increasing the percentage of good carbon black obtainable from natural gas offer a field alluring both from the industrial and from the pure science standpoint. If natural gas is subjected to sufficiently high temperature, it is completely broken down into carbon and hydrogen, and in that case the yield of carbon obtained is about 40 pounds per 1000 cubic feet of gas. The carbon obtained in this way has a relatively high specific gravity, is grayish in color, and is somewhat gritty, instead of having the low specific gravity, the desirable velvety black color, and freedom from grit demanded of commercial carbon black. I n the operations for the manufacture of casinghead gasoline from natural gas, the casinghead gasoline obtained usually contains very considerable percentages of the lower members of the paraffin series of hydrocarbons, particularly the propanes, butanen, and pentanes. These very low boiling hydrocarbons are allowed to distil from the casinghead gasoline either in special apparatus designed for the purpose, or very often by a simple process of weathering. They offer a cheap raw material for the synthesis of many classes of compounds containing three, four, or fire carbon atoms, and the amount of such material available is sufficient to supply a very largo industry.
TREATMEXT OF DISTILLATES It is the practice of the petroleum industry to treat various distillates with acid and alkali for the purpose of removing the color and certain undesirable constituents and improving the odor. In this treatment the acid that is virtually always employed is a strong sulfuric acid, and in the case of most gasoline and burning oil distillates the refining loss from such treatment is rather small. In the case of the higher boiling oils, such as lubricating oils, the treatment loss is often very considerable, so that the study of methods of “treating” higher boiling petroleum distillates is a subject very worthy of investigation. Sulfuric acid probably acts in two mays in the treatment of petroleum distillate. I t acts chemically on certain unsaturated hydrocarbons, polymerizing them, and it also acts physically as a solvent for some of these polymerized tars and for certain other tarry or nitrogenous materials which are in the oil. Very often its action may go too far and compounds are formed which are of an emulsifying nature and which render separation of the oil from the alkali or from mater, a subsequent operation, very difficult. Similarly, treatment for the refining of cracked gasoline also is apt to cause heavy refining loss. It used to be thought that the treatment with acid in any case was for the purpose of removing unsaturated hydrocarbons, and that unless these unsaturated hydrocarbons were removed the distillate would after a certain length of time lose its color, take on offensive odors, and in many cases separate gummy matter. It has been shown that it is not the unsaturated hydrocarbons per se which cause these phenomena, although when certain other objectionable substances are present reactions are started in which the unsaturated hydrocarbons probably take part and probably do cause part of the phenomena mentioned. There is, however, good reason to believe that the removal of only exceedingly small amounts of the offending materials from any petroleum distillate will give a product of proper color and of sufficiently good keeping qualities for commercial purposes, and that the present large refining losses on certain petroleum distillates are unnecessary. The problem is to find cheap commercial methods of reaching this ideal.
890
INDUSTRIAL A N D ENGINEERING CHEMISTRY POSSXBILITIES OF IXDUSTRY
The problen~swhich have been mentioned are those which are intimately connected with the present practical operation of the industry and are, in the writer’s opinion, problems of a character for which a satisfactory solution can be found, In addition, there is an immense field of problems whose solution is more chimerical. We have all heard the petroleum industry compared with the coal-tar industry and the belief that some day there will be a great organic chemistry of the petroleum products, the same as there is a great organic chemistry of the coal-tar products. The budding young organic chemist should be reminded that the reputations of most of the great organic chemists of the last century were based on the solution of problems connected with products from coal tar and that the time will come when some new Baeyer will open up the chemistry of petroleum products. It will probably be many, many years, however, before real progress has been made in systematically ordering and arranging the rea$ions of chemical compounds derived from petroleum. Nevertheless there are certain fields along these lines which appear somewhat less difficult than some of the others and which have great industrial importance. One is the manufacture of resins from petroleum. Fossil resins are rapidly being exhausted. Certain synthetic resins of the type of Bakelite are almost ideally adapted for various industrial uses, but resins of this type are necessarily somewhat high in price and cannot be used for all purposes. The coumarone resins, prepared by polymerization of certain liquid fractions from coal tar, are supplying a certain need for lower priced material, but there is still a big field, es-
Vol. 15, No. 9
pecially in light-colored, durable resins to be prepared from fractions of petroleum. The writer believes that this will be done within the next few years. Another similar field which offers promise is the preparation of true drying oils from petroleum. The drying oils are characterized by containing certain double bonds which in drying absorb oxygen, making the hard elastic film demanded by the paint industry. In other fields of chemistry it is possible to put double bonds into compounds a t will, and there is little doubt that properly directed work could ascertain how to do this in the field of petroleum hydrocarbons. Another field is the manufacture of acids from the higher petroleum hydrocarbons, it being assumed that such acids would be suitable for the manufacture of soaps. Much work has been done on this subject, so far without any commercial success. It is probable that this problem is a much more difficult one than those mentioned previously. The solution of chemical problems of this character will be a benefit, not only to the industry itself, but to the great general public along the lines of conservation. Our descendants will, no doubt, be shocked that the people of this generation burned as fuel oil useful hydrocarbons from which they will know how to manufacture many very valuable and necessary materials; but the use of certain fractions of petroleum for fuel is justifiable a t the present time because u-e know of no better utilization of this material. Workers in pure science can find no field of investigation offering more promise from the purely scientific standpoint, nor from the standpoint of benefiting industry and their fellow men, than in taking up some of these problems of the great petroleum industry.
Radiator for Platinum Crucibles’ By Manuel M. Green IVIASSACHUSETTS INSTITUTE OF TECHNOLOGY, C A M B R I D G E ,
MASS.
SHORT time ago while carrying out an investigation for a radiator, claiming that only a small flame is needed to on the determination of potash in acid-insoluble heat the platinum crucible uniformly. While Thornton’s silicates,2 the writer decomposed the samples with apparatus is more desirable than the other, it was deemed hgdrofluoric and perchloric acids, a t first evaporating the advisable to improve on it if possible, and the following solutions of perchloric acid fumes by hand. Owing to the piece of apparatus was constructed to replace the older type. fact that there was h piece of wire gauze, 12.5 cm. square, is bent into the some loss by spatter- capsule shape indicated in the diagram, by simply hammering ing, the type of radi- the center, A , of the gauze, supported on a metal knob, as ator made of sheet iron far in as it will go, then bending back the corners, B, so as to recommended by the provide a means of suspending the apparatus on a ring stand. Geological Survey3 From a second piece of gauze a round piece, C, is cut of such was used. For such a size that when fitted into the first part it is held about a radiator, when a 2 cm. above the center, A . A triangle, D, is next fitted in platinum bottom is not 1.5 cm. above C. The triangle D may be macle froin an used, it is necessary to ordinary chrome1 triangle used in ignitions by cutting off all use the full heat of a the curled part at the corners with the exception of just enough Tirrill burner, or else to keep the triangle together. a MBker burner. As If, now, the crucible containing the solution to be evapthe investigation was orated is placed in the triangle, the bottom of the crucible carried out during the comes about 0.5 em. from the bottom C. A very small A summer months, the flame, the smallest obtainable from a Tirrill burner without discomfort accompanying the continuous use of so large a having it go out, if directed a t point A (the apparatus being flame led to a search for a more comfortable means of get- supported so that the tip of A comes about 3 cm. above the ting the desired result. tip of the flame), causes the solution to evaporate rapidly Thornton4recommends the use of a 100-cc. nickel crucible and smoothly, without spattering, to fumes or drynese as desired. 1 Received August 3, 1923. a THISJOURNAL, 15, 163 (1923). This new type of radiator has the advantage over the older 8 Hillebrand, “Analysis of Silicate and Carbonate Rocks,” U. S. Geol. types in economy of heat, economy and ease of construction, Survey, Bull. 700, p. 33. and elimination of discomfort. 4 THIS JOURNAL, 3, 419 (1911).
A
