EXTRACTION PROCESSES FOR THE REFINING OF OIL Chairman: DR.-ING.J.ROSENBERG.General DR.-ING. J. ROSENBERG. General Reporters: F. H. GARNER, Pa.D., M.SC., F.I.C., M.INST.P.T., and DR. W. J. D. VAN DYCK. GENERAL REPORTERS'
. THE most outstanding development in recent years in connection with the refining of petroleum products, apart from hydrogenation, has been that of solvent extraction processes. The Edeleanu process, utilising liquid sulphur dioxide, has been widely and successfully used in the refining of kerosines to give good quality burning oils for a number of years past. The history of the development of. this process, which began with the pioneer plant at Rouen in 1911, is described in the paper by Rosenberg. Dr. Edeleanu first confined his experiments to kerosine distillates, and very soon after, thisprocess, with his co-operation, was extended to lubricating oil distillates and to other constituents of the mineral oil. The use of liquid sulphur dioxide in 'conjunction with other solvents such as benzene or chloroform has also been thoroughly worked out by the Edeleanu company as regards its industrial suitability, and tested in an experimental plant. In the last few years a number of processes using selective solvents have been developed, notably those employing phenol and nitrobenzene., primarily for the production of high-grade lubricating oils suitable for all the most exacting requirements of modern lubrication, such as aero-engine lubricating oils or turbine oils. The paper on the Phenol Process, by Stratford, Moor and Pokorny, describes the results obtained on a commercial scale during the last three years on the application of this reagent in the refining of lubricating oils. It is pointed out that the plant consists of equipment with which the ordinary refinery operator is familiar, and no refrigeration is employed; details of the cost of operation are also given. The plant used in connection with the Nitrobenzene Process for lubricating oils is described in the paper by Ferris and Houghton and it is stated by the authors that of the known solvents, nitrobenzene is unique in its versatility, in its ability to produce from any lubricating stock from residuals to light distillates, and from extreme naphthenic to Pennsylvanian crudes, oils of superparaffinicity having a. high resistance to oxidation and low carbon-forming characteristics. Two papers deal with the general principles underlying solvent extraction processes for the refining of oil, and Hunter and Nash point out that it is possible by means of mathematical -calculation based on established facts, to reach reasonably correct calculations as to the size and nature of the equipment required, results of the process, and capital and running costs, well in advance of actual installation. An attempt is made to classify and compare extraction methods and to show how the results obtainable by such methods can be forecasted, and in the second part of the paper,
CONTRIBUTION A L'éTUDE DES PHéNOMèNES QUI ACCOMPAGNENT LES ACCUMULATIONS DE GAZ DANS LE RECOUVREMENT D'UN GISEMENT PéTROLIFèRE Par Dr. D. CHAHNAZAROFF
. THE author first states the general conditions under which gas may occur in oilfields and then proceeds to give the results of his studies of the occurrence of gas in the Comodora Rivadavia oilfield in the Southern Argentine. The geology of the Comodora Rivadavia field is briefly sketched and the oil-bearing horizons noted and described. Certain anomalies noted with regard to the distribution of gas in the cover rocks of the field, the Pehuenche formation, are referred to. Accumulations of gas, worthy of note, occur irregularly in these beds at few places. The author does not accept the view that this is due to lithological conditions being favourable in such places while being unfavourable over the-greater part of the area covered by these deposits.He states that the Pehuenche beds are such that the gas cannot have originated in them and that it must have reached that formation from lower horizons. Gas may be freed from oil-impregnated strata by changes in thermodynamic conditions, temperature and pressure. The effects of rise of temperature as a function of depth, the neighbourhood of magmatic masses and the presence of faults are discussed: first, with especial reference to the Comodora Rivadavia field, where he notes that in neighbouring wells one may be extremely rich in gas while in the next gas may be present in negligible quantity; secondly, in more general terms. Finally, he stresses the importance of studying the dislocations present in the cover beds of an oilfield area and connects the presence of these anomalous accumulations of gas with such dislocations. Dans le cas général une Coupe complète d'un complèxe pétrolifère peut renfermer les séries suivantes des sédiments: - 1. Le recouvrement improductif. 2. Les dépôts renfermant, de préférante dans sa partie supérieure, les accumulations du gaz, dérivé des pétroles liquides sous-jacents. Ce gaz est secondaire, car il se trouve dans les roches-magasins qui n'appartiennent pas à la même période de sédimentation, qui a donnée lieu à des roches-mères. C'est à l'état d'occlusion dans les espaces interstitiels de la roche que se trouve ce gaz. 3. Les sédiments naphtogéniques proprements dits, qui peuvent bien entendu, renfermer non seulement les accumulations du pétrole, mais aussi celles de gaz, qui est dans ce cas le gaz primaire, car il se trouve dans le lieu d'entassement originel des débris organiques. L'état dé gisement de gaz dans ces dépôts de sédimentation primaire, est beaucoup plus compliqué. Ce gaz peu se
DISCUSSION. Dr. Frederick G. Clapp expressed his regret that some of his fellow-countrymen who had made extensive aerial surveys had not had the opportunity to be present or to send papers.He felt sure that their work would have been helpful in this connection.His own experience with this branch of geological activity had been entirely with limited reconnaissance and with the interpretation of aerial photographs rather than the making of actual aerial surveys personally. He thought that the best detailed geologic results had generally been obtained from vertical photographs rather than from those made at an angle, especially when the pictures were taken in the form of a grid with each one overlapping the adjoining ones by about 50%. A very simple laboratory device enabled the absolute adjustment to verticality of those that depart somewhat from this position owing to the exigencies of air work. From vertical photographs and the aid of the stereoscope we had, in several countries, been able to map contacts, fault lines and structural trends with great exactness. The outlines of salt domes and of structures bounded by numerous beds of varying character and having steep dips had been found especially susceptible to exact platting by observation of the photographic prints. He also happened to be familiar with some of the results accomplished by Dr. Woolnough in his great Australian flight that may be considered an epochmaking geologic reconnaissance. He was fortunately able to confirm some of the structural discoveries made, for they furnished final proof to conclusions which he had drawn in 1924 on the basis of ground'reconnaissances. He complimented Dr. Woolnough on some particulars in which his researches appear to have reversed the surficial findings of earlier work. This all indicated the vastness of the unexplored areas and the great amount of additional geologic work that was necessary, both by air and on land, in northern and western Australia. In fairness to cartographers in some parts. of the world he made reference to the paper by Lieut. Salt, and especially to the index map; for some countries are not so devoid of detailed maps as might appear at first glance. The United States and Canada, in particular, had been mapped by three-colour contour sheets over very great areas (those in the first-named country covering something like half its total area). For their purposes on that side of the Atlantic they preferred such maps with a scale of 1 : 62,500 or of 1 : 125,000 rather than the type of many of the European maps on larger scales, but having often no contours and printed only in a single colour, by reason of which the topographic features were often quite illegible in the more hilly sections. If Lieut. Salt's index map were modified so as to include the American maps having a scale of 1:125,000 he thought it would give a more correct perspective of the detailed mapped area in the United States and Canada at least. He assumed
ARTIFICIAL AGEING OF LUBRICATING OILS By FACHINI and SPORER
. TaE authors have studied the formation of petrol-insoluble oxidation products when the oil under examination is heated in a crucible to 150 C. They find that oils can be graded into four classes . 1. Those which.are unstable and sludge rapidly. 2. Those which sludge slowly at first but afterwards sludge more rapidly. 3. Those which sludge rapidly at first but subsequently oxidise slowly. 4. Those which are very stable overlong periods. In order to distinguish between oils, especially between classes 2 and 3, it is necessary to determine sludge formation at intervals of time up to 130 hours and to plot a curve connecting time and sludge formation. The curves for classes 2 and 3 will in many cases intersect, and oils of class 3 are frequently better than those of class 2, a fact which would not be apparent if a sludging test of short duration were employed. The great importance which the oxidation test has now acquired in the field of insulating oils, because, besides allowing a judgment to be given as to the quality of a new product, it also provides a picture of its working behaviour, has led us to follow a similar path in the wider and perhaps more important field of lubricating oils, where even more valuable information as to the merits of an oil may be anticipated. While special working conditions in a transformer require particular care in establishing the conditions of the artificial ageing test, as, for instance, the temperature, which should not be more than 120 C., and the choice of a metal catalyst, it would perhaps be risky to fix too closely defined limits of comparison in one way or another for oils in general. As a matter of fact the classes of oil vary very greatly, and consequently the " life " of an oil depends on the nature of the apparatus and the period of use. This is the reason why we were anxious in the beginning to create a resistance test as mild as possible, which first of all will not distort judgment on the real quality of the lubricant by too violent â treatment and which, secondly, will not create too abnormal test conditions in comparison with actual conditions, and which at the same time will have sufficient flexibility to meet with all special requirements. Care was taken to establish testing conditions suitable for all the oils, both because absolute tests . giving a constant comparison do not yet exist, and because development of the technique for refining oils on one hand, and that of modern machinery for the oils on the other, often lead to modifications of the conventional check tests as a consequence. There are three phenomena (the third is implicit in the first) which usually have the same influence on the chemical and physical structure of the oil, to wit, the oxygen (or the surrounding air) the temperature and the time. We will call the different metallic materials secondary phenomena, together with the fibres and animal substances
THE MEASUREMENT OF INJECTION-ENGINE FUEL IGNITION PROPERTIES By A. W. POPE, Waukesha Motor Co., Waukesha SVMMARY. THE paper read by Ricardo before the Institution of Automobile Engineers in March, 1930, fell on ground that had been developed and kept fertile by the patience and faith of Swedish and German engineers who have worked persistently through the years for the success of the Diesel cycle. Ricardo's paper outlined the three combustion. phases of the high-speed Diesel cycle and probably did more than any other one piece of work to lift the subject of high-speed Diesel engine design from the status of a dark, misunderstood art to the level of an engineering science. This paper, among other things, focused attention on the importance of the ignition property of the fuel. It indicated the fact that the ignition delay period of the combustion cycle was largely a fuel characteristic and showed the influence this delay period had on engine knock and roughness.During the following year, the work of Le Mesurier and Stansfield corroborated Ricardo, and the very comprehensive work of Boerlage and Breeze in the Royal Dutch-Shell laboratories at Delft culminated in a practical method of measuring the delay period in an engine. American oil companies and engine manufacturers have been quick to apply the principles of these researches to their products and, thereby, have greatly shortened the time when successful, high-speed injection engines will be available for applications to which they are suited. During this same year the laboratory of the Waukesha Motor Company developed a method for the measurement of the critical compression ratio of injection engine fuels. This method has the time factor and other engine operating conditions under rigid control.The apparatus used is a standard C.F.R. knock test engine equipped with fuel injection pump, injector, and a cupped piston to provide suitable injection space.The engine is motored over at constant speed without injection. The air inlet temperature, jacket temperature, injection angle, pressure, and quantity are all standardized. The engine being motored under these conditions can be considered as a dynamic bomb ready for the introduction of fuel.In making an observation, fuel is injected for a three-second interval and the critical compression ratio is selected at which audible combustion is just detected in the exhaust. This ratio is critical to within 0-08 of a unit of ratio at 8 : 1. Critical compression ratio determinations made at different engine operating conditions on a series of eight fuels from various parts of the world emphasize the fact that all fuels do not react the same to altered engine conditions. There also appears to be evidence to the effect that different hydrocarbons react differently to the temperature and the time factor of the ignition process, some fuels being relatively more sensitive to the time factor and other fuels more sensitive to the temperature factor. Carburet
THE USE, OF GUM-INHIBITORS IN THE REFINING OF MOTOR FUELS By W. H. HOFFERT, M.A., B.Sc. F.I.C., and G. CLAXTON, M.Sc. Research Chemists to the National Benzole Company, Ltd. ,
. TaE principles governing the application of inhibitors to the refining of motor fuels are discussed and the following, conclusions drawn 1. Accelerated gumming tests involving the use of oxygen are suitable for studying the action of inhibitors, but the test should be such that a sufficient factor of safety is provided to outweigh any possible variations in the conditions of actual storage. The behaviour of the fuel during the test, however, should be determined with respect to gum formation and not merely with respect to oxygen pressure. 2. The suitability or otherwise of an inhibitor is governed both by the length of the induction period and by the quantity of gum or non-volatile material formed in the fuel during the induction period. 3. By selecting an inhibitor that is effective for a predetermined period in an accelerated gumming test, at a temperature appreciably higher than the maximum temperature to which the fuel is likely to be subjected during storage, the effectiveness of the inhibitor under any normal storage conditions can be guaranteed. 4. In order to determine whether a given substance has a satisfactory inhibiting effect, it is necessary to carry out tests over a fairly wide range of concentrations. 5. The choice of an inhibitor is governed by the character of the fuel, its effect on colour stability during storage, solubility in the fuel and in water, volatility, corrosiveness, combustion characteristics, quantity necessary and cost. The best inhibitor for any particular fuel is dependent on the relative importance of these factors, according to the conditions under which the fuel is to be used. 6. In order to obtain the best results, any compounds present in the crude fuel that are capable of acting as inhibitors,, as well as those accelerating gum formation, should be removed as far as possible from the fuel before the addition of an inhibitor. When appreciable amounts of such compounds are present, the addition of an inhibitor may produce little effect or may even increase gum formation. 7. Any additional refining. treatment for removal of sulphur compounds, or of coloured or malodorous compounds, should be applied in such a way as to cause the minimum destruction of unsaturated constituents. 8. By a combination of the use of gum-inhibitors and suitable refining treatment, it is possible to obtain a satisfactory motor fuel that is stable on storage for periods far longer than is usual in practice. 9. The use of inhibitors enables both unstable and stable unsaturated hydrocarbons to be conserved for use as motor fuel, and hence the yields obtained are greater than those obtained by any other processes that aim at conserving these hydrocarbons, as such. An account is given of the application of grim-inhibitors to various motor fuels, with parti
ANWENDUNG .VON ULTRAVIOLETTEM LICHT IN DER ERDöLGEOLOGIE Dr. A. BENTZ * und Dr. E. STROBEL t Von
. THE application of ultra-violet light in oil geology has as its basis the fact that natural crude oils show under ultra-violet light a typical yellow to brown fluorescence, so that by this means distilled and refined oils are easily distinguished from crude oils. For the tests made an " Original-Hanauer Analysen-Quarzlampe " was used, adapted either for direct or alternating current. The simplest method of testing crude oil by this method is to put a drop of the oil on filter paper and expose it to ultra-violet light. Alternately a few millilitres can be put in a watch glass or in a container of the thinnest possible glass and the ultra-violet light allowed to act directly on the sample. The results of investigations with German crude oils show a continuous scale of colour from light yellow fluorescence with the light crudes to dark brown with the heavy crudes.Few tests have been made with foreign oils, but the Rumanian crudes show the same effects. Furthermore, the method serves to identify real crude oil-shows as against accidental contamination with kerosine or similar refined products, even if these have been altered to a certain extent by storage in the subsoil or contact with surface water, thus departing from standard specification.This method may often save expensive geological or geophysical investigation. A useful application of the method serves to determine the quality and distribution of oils in core-samples. From this, in turn, useful conclusions may sometimes be drawn as to the origin of the oil in the samples.Where the oil-shows are connected with faults and fissures and the oil has only impregnated parts of the adjoining strata, we may assume that the deposit is of secondary origin.On the other hand, there may be, as in the " Hauptdolomit " of Thuringia, small lens-shaped interbedded accumulations of bitumen indicating a primary deposit. In investigating core-samples the method described is of major importance owing to the marked difference between crude and refined oil when observed under ultra-violet light. Thus contamination of core-samples or mud flush by lubricating oil is easily distinguished from genuine crude oil-shows. The cause of the fluorescence of crude oil is as yet unknown, but it may either be due to impurities always present in the crude or to the effect of complex hydrocarbons of high molecular weight. In Germany the method is now successfully employed by nearly all the major companies. ZUSAMMENFASSUNG. Die Anwendung des ultravioletten Lichts in der Erdölgeologie beruht darauf, dass natürliche Rohöle eine hellgelbe bis braune Lumineszenz aufweisen.Destillierte und raffinierte Oele lassen sich sehr leicht davon unterscheiden.Zur Untersuchung wurde eine Original-Hanauer Quarz-Analysen lampe verwendet, die für Gleichstrom oder Wechselstrom eingerichtet ist. Die Untersuchung von Roh&ou
SCIENCE IN THE PETROLEUM INDUSTRY By SIR JOHN CADMAN, G.C.M.G., . D.Sc. THE Royal Institution and the Lecture Theatre in which we are assembled to-night are associated with a long tradition of scientific work. Many famous scientists have spoken; from this table and have performed here experiments which were destined to revolutionise wide phases of life and to throw light upon mysteries which had previously been enshrouded in obscurity. Humphry Davy was one of the first Professors at the Institution. His chemical researches brought him the world-wide fame which has ever since been accorded to him: His research on the miner's safety lamp and the control of methane ignition by means of a wire gauze. was epoch-making; and the oil safety lamp of to-day is designed on the principle which he evolved. Davy was followed, after an interval, by Michael Faraday. Faraday's career is an object lesson to all aspiring young men. Apprenticed as a youth to a book-binder, he had high ideals respecting education and culture. After being taken, in 1812, by a customer of his master to hear lectures by Davy, he made notes, amplified them, and finally sent a report of the lectures to Davy himself. In the following year, Faraday became Davy's assistant. In 1825 he was appointed Director of the Laboratory; and in 1833-just 100 years ago-he became the first Fullerian Professor of Chemistry, an appointment which he held till the end of his life. The petroleum industry is under a great debt to Faraday. It was he who first isolated benzole in the course of studying the gas from cracked oil, and by so doing may be said to have laid the foundation of the petroleum industry. This audience, composed of delegates to the World Petroleum Congress, owes a tribute to the memory of Faraday.t Davy and Faraday have been succeeded by men no less worthy than they of this Institution. Dewar carried on the work of Fullerian Professor of Chemistry from 1877 to 1923. The brilliance of his lectures was equalled by that of his laboratory work on the liquefaction of gases and the properties of matter at low temperatures. It was Dewar who made possible the commercial extraction of helium and the low-temperature rectification of liquefied gases.. He was followed by the present Resident Professor, Sir William Bragg, who is noted in the world of Science for his . work by X-ray analysis on the elucidation of crystal structures and of solid substances generally. His achievements here will entitle him to a high place' in the history of scientific research and in the future his name will be coupled with those of the other distinguished. men who have preceded him. Before proceeding with the experiments which it has been arranged to show you to-night it is appropriate to draw attention to two interesting landmarks in the recent history of petroleum: * Lecture delivered at the Royal Institution on July 21st, 1933. t At this point the audience rose and stood in silence in memory of Farad
üBER FLIESSKOHLE AUS BRAUNKOHLE BENTHIN, Freiberg in Sachsen Von Dr. G.
. THE more active character of the humic acid of lignite in contrast to that of coal, favours the successful production of " Fliesskohle " (disperse fuel) from lignite. For the peptisation of lignite, creosote obtained by the distillation of lignite is the most suitable because, it contains constituents with OH- and COOH-groups polar to the same groups in the lignite humic acid. The more concentrated the creosote employed, the better is its peptising power, and the addition of a small quantity of caustic alkali solution or pyridine promotes this function.If it were possible to peptise the Restkohle (the constituent of lignite which is insoluble in organic solvents and caustic solution), the ash content, which is not combined with the humic acids, should be capable of being reduced by centrifuging. ZUSAMMENFASSUNG. Der im Gegensatz zur Huminnatur der Steinkohlen chemisch aktivere Charakter der Braunkohlen lässt die Verwendung der letzteren zur Herstellung von Fliesskohle ohne Feinstmahlung als aussichtsreich erscheinen. Zur Peptisation der Braunkohle ist wegen seiner, den OH- und COOH-Gruppen der Huminsaurebestandteile der Braunkohlen polaren OH- und COOH-Gruppen das Braunkohlenkreosot besonders geeignet. Je konzentrierter es angewandt wird, um so tiefer greifend ist seine Quellungswirkung. Zur Erhöhung der Peptisationswirkung ist der Zusatz von Alkali oder noch besser Pyridin in geringer Menge günstig. Sollte auch eine Peptisation der Restkohle, des in organischen Lösungsmitteln und verdünnter Kalilauge unlöslichen Anteils der Braunkohle, gelingen, so dürfte eine teilweise Entgasung der Fliesskohle durch Abfiltrieren oder Abschleudern der nicht an Huminsäure gebundenen Asche möglich sein. Ein den Brennstoffchemiker in den letzten Jahrzehnten stark interessierendes Problem ist die Verflüssigung der Kohle. Auf drei Hauptwegen suchte man dieses Ziel zu erreichen, auf dem der vorsichtigen destruktiven Destillation, dem der Hydrierung und dem der synthetischen Umwandlung der Kohle in Verbindung mit vorheriger Entgasung. In der letzten Zeit hat ein vierter Weg der Verflüssigung von Kohle an Bedeutung gewonnen, aus Kohle als Ausgangsmaterial einen Brennstoff zu gewinnen, der alle die Vorzüge des Oeles in Bezug auf leichte Transportfähigkeit, leichte Entzündbarkeit und Regelfähigkeit auch in sich vereinigt, ja nachteilige Eigenschaften des Oeles wie die schwere Löschbarkeit bei Bränden und die Möglichkeit von Verdampfungsverlusten vermeidet. Unter den Begriff der Verflüssigung von Kohle wird man jetzt auch die Herstellung von Fliesskohle einbeziehen müssen, wie man ein inniges Gemisch von feinsten Kohleteilchen mit Oel nennt, das wie Oel flüssig ist und sich in seiner Handhabung und Verwendung in seiner Gesamtheit nicht unterscheidet. Das Wort Fliesskohle ist zwar de
DRILLING Chairman: C. DALLEY, M.I.E.E., XINST.P.T. General Reporter8: B. J. ELLIS, KINST.P.T., and E. A. SATCHELL, KINST.P.T. GENERAL REPORTERS'
. CONSIDERABLE interest was shown in the four papers dealing with pressure drilling, but the comments, many of which have not, been sent in for publication, were mostly in the form of queries, as members, other than the authors, had very little experience of the method. It; appeared to be accepted generally that the combined use of mud weight and pressure would become more necessary for the control of formation pressures during drilling as the depth of wells increased. There were lively discussions on the subject of mud for rotary drilling, and it was apparent that, despite the large amount of experimental work that had been done, there was much still to be learnt before the qualities and functions of a mud fluid could be correlated. There have been suspicions for some time past that casing head pressures which accumulated at closed-in mud-filled wells could not be added to the mud head to determine the formation pressure; members were consequently most interested in the theoretical considerations of the matter given in one of the papers, and the experimental proofs that such pressures are due to the upward movement and accumulation of the gas bubbles from the mud and may bear any relation to the rock pressure up to equality with that pressure. There was little discussion on the suggested specification for oil-well cement, but it appeared to be the general opinion that the whole question of cements needed investigation, particularly owing to the continually increasing depths of wells and the higher temperatures to be dealt with. The paper entitled " Oil-Well Cementing in. Deep Wells " arrived too late for presentation at the Congress. Three new types of directional inclinometers were described by their inventors and there was considerable discussion, some of which is recorded, as to the effect of well' casings and extraneous pieces of iron and steel in bore-holes on the accuracy of instruments embodying magnetic compasses. It appeared to be generally agreed that the latter were sufficiently accurate in uncased hole for most oilfield purposes, but that instruments employing gyro compasses were necessary for use in cased hole. IThe importance of tool-joint and drill-pipe design was clearly put forward in the paper by L. S. Dawson, and the hope was expressed that the Standardization bodies in the various countries interested would soon produce standards for both " full hole " and " flush joint " tool joints.