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By R. E. Boehler, N. C. Ludwig

At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory's thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers' experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman's observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph' and also in a textbook.' Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very

Jan 1, 1961

By W. M. Robertson

The rate of crack Propagation thvough a solid meta1 in the presence of a liquid metal has been calculated. The crack is assumed to propagate by solution of the solid in the liquid under the influence of an applied stress, with volume diffusion of the dissolved solute through the liquid controlling the propagation. The calculated velocities can be tens of centimeters per second or higher. THE embrittlement of normally ductile solid metals by liquid metals has been the subject of extensive study, as summarized in the book by Rostoker, McCaughey, and arkuus.' In experimental studies of liquid-metal embrittlement it is usually concluded that the observed crack-propagation rates are too high to be accounted for by diffusion processes. Diffusion is considered to be an unimportant factor and various other mechanisms are invoked to account for the experimental observations. The similarities of liquid-metal embrittlement to stress-corrosion cracking, to hydrogen embrittlement of steel, and to low-temperature embrittlement of bcc metals are frequently used as analogies for these mechanisms.1"3 The present paper assesses how rapidly a crack could propagate by a mechanism of volume diffusion through the liquid metal. We assume that the crack propagates by solution of the solid in the liquid at the crack tip under the influence of the applied stress and diffusion of the dissolved solute away from the crack tip. The model uses only macroscopic thermodynamic, kinetic, and elastic concepts. The calculations indicate that this dissolution-diffusion mechanism can give high crack velocities. In some previous treatments4'' of crack propagation in a liquid-metal environment the fundamental step has been the breaking of atomic bonds at the crack tip. The liquid greatly decreases the energy necessary to break these bonds. The present model assumes the crack is filled with liquid metal; the presence of the liquid is essential because diffusion through the liquid is assumed to control the rate of propagation. With proper modification this model could also apply to stress corrosion in a liquid environment. THEORY Consider a crack in a homogeneous elastic continuum, ignoring all the structural details of the solid. This neglects a host of metallurgical details which can be significant in the problem of liquid-metal embrittlement;' but this simple assumption is a useful approach in evaluating the role of diffusion through the liquid. The stress distribution around the crack tip establishes a gradient in the chemical potential at the tip, which causes a diffusion flux through the liquid away from the tip. The solid-liquid interfacial tension works against crack propagation, since propagation requires creation of interfacial area. From these two considerations we derive the diffusion flux, which then yields an expression for the velocity of the crack tip. The concentration of the solute in the liquid, C, is equal to the equilibrium concentration in the presence of an unstressed, flat surface, Co, plus the excess concentration due to the stress, AC(a), plus the excess concentration due to capillarity, AC(y): We calculate AC(o) and AC(y) and then obtain the diffusion flux. Consider (Fig. 1) a long flat crack of length 2L, thickness 2r, and tip radius r, where r remains constant as the crack propagates in the positive x direction. There is no stress ay in the y direction across the flat surfaces of the crack. The magnitude of the stress at the crack tip due to the applied stress, a,, is given by the relation6 ^=^[l-2^] 12] which, for long narrow cracks, becomes The stress increases the chemical potential in proportion to the strain energy.? The excess chemical potential due to the stress, Ap(a), is given by where 52 is the atomic volume of the solid and E the Young's modulus. Inserting Eq. [3] gives Now consider the crack to be filled with a liquid metal. The excess solubility due to stress, hC(a), is given by the excess chemical potential due to capillarity, Ap(y), is given by8 where y is the solid-liquid interfacial energy, and v1 and YZ are the two principal radii of curvature of any surface point. At the crack tip, r1 = -r and vz = m, so TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME

Jan 1, 1967

Diesel powered machines are doing some specific operations in the cyclic order required by the technical process. The dynamics of this process in certain conditions has an essential influence on environmental health conditions in the working area. The main purpose of this paper is to show, using computer simulation, how the movement (dynamic) of diesel vehicles effects environmental health standards and also how to determine the required air quantity for ventilation.

Jan 1, 1985

By I. M. Roberts

The war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-%urnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. Coking Characteristics OF Coals Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By Maurice Cook

NORMALLY the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 min., for example, would, for many purposes, he regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals and alloys that take place on annealing, and a number of generalizations have been reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results, however, that are not covered by these generalizations can be obtained, which, in some instances, may even appear to he contradictory to them. According to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which, according to ordinary standards, would be classified as coarse or large.

Jan 1, 1938

By I. M. Roberts

The war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-%urnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. Coking Characteristics OF Coals Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

Jan 1, 1925

Jan 12, 1950

By W. G. Matteson

In 1915, the State of California passed a law of great scope and importance. This law has been in successful operation for a year and may be briefly described as an act " establishing and creating a department of the State Mining Bureau for the protection of the natural resources of petroleum and gas from waste and destrucbion through improper operations in production; providing for the inspection of petroleum and gas wells; requiring all persons operating petroleum and gas wells to make certain reports" and providing the necessary officers and assessments to carry out the provisions of the act. The statute provides for a separate department of the State Mining Bureau, under the general supervision of the State mineralogist, with a staff composed of a "state oil and gas supervisor" and four deputies. It rules that all petroleum and natural gas wells shall be drilled, operated or abandoned under the supervision of the State supervisor, who shall order such tests or remedial work as seems to him necessary to protect the interests of property owners and the general public. It also provides for a board of arbitration to consider orders given by the supervisor which are not acceptable to the well owner. Section 18 of the act, which is the provision that is directly related to this paper, requires ('the owner of any well referred to in this act to keep a careful and accurate log of the drilling of such well," and further requires that this log shall show the character and depth of the formations passed through or encountered in the drilling, particularly the location and depth of the water-bearing strata; the character of the water encountered (so far as ascertained); whether the water was shut off, and, if solat what point; that it shall show completely the amounts, kinds and size of casing used; the depth at which oil-bearing strata are encountered; the depth and character of the strata, and whether all water was successfully and permanently shut off so as to prevent percolation or penetration into the oil-bearing strata. This log is to be kept in the local office of the owner or operator, subject to the inspection of the supervisor or any of his deputies at any

Jan 1, 1917

OPEN-HEARTH refractories are not merely an accessory to the furnace. They are the furnace, to all intents and purposes. The steel work of the main structure is merely an open frame which helps to support the refractories; and the regenerators, a necessary part of the furnace system, consist almost entirely of refractories. Not only do refractories constitute the essential part of the furnace, but they also carry the liquid steel all the way 'to the point where it begins to solidify. On leaving the furnace the liquid passes through a refractory runner into a refractory-lined ladle, then through a refractory nozzle closed by a refractory stopper on the end of a rod protected by refractory sleeve bricks. The liquid is sometimes sent through an additional refractory- lined tundish, a supplementary ladle, or a refractory runner for bottom pouring, until it finally enters the iron mold in which it solidifies. Even in the mold, refractory materials are sometimes used to provide a nonconducting "hot top." This series, from runner and ladle to hot top, inclusive, is often referred to collectively as the "pouring-pit refractories." REFRACTORY RAW MATERIALS The raw materials available are best classified into basic and acid types. The principal basic raw materials are magnesite, dolomite, and chrome ore. The principal acid materials are silica in various natural forms, and fireclay. Magnesite. Austria was the principal source of magnesite (MgC03) until recent years, when the Province of Quebec, in Canada, and the states of Nevada and Washington became important sources for the American steel industry. More recently these natural sources have been supplemented by the so-called "sea-water magnesite"-which is the name somewhat incorrectly given to magnesium hydroxide obtained as one of the products

Jan 1, 1951

By S. Ramachandran, L. A. Vazquez, N. L. Grauerholz

A novel process is described for the selective flotation of scheelite from low-grade (- 0.5% W03) tungsten ores having appreciable quantities of calcareous and siliceous gangue minerals. Specifically developed for the Tempiute, Nevada facility of Union Carbide, the process yields tungsten concentrates exceeding 15 percent W03 with at least 85 percent recovery. This condition was not achieved through conventional processes. This process consists of conditioning the ore pulp with judicious amounts of lime, followed by soda ash and sodium silicate as modifiers. The scheelite is then floated using a mixture of oleic and naphthenic acids as collector. Contrary to the common observation as to the deleterious effects of calcium in fatty acid flotation systems, lime addition is found to be beneficial in achieving satisfactory results. The process has also shown excellent results on a Brazilian scheelite ore.

Jan 1, 1976

By J. Kent Smith

Vanadium is generally spoken of as a rare element; but, even in the light of our resources as known a couple of years ago, this description could be accepted in a qualified sense only. In fact, vanadium is very widely distributed, being a constituent of most clays, while even caustic soda has been shown to contain almost regularly a minute proportion of it, although the quantity in each case is so small as to render impracticable the extraction of the metal therefrom with profit. The opening-up of a large deposit of vanadium sulphide ore in South America has put a new phase on the commercial outlook of vanadium, the technical value of which for the improrement of steel has been proved by rigorous scientific investigation. This sulphide ore has the following analysis: Per Cent. Vanadium sulphide,.39.84 Molybdenum sulphide,.1.57 Nickel sulphide,.........1.49 Iron sulphide,.........4.07 Arsenic sulphide,.. nil. Copper sulphide,.. nil. Manganese sulphide,..nil. Free sulphur,..30.57 Phosphorus,...nil. Silica,....13.60 Alumina,..........2.46 Combined water, 5.00 Carbonic acid, Lime, magnesia, potash, soda and unaccounted for, 100.00 Being a free-burning ore it is calcined with ease, losing 45 per cent. of its weight in the process. The calcined ore has the following analysis:

Jan 1, 1908

By R. B. Tippin, J. S. Browning

Inasmuch as the higher grade potash deposits are rapidly being depleted, it is important that economic beneficiation techniques be developed for recovering potassium compounds from lower grade sylvite ores and deposits containing clay materials. The Federal Bureau of Mines has conducted research to develop processes for heavy liquid concentration of potash ores, This method of concentration is discussed, and results of tests made on potash ores from New Mexico are presented. The tests demonstrated the technical feasibility of producing near commercial-grade potash concentrates, with a high recovery of the contained sylvite. The concentration of minerals based on their differences in specific gravity dates back to the very beginning of mineral dressing, and the use of heavy liquids in the laboratory to achieve optimum mineral separations has been utilized for many years. With the advent of froth flotation and its success, the incentive to develop new processes has remained relatively dormant. However, flotation refinements in the nonmetallic ores have not progressed as rapidly as in metallic (sulfide) ores because of the complexity of the deposits and the chemical similarities of the minerals.

Jan 1, 1967

By George I. Smith

Jan 1, 1985

Just three years after researchers announced its development, Dravo is putting the finishing touches on a new $60-million Thiosorhic lime mine/kiln complex near Maysville, Ky. Electric utilities in western Pennsylvania and Ohio have already signed long-term contracts for over three-quarters of the projected 907 000-t/v (1-million-stpy) production. Thiosorbic lime, a flue gas desulfurizing agent, proved in industrial testing that at high emission levels (greater than 3000ppm SO2) it could be twice as effective in SO2 capture as conventional lime, while eliminating the major problem of scaling and plugging of scrubber equipment.

Jan 4, 1977

By T. A. Rickard

The question of the original extent of the anthracite-beds of Pennsylvania has often been raised; and even discussed with reference to the probability of their present existence under the New Red, a matter of immense practical importance. So high an authority as my revered master, J. P. Lesley, Honorary

Jan 1, 1903

By Peter G. Chamberlain

Many mining engineers considering in place leaching for the first time are uncertain as to how to evaluate ore bodies for potential leachability. Evidence presented in this report emphasizes the critical role of permeability in such evaluations. Whether an engineer is considering leaching "tight" formations typified by the porphyry copper deposits of the southwest or the permeable uraniferous sandstones of Texas and Wyoming, permeability measurements are the keystone of any testing program. Permeability tests range from cheap and easy to highly expensive and sophisticated operations. Constant head, variable head, and pumping tests all have application in evaluating ore bodies for in-place leaching. Costs of these tests will not unduly deflate the pocketbooks of most mining companies. The basic procedures for selecting and running these field tests--including preparing suitable wells--are reviewed for the benefit of newcomers to in-place leaching.

Jan 1, 1979

The second special war meeting of the New York Section was held on Thursday evening, Aug. 23,-preceded by is an informal dime The topic for discussion -was the supply of sulphur and pyrite, the raw materials for the manufacture of one of the most important of till war materials-sulphuric acid. The first speaker was William Young Westervelt, the Institute's representative on the War Minerals Committee. Before taking up the subject of the evening, Mr. Westervelt briefly described the organization and plan of operation of the War Minerals Committee.

Jan 10, 1917

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969