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By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.' showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.' Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By George E. Roberts

THE gains of society from the state of primitive conditions in the past to the standard of living which prevails in the advanced countries today have been accomplished mainly by the increasing productive capacity of the population under the leadership and services of the engineer. Without improvements in the arts and industries the growth of population tends to place succeeding generations always at a disadvantage. In this country we have been exploiting with reckless prodigality a wealth of soil and minerals and timber that has been in preparation for thousands of years. We know that the prices of all national products have been advancing, and were on a rising scale even before the phenomenal increases resulting from the war. Over against this depletion of natural wealth we have the influence of improvements made in the methods of production and distribution-and the accumulation of wealth in the form of productive equipment. The net result of these opposing influences determines whether society moves forward or backward.

Jan 1, 1926

THE fifth annual convention of coal-operating men, with the usual exposition of coal-mine equipment, was held at Cincinnati, May 7 to 11 inclusive, and was fully up to the high standard set by previous years. This spring meeting has come to be one of the most helpful services to industry performed by the Ameri-can Mining Congress and a center at which operators and engineers easily and quickly get into touch with the newest and best things in practice and equipment. Over 200 exhibitors showed this year and very little if anything that is new `failed to be shown. The ex-hibits were well arranged and adequate rather than elaborate. They attracted the careful attention of the members and guests of the Congress, admission being by badge rather than by ticket sold to, the general public. Eight sessions were held for reading and dis-cussion of technical papers, one for Management and

Jan 6, 1928

By Allen R. Rowen

One of the greatest deterrents to more widespread use of manufactured lightweight aggregate is the fact that no industry-wide standards for its application exist. It is true that ASTM has specifications covering lightweight aggregate, but they are so broad as to be of little assistance in mix design work. Today even an engineer who has worked with one lightweight aggregate may be faced with re-education on his next light- weight concrete job if he is in an area served by another producer. Manufacture of lightweight aggregates has grown with the country, appearing in the patent literature at least as early as 1875, when a patent was issued covering use of burnt clay aggregate as an admixture in manufacture of artificial stone. The widely known Haydite came into the picture prior to 1920 as a result of work by Stephen J. Hayde, and there have been many others since who have contributed significantly to the growth of the industry and its technology.

Nov 1, 1956

By G. R. Alther

Finely ground dried bentonites were compacted with a laboratory size Komarek roller compactor. Before compaction the moisture content of the bentonite was adjusted from 8-12% by adding water in a mixer. Predetermined amounts of Nat CO3 activator were dissolved in that water and added to the bentonite. Comparative rheological tests were then run with the compacted, activated bentonite versus unaltered bentonite. Compaction and activation of the bentonites improved their viscosity and water loss properties considerably, more so than extrusion and slurrying. It was concluded that, by using a compactor, bentonite reserves can be extended because low quality material can be improved without adding organic polymers. Introduction Many bentonites mined in Wyoming, South Dakota, and Montana are naturally of drilling mud quality. Those of low sodium content, and those of predominantly potassium, calcium, and magnesium exchangeable cations need altering to meet drilling mud requirements. Most foreign bentonites require sodium activation to meet drilling mud standards set by the American Petroleum Institute (API).

Jan 1, 1984

By A. D. Mutch

This contribution is prompted by the fact that the writer has recently published an article" which has in part the same general conclusions as B. S. Butler's, namely, the form of the standard mineral paragenesis in hypogene deposits and the parallel transition from early high temperature acid to late low temperature alkaline or neutral solutions. Since the writer also recognizes that he is not fully qualified to discuss the formation of ore deposits as a chemical problem, this discussion will be limited to summarizing other observations and will suggest how Butler's Table II might be made more effective. The form of Butler's table is not unlike that widely used by European geologists30 in which the various minerals are related to the types of ore fluids-pegmatitic, pneumatolic and hydrothermal. Thus the decrease in temperature and change in pH of the ore- bearing fluids as recognized by Butler may also be paralleled by perhaps even greater changes in composition, density, and character.

Jan 5, 1958

By E. A. Sondreal, P. H. Tufte

Flue gas desulfurization when burning western U.S. coals can be expected to be easier to achieve and less costly than when burning higher sulfur eastern and central coals. However, western coals cannot generally be burned in compliance with federal and state new source emission standards without some degree of control. Western coals and lignite represent about 20% of total U.S. recoverable reserves with 90% of that strip minable, and their production is predicted to increase from the 60 million tons mined in 1973 to 300 million tons in 1985. Most will be used for electric power generation, where low sulfur content is a paramount concern. Western coals are predominantly below 1% sulfur; low compared with typical values of 2 and 3% for eastern and central coals. Coal cleaning for removal of sulfur is not commercially practiced on Western coals, which typically contain half organic and half pyritic sulfur. A fraction of the pyrite sulfur could possibly be removed, but the

Jan 1, 1976

Mr. Joseph P. GAZZAM,Germiston, Transvaal, So. Africa (communication to the Secretary*) :—About fourteen years ago, in southeastern Missouri,I used a method for the wet determination of lead which closely resembles the modified sulphate-chromate method described by Mr.. Guess. The principal difference, however, is, that after dissolving the lead chromate in hydrochloric acid, the chromic acid is determined by means of a standard solution of ferrous sulphate. The method, which I believe is still in use in southeastern Missouri, was found to be convenient and accurate for the determination of lead in the ores and various products of the mills and furnaces in that district, but it was never used for complex ores. A number of determinations of lead in mill-tailings were made in the year 1891; a few of these results are given in Table I. Table I.—Determinations of Lead in MilL-Tailings by Wet Assay.

Jan 1, 1905

By H. Krueger, H. N. Hersh

USE of autoradiography in diffusion studies offers the advantage that no repeated sectioning is necessary and that the analyses are performed in a simple manner over the continuous range of penetration depths. As part of a program of solid-state physics, it was desired to develop the autoradio-graphic method' quantitatively for use in diffusion studies. Results are reported here for the self-diffusion of silver. Silver was chosen because the existing data are good enough to evaluate the technique." The silver used in this investigation was obtained in the form of ¼ in. diam rods of polycrystalline material, 99.99 pct purity. The radioactive silver, Ag110 (ß, y), was obtained as the nitrate and converted to the chloride for use in a standard cyanide plating bath. The diffusion specimens were 1/2 in. lengths of the rod. They were mounted in bake-lite and the exposed circular face carefully ground and polished. Prior to electrodepositing radioactive

Jan 1, 1956

By M. N. Qureshy, D. D. Sarma, B. K. Verma

Kolar Gold Fields are one of the best known gold deposits in South India where gold occurs in quartz reefs in Archaean hornblende schists and shows large variation in grade. The history of mining goes back to 18th century. The workings at Nundydroog Mines, chosen for Operations Research studies, have entered a depth of 2150 meters. The gold values in these mines were thought to be erratically distributed. However, by using 10540 samples from 49 blocks of ore, it is established that the gold value properties in inch- pennyweight units follow a two parameter log-normal distribution. Emperical relationships between arithmetic means and estimates based on peripheral and internal block values have been worked out using the estimator suggested by Krige (1951) instead of 't' estimator suggested by Sichel (1952). These relations can be used in arriving at block estimates with respective standard errors. There is no significant emperical relationship between depth and the grade of ore.

Jan 1, 1969

THERE are two general classes of problems in connection with electric furnaces. First, those relating to the best utilization of the electrical power inside the furnace; second, those connected with the bringing of the electrical power to the point where it is to be utilized. Referring particularly to the latter class of problems, many calculations have been made, covering a wide variety of furnaces, to check the electrical capacity and power factor found from test. The following analysis, made for the purpose of determining the maximum capacity and approximate performance of a new furnace, to operate at 160 volts on a 60-cycle circuit, may be of interest. The first characteristic necessary to determine is the inductance, since this is the factor that limits the amount of power which can be put into the furnace. Inductance is calculated from the dimensions of the furnace, according to formulas of the U. S. Bureau of Standards,1 as

Jan 10, 1918

By N. Mao

This paper presents the results of a research effort to develop a technique for estimating in situ stresses by measuring stress-induced velocity anisotropy around a borehole. Relevant parameters required to make the estimate were identified and measured in the laboratory on a 35.6 cm (14.0 in) cube of Nugget sandstone with a 10.2 cm (4.0 in) diameter hole, under biaxial loading. Two pairs each of radially and tangentially polarized transducers were placed inside the hole with displacement directions either parallel or perpendicular to the principal stress directions. With this configuration, relative travel times were measured by both a pulsed phaselocked loop technique and a cross correlation of digitized waveforms. The biaxial velocity data were used to back-calculate the applied stress. The standard deviation of the differences between the calculated and applied stresses is 0.62 MPa (90 psi) for a stress level up to 8.63 MPa (1250 psi).

Jan 1, 1984

By E. S. Noe, D. S. Arnold, C. E. Polson

Reactors of today and tomorrow require a high uniformity of their fuel elements despite the wide variety of uranium raw materials from the far corners of the earth. To meet these quality standards metallurgists have been working to design production methods capable of yielding reactor feed materials whose maximum impurities are specified in parts per million, whose physical limits are expressed in thousands of an inch, and whose density variations are less than 1 pct. Such requirements are necessary to maintain normal neutron flow in the atomic reactor and to insure that the isotopic content of the feed material is maintained within narrow limits. Uranium ores and concentrates are produced in many sections of the world, including the Belgian Congo, South Africa, Australia, Canada, and the Colorado Plateau of the U. S. Ores from many of the larger deposits are relatively low grade, and these are concentrated near the mine site before shipment to refining centers, but high grade ores may be shipped directly to refineries.

Jun 1, 1956

By R. P. Aikman, F. G. Miller, J. M. Podgursky

In response to the growing demand for low-sulfur coking coal for iron-making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, (i.e., +28 mesh) at almost any desired specific gravity. However, in the case of fine coal (i.e., -28 mesh) neither of the two existing processes-froth flotation and hydrocycloning-in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this article is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods.

Jan 7, 1967

By H. N. Herrick

THE flow characteristics of drilling muds, as described in this paper, and the method given for solving problems relating to the flow of these muds through pipe and accessory equipment, are based on a conception that drilling muds are plastic solids like paints or greases; not liquids. The data presented in this report have been obtained from studies of California muds, chiefly those used in the Kettleman Hills field, by the Producing Department of the Standard Oil Company of California. Although no claim of scientific exactness is made for the formulas and diagrams, since the data upon which they are based, are not. complete even for California muds, the method has proved to be a convenient means for estimating, closely enough for practical purposes, the pressures required to force muds at various rates through pipe systems in which they are handled. Certain approximations have been made to simplify the procedures so that they can be used easily in the field.

Jan 1, 1932

By Charles D. Hoyt

T IME studies and cost accounting were combined to increase the efficiency of the overall mining method and thereby reduce costs at the Titania mine of the National Lead Co. in southern Norway about 70 miles southeast of Stavanger. From these studies a more effective drilling system was developed, standards were adopted for setting base pay rates, shrinkage stoping was abandoned for open stoping, a new mechanical loading chute was adopted, and the loading and haulage system was changed. Ore minerals at the Titania mine are ilmenite and magnetite; gangue minerals are plagioclase and hyperstene with accessory minerals of biotite, pyrite, chalcopyrite, and spinel. The average content of the ore is 17 pct TiO2 and from 20 to 25 pct iron. The ilmenite crystals contain microscopic lamels of hematite, making it impossible to obtain a high TiO2 content in the concentrate. An ilmenite concentrate with 44 pct TiO2 and 36 pct Fe, and a magnetite concen-

Jan 9, 1950

By Glenn Southward

This describes a highly concentrated mining system consisting of a series of short faces arranged to get complete recovery of coal with the maximum protection for the men and equipment. A series of conveyors collect the coal from eight faces and discharge into mine cars at a central loading point on a main haulageway. The conveyor is sectional and, by a multiple-drive arrangement, the same standard parts are used to construct a unit of any length. THE. V system of mining used at the Norton mine of West Virginia Coal & Coke Co. was designed as a modified longwall with face conveyors, FIG. 1.-GENERAL DESIGN AND ARRANGEMENT OF FACES IN V SYSTEM. for use under roof conditions that would not permit regular longwall methods. This mine is in the Lower Kittanning seam, which averages about 6 ft. in height. There is from 20 to 30 ft. of slate and shale immedi-

Jan 2, 1924

By L. W. Bahney

Many methods for the determination of gold or silver, or both, in cyanide solutions have been published, which with care in manipulation, and modification in some cases, will give results that are satisfactory. It is possible to classify or group these methods as follows: 1. Evaporating the solution in a porcelain or agate-ware dish containing litharge,l or in a "boat" made of lead foil. 2. Forming a lead sponge containing the precious metals by means of zinc shavings,2 zinc dust,3 or a piece of aluminum.4 3. Decomposing the cyanide solution with an acid and precipitating the precious metals by the use of one or a combination of some of the following: Copper sulphate,5 sodium sulphite,6 hydrogen sulphide,' cement copper.ll 4. Precipitating the silver by zinc dust held in a Gooch crucible and determination with a standard solution of sulphocyanate.9 5. Electrolysis.l0 . 6. Colorimetry.ll

Jan 1, 1915