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By C. Feng, C. Elbaum

Knoop hardness measurements were carried out on large grains of iodide titanium containing different amounts of oxygen. For each oxygen content the hardness is recorded ainingas a function of the crystal orientation and of the angle 4 between the indenter diagonal and the projection of the C (hexad) axis in the surface. The results can be expressed by the following relation; hardness = n-k cos 2ø, where n and k are constants for a given oxygen content and crystal surface orientation. A NISOTROPY of hardness is a well-known phe-nomenon and has been reported for many metals.1-3 At the present time, however, such information is not available in the literature for titanium. Consequently, a systematic study of the simultaneous effects of oxygen content and crystallographic orientation on the hardness of titanium was undertaken in this laboratory. Evaluations of oxygen content in titanium are frequently carried out through hardness tests. Although such procedures may be justified in small grain specimens, the results of the present investigation indicate that the anisotropy of hardness should be taken into account in the case of coarsegrained specimens as well as in the case of pronounced preferred orientation. Materials and Experimental Procedures Iodide titanium, 99.99 pet pure and containing of the order of 0.002 wt pet O, was used throughout this investigation. The metal was arc melted in an argon atmosphere and cold rolled into strips 1/16 in. thick. These strips were subsequently recrystal-lized and strain annealed in vacuum (10" mm Hg or better) at 850°C in order to produce crystals varying in diameter from 10 to 25 mm. Oxygen was introduced into selected large crystals by heating at 700°C in an atmosphere of pure oxygen under an observed pressure of approximately 50 mm Hg. Each sample was subsequently annealed in vacuum at 850°C for 100 hr, in order to homogenize the oxygen content throughout the specimen. It was found that longer annealing was not necessary, for no change of surface hardness in a given direction was detected after prolonged annealing. The oxygen content was determined by the difference in weight of the specimens before and after the oxidation-annealing cycle. The accuracy of oxygen determination is within ±0.1 mg in samples weighing 0.5 to 1 g. A vacuum fusion analysis of oxygen was performed on several samples and gave results in good agreement with the ones obtained by the weight change. It should be emphasized that expected weight losses through evaporation of the metal in vacuum at 850°C' are many orders of magnitude lower than the precision of these measurements. Following the annealing treatment, both oxidized and unoxidized crystals were carefully polished. All detectable traces of surface cold working were removed by repeated polishing and etching. Laue back reflection X-ray patterns were taken for each crystal for the purpose of determining the orientation and ascertaining the absence of substructures detectable by this method. Hardness measurements, using a 1 kg load, were subsequently carried out on a Tukon hardness tester equipped with a Knoop indenter. The Knoop indenter was used throughout this work because indentations obtained by means of a Vickers indenter are considerably distorted due to the anisotropy of the elastic constants in titanium. Such distortions are much less pronounced in the case of Knoop indentations, although for some orientations a cer-

Jan 1, 1959

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By J. D. Rice, S. C. Pitzer, C. E. Thomas

Interpretation of pressure build-up data obtained in the conventional manner has often been difficult because of the deviation from theoretical behavior. Major causes of this deviation have been attributed to damage and afterflow, and to fluid redistribution in the wellbore which, in extreme cases, can result in a pressure hump in the early portion of the build-up curve. Theoretical investigations show that bottom-hole pressure is definitely influenced by phase redistribution in the tubing column during surface shut-in tests, and that the magnitude of the effect is sensitive to the producing gas-oil ratio and stabilized rate of flow in the well. For field experiments a wire-line tubing packer, which can be run in the tubing against a stabilized flow rate, was developed for bottom-hole shut-in tests. By use of this bottom-hole .shut-in method, pressure humps previously observed in surface shut-in tests were completely eliminated and the effects of afterflow minimized. Analog and digital computer studies have been made to obtain theoretical curves for comparison with field curves, and remarkable agreement between the results of bottom-hole shut-in tests and theoretical curves has been obtained. INTRODUCTION Pressure build-up data from shut-in wells have been used by the petroleum industry to determine the permeability of the formation, to estimate wellbore damage, to evaluate the static reservoir pressure and to speculate reservoir volume. Calculation of these factors is based on methods of analysis developed for theoretical systems whose build-up curves have a charac- teristic shape when the wells are shut-in at the sand faCe.1,2,3,5,8,10 However, field curves obtained by conventional surface shut-in methods do not always exhibit this characteristic. Such factors as stratification, rock heterogeneities and irregular reservoir geometry can cause the character of a build-up curve to deviate from that predicted by theory for a simple system. In addition, all field build-up data are affected by the methods utilized in obtaining the measurements. Conventional surface shut-in techniques allow two effects to occur which contribute directly to the manner in which pressure builds up at the sand face. The first, afterflow, has been recognized for some time and methods are available for estimating the magnitude of its effect and for correcting its influence.' The second, phase segregation in the tubing column after shut-in, has been reported only recently and appears to exert a considerable influence on the character of field build-up curves.!' In extreme cases, phase segregation can produce "pressure humps" in the early portion of the build-up curve. Such curves have been considered anomalous and have defied analysis. It is the purpose of this paper to discuss the effect of phase segregation in the tubing string during build-up and to present a bottom-hole shut-in technique for obtaining field build-up data which minimizes the influence of afterflow and eliminates phase segregation effects. It will be shown that reliable reservoir information can be calculated from build-up measurements obtained using this method, even though conventional surface shut-in tests on the same wells yield anomalous data. DISCUSSION OF PHASE REDISTRIBUTION EFFECTS Some of the effects of phase redistribution on pressure build-up curves have been described previously by Matthews and Stegemeier" who have presented evidence that phase segregation is responsible for the pres-

By F. A. Seward

A1though the expanding Eltran1 configuration has been used in induced polarization exploration for several years, there has been little application of this method to straight resistivity problems. A comparison of results of resistivity exploration by this technique versus those obtained from Wenner configuration surveys reveals a number of advantages in interpretative resolution as well as in field operation. The application of electrical resistivity to ground-water exploration is well known.= In the past a major portion of this work has been accomplished by use of one or more variations of a technique employing the Wenner3 electrode configuration. With the introduction of the frequency domain technique of induced polarization measurements, used primarily in the exploration for disseminated sulfide deposits, there arose the need for an electrode configuration by which potentials could be measured externally to the current electrode spread in order to minimize coupling between current sending and potential receiving circuits. It was also deemed desirable that the configuration would provide information laterally along profile as well as with depth. To reach these objectives the expanding dipole-dipole configuration (which probably first was used in the electrical transient method of exploration and from which the name 'Eltran' was derived) has been adapted to induced polarization exploration. The author has successfully applied the same techniques

Jan 1, 1963

By R. H. Adams, A. M. Khan

The Huntington Beach oil field is on the Pacific Coast, southeast of the City of Los Angeles (Fig. 1). It lies both onshore and offshore. Most of the onshore section is operated by Standard Oil Co. of California, WOI. The Tar reservoir is of upper Pliocene age, about 200 ft thick, and consists principally of fine-grained, unconsolidated, somewhat shaly sand, with thin inter-bedded shale stringers throughout (Fig. 2). The reservoir is a broad, highly faulted, elongated anticline, with an areal extent of about 370 acres. Most of the faults bisecting the structure are normal, trend north-south, and are the main cause of reservoir discontinuity (Figs. 3 and 4). From 1964 to Dec., 1967, 259 steam stimulations were performed on a total of 125 Tar sand wells. Eighty-six new wells were drilled and steam stimulated. Of the total, 96 have been stimulated twice, 34 three times and 3 four times. During this same period, a two-injector steam drive pilot has been in progress. The response obtained from this project has been compared with the response to cyclic stimulation. This paper presents an analysis of the field observations for the two methods of thermal recovery. History of Development Drilling to the Tar pool commenced in 1924 with an initial well production of 40 to 50 B/D of 12o API gravity oil. Complete primary development of the pool has been spread over several years. Approxi- mately 40 wells were drilled during the first phase of development, which was completed in 1945. The subsequent primary development started in 1960 with initial well productions of 30 to 40 B/D oil. Thirty-seven wells were completed in the Tar pool during this phase. For the most part, slotted, gravel flow packed liners have been used in the wells in this pool. A cyclic steam stimulation pilot was initiated in March, 1964. Based on the very successful stimulation in the pilot area, the cyclic stimulation project was expanded to include all of the Tar pool wells producing at the end of 1965 (Fig. 5). Also, a development drilling program was begun at this time. To date, 86 new wells have been drilled under this program. The number of wells drilled each year in this secondary phase of development is also shown in Fig. 5. New Well Completion Practices Most of the new wells have been completed to produce from both the Upper and Lower Tar zones. Generally, a casing stub is cemented from the top of Lower Tar to the base of clean Upper Tar sands to exclude intermediate water-bearing sands. The water string is then cemented from the top of Upper Tar to about 1,500 ft with neat cement and 30 percent silica flour. The annulus from 1,500 ft to surface is then filled with a petroleum-based gel through a high-temperature port collar. Once again, a history of sand-free production dictated the use of 60-mesh gravel flow packed liners. The Upper and Lower Tar

Jan 1, 1970

By J. H. Bain, D. C. Haigh, L. C. Parsons

Jan 1, 1964

By W. L. Connell, O&apos

The properties of some heavy liquids which can be used in sink-float separations are discussed with major emphasis being given to the halogenated hydrocarbons. Data are presented on density, viscosity, thermal characteristics and the effects of moisture and temperature on the corrosiveness of the liquids towards various materials of construction. The toxicity of these materials, the hazards involved in handling them, and the procedures for handling them safely are also discussed. True liquids have certain advantages over colloidal suspensions for sink-float separation of minerals which makes their use especially advantageous when close separations, fine particle sizes or water-soluble minerals are to be treated. For best separating results, the medium should have an easily controlled, uniform, stable density. Here, true liquids have the advantages of allowing closer control of density and of not requiring agitation to maintain a uniform den- sity in the equipment. Low viscosities are desired in a separating liquid so that rapid separations of fine material can be made. Many liquids have lower viscosities than the colloidal suspensions at operating gravities of 1.4 to 5.0. For economic reasons and to prevent contamination of the product, the separating medium must be easily and completely removed from the ore. Normally, true liquids must be more completely removed than the cheaper suspensions and thus cause more problems in this area. The fact that the medium should not react with the minerals, air, water or the common materials of construction limits the choice of liquids which can be used, but many are available which are sufficiently stable. A more serious objection to the use of true liquids is that many of them present a toxic hazard to operating personnel and users of the product. Most true liquids are toxic to some extent, but modem knowledge of toxicity allows us to recognize the hazards inherent in handling them and enables us to design around them. Three types of true liquids are available for this use: 1) Halogenated hydrocarbons cover the gravity range from 1.2 to 3.3. They are generally more volatile and less viscous than the other liquids.

Jan 1, 1963

By Reno H. Sales

Our colleagues cannot in the future earn reputations and medals for achievements in milling and smelting ore and for successful management of mining companies, if some one doesn't keep finding and mining the ore to mill and smelt and to provide the basis for the good management. Good ore seems sometimes to be quite helpful to good management, and good ore is not as easy to find as it used to be. And there are still more reasons, why—when this honor had been decided upon and named for Mr. Daniel C. Jackling—it should be initially conferred on Reno H. Sales. . The terms of reference of the award are that it should be conferred upon an individual working in the fields of mining, geology, geophysics, who has made an outstanding contribution to the progress of technology in one or more of those fields. And in this initial year (the earlier years are the easiest) just that was done. I think I could get away with it amongst the old-timers of my generation if I say that this time they made the award to the individual, who made the outstanding contribution. But, as Al Smith used to say, "Let's look at the record." Really, the record is mixed up a little with extra-lateral litigation—the old-time "apex cases" under Section 2322 of the Revised Statutes. Reno Sales doesn't like such litigation, but there is little question that the urgency, generated by conflicting claims of intra-limital and extra-lateral rights, and consequent necessity for committing to records and maps the complications of Butte structure, did advance—and by several years—the first continuous, accurate, systematic, and scientific portrayal of the geological and mineralogical details of what is, after all, the most important and the most complicated copper district—at least in North America. Prior to Sales' time, some of the most eminent of geologists often waived details. One geologist took the judge to the window to show him the Rarus fault going through a notch in the Continental Divide. The entertaining testimony in the Bluebird litigation was as perfect in literary style as it was innocent of the criteria by which faulting and lack of continuity of vein structure are now recognized. At any rate, this need for an accurate record of structure was in the background—to whatever extent it was, or was not, the etiological agent—for formation of the Geological Department of the Amalgamated Copper Co. in and about the year 1900. Charles W. Goodale was at that time the head of the Boston & Montana, and John D. Ryan succeeded William Scallon as the president of Anaconda Copper Mining Co. in 1905. Horace V. Winchell, for years a specialist in extra-lateral litigation, was perhaps the man who at that date had the vision, the persuasive weight with the management, and the willingness to defend the idea of large current expenditures (as then viewed) for a complete and sys-

Jan 1, 1955

By A. Alonso, J. Daubenspeck

In the nickel extraction process at Nicaro, Cuba, dried and ground nickel bearing laterites are reduced at 1300-1400F in multiple-hearth furnaces. Nickel is leached from the reduced ore by aeration in an aqueous solution of ammonium carbonate. Nickel carbonate is precipitated from the liquor and calcined to yield nickel oxide. The following are the more important modifications of the Nicaro process since plant rehabilitation and expansion. Ten percent increase in tonnage was achieved without decreasing the fineness of the ore by minor mechanical modifications of the grinding plant. Another five percent increase in tonnage was attained by intentionally overloading the ore prepration and leaching circuits in an effort to control cobalt extraction. Modifications at the sintering plant allowed it to handle the entire output of the expanded plant. A fifty percent increase in leach liquor cooling facilities alone provided an increase in nickel production of five percent. Stronger fresh leach liquor for increased nickel washing efficiency was obtained through improved distribution of water to the ammonia absorption towers. Advantage was taken of the reduced calcine's capability to precipitate cobalt, and modifications in the leach liquor circulation provided controlled cobalt solubility with minimum harm to nickel extraction. Several process changes at the drying plant brought about a ten percent reduction in the fuel oil consumption at this pint. Controlled air addition to the reduction furnaces' upper hearths burned formerly wasted combustibles thereby reducing oil consumption by twenty percent. The nickel extraction process successfully emplayed on the extensive but lowgrade lateritic ores of Eastern Cuba at the U. S. Government owned Nicaro plant, has been previously described in various publications. The large mine and plant operated by the Nickel Processing Corporation, located on the northeastern shore of Oriente Province, have been recently expanded to a yearly capacity of about 50 million pounds of nickel. Essentially, the operation involves open pit mining of a limonite-serpentine ore mixture containing 1.3 to 1.4 percent nickel and 34 to 38 percent iron. The comparatively lumpy, wet (25 to 30 percent moisture) ore is first dried and ground prior to chemical treatment, to which the entire 7,000 tons per day feed must be subjected. In the initial chemical action the dried and ground ore is reduced with carbon manoxide and hydrogen at 1300-1400° in multiple-hearth furnaces. The resulting metallic nickel is selectively leached from the reduced calcine by aeration in an

Jan 1, 1961

By H. D. Outmans

A method has been developed for determining the relative water wet-tability (fraction of the surface wet by water) of porous media. This method involves the adsorption of methylene blue dye from an aqueous solution onto the solid surfaces of rock contacted by the injected dye solution. Experiments on Berea snndstone cores have shown that water-wet cores adsorb a large amount of dye from solution. In oil-wet cores, however, the injected aqueous dye solution is prevented from contacting the adsorptive surfuces by a film of oil and virtually no dye is adsorbed. This method was tested by experiments on mixtures of water-wet and oil-wet sand. Using the dye adsorption method, it was possible to determine quantitatively the fraction of water-wet and oil-wet sarzd in such mixtures. The dye adsorption test is readily applied to determinitrg the relative water wettability of fresh oilfield cores. The cores are not extracted before testing. Observed values of the wettability of field cores tested to date have varied from 100 to 6 per cent water wet. INTR OD UCTIO N Recent articles1 ' have emphasized the important role that wettability plays in almost all phases of reservoir rock behavior. It has been shown that wettability has a profound effect on the interstitial water saturation, residual oil saturation, capillary pressure, relative permeability, waterflood behavior, and resistivity index of oilfield cores. A quantitative investiga- tion of the effect of wettability on these core properties is severely handicapped by the lack of a simple technique for measuring the wettability of a porous medium. If such a technique were available, it would provide investigators with a means of gaining insight into the distribution of phases within a core. A number of qualitative methods of estimating wettability are known. These include contact angle measurements, flotation tests and studies of displacement pressure: imbibition7 and relative permeability data.' Using these tests, it is usually possible to classify a core as water-wet, oil-wet, or some intermediate degree of wettability. One recently proposed method involving measurement of nuclear magnetic relaxatione offers promise of determining quantitatively the fractional wettability of cores. The equipment is rather elaborate and necessary treatment of the cores before testing probably alters the natural wettability. This latter point also applies to most of the cited qualitative methods. This paper presents a new technique for determining water wettability of cores; it is based on measurements of the dye adsorption capacity of the core. This method has the advantage of requiring relatively simple equipment and involves minimum handling of the core before testing. It is important to distinguish between the various concepts of wettability referred to in the literature. The term "wetting" is defined by Bartell as that phenomenon which occurs when a solid and liquid phase come in contact in any manner so as to form a solid-liquid interface. A preferentially water-wet solid is defined by Jennings in terms of the advancing contact angle in the solid water-oil systems. Brown and Fatt regard fractional wettability as the fraction of the total surface area that is preferentially oil-wet or water-wet. However, none of these definitions adequately describes the type wettability measured by the dye test. This calls for the introduction of a new term, "relative water wettability", which we define as the fraction of the total surface area of a core contacted by injected water. DESCRIPTION OF METHOD The ability of a porous medium (especially the clays) to adsorb large quantities of surfactants, dyes, etc., is well known. It is reasonable to assume that a substance can be adsorbed from solution onto a solid surface only if the solution contacts the surface. In this connection Shapiro" has shown by experiments on silica gel that completely dry gel will adsorb methyl red dye from a benzene solution. On the other hand, if a film of water more than several molecules thick is present on the silica gel, the adsorption capacity of the gel for the dye is drastically reduced. Thus, a study of the dye adsorption capacity of cores should give some clue as to the fluid distribution on the surface of the core. TEST OF METHOD As a qualitative check on this theory, dye adsorption tests were run on similar Berea sandstone cores (Table 1, Cores 1-5). Cores saturated initially with water and flooded with 0.01 per cent aqueous methylene blue adsorbed 0.58 mg dye/gm of core. Similar cores saturated initially with water, driven to irreducible water with oil, and then flooded with the same dye solution also adsorbed 0.58 mg dye/gm of core. Another core, treated with a 5 per cent Dri-Film solution, dried and saturated with oil (Soltrol) adsorbed no dye when the dye solution was injected. These tests confirm

By A. M. Gaudin

Jan 1, 1962

Jan 1, 1963

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

Jan 1, 1964

By R. S. Olson

An analysis of the wash thickener-two stage filtration circuit was undertaken to quantitatively describe the circuit performance. On the basis of information developed in this study, the factors of major importance in reducing soluble loss are: filter wash, wash zone size, filter capacity, filter feed pulp dilution, blow back, filter cloth, water to repulp, water to primary wash, water to feed pulp and thickener underflow. The wash thickener-two stage filtration circuit has been used in many hydrometallurgical plants to separate solute from leach solids. As many as 20 to 30 plant operating variables determine the performance of the wash circuit and hence the soluble loss. The complex relationships of these variables, with each other and with soluble loss, make the evaluation of their effect on mill performance difficult. An analysis of this type of circuit was undertaken to quantitatively describe the circuit performance. THE CIRCUIT The diagram in Fig. 1 represents the operation of the wash thickener-two stage filter circuit. This circuit provides for counter current, cross current or for a combination of countercurrent-cross current operation. The feed pulp stream, J, is intended to include any solution or water, other than primary and secondary filtrate, which enters the wash thickener. Except for filter washing, the operations in the circuit are simple mixing operations which can be described by material balance. The concentration of solute in the filtrate and cake solution after application of wash liquor cannot be described by simple material balance. The displacement washing equation, derived by Rhodes1 and extended by Choundhury and Dahlstrom,2 appears to best describe this case of miscible displacement in porous media. In a useful form, it is

Jan 1, 1963

By Albert Zima

ACCORDING to recently published statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet.

Jan 1, 1935

By P. C. Hodges

WHILE there is very little romance connected with the operation of a stone quarry, yet to those who have participated in the growth and development of a business that has been a pioneer in its field and that FIG. 1.-LOCATION OF PROPERTY OF MARBLE CLIFF QUARRIES COMPANY. has been in continual operation two-thirds of a century there is bound to be a background of experience, which if properly capitalized, brings progress as well as satisfaction in its accomplishment.

Jan 1, 1936

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

EXPERIMENTAL work on the properties of high-purity alloys of the copper-manganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. PREVIOUS WORK Heusler1 conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilibrium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alphabeta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350° to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur5 have also noted this precipitate Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,' or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967