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By R. E. Holmes, T. W. Leland

The solution to the unsteady-state mass- and heat-transfer equations describing the adsorption of a dilute component from a gas stream flowing through a packed bed is readily applicable to the design of hydrocarbon recovery units. The solution to these equations depends on the assumption of a linear equilibrium equation to relate concentrations on the surface to concentrations in the gas. This assumption is shown to be justifiable for components which are very dilute in the gas stream. This approach permits the prediction of the effects of bed shape and size, cycle time, and gas mass velocity on the recovery of each component. It also allows the time and gas flow rate needed for regeneration to be determined. The equations involve a constant for each component and another constant characterized by the type of adsorbent. These constants must be evaluated from operating data. Values of these constants determined for silica gel are presented. This paper points out the type of experitrrental data needed for a thorough design of hydrocarbon adsorption units. INTRODUCTION The growing importance of adsorption processes to recover hydrocarbons from natural-gas streams has created an urgent need for better methods to design and predict the performance of these processes. Since the original use of solid adsorbents in natural-gas processing was for dehydration, most of the current design methods for hydrocarbon recovery re extensions of those developed earlier for dehydration. These methods are based on an adsorptivity or bed loading factor defined as the amount of a particular component adsorbed per unit weight or per unit volume of the packed bed. The recovery of a given component is then expressed as an empirical function of its adsorptivity on a given adsorbent. In spite of the simplicity and initial utility of these methods, they are not completely satisfactory in that they do not predict the effect of the dimensions of the bed in relation to flow rate and cycle time, and do not predict the distribution of various components along the length of the bed. It is possible, however, to make a considerable improvement in the design of these processes by applying the basic equations of mass and heat transfer applicable to gases containing small concentrations of adsorbing components flowing through granular beds. These equations have been developed and solved by Anzelius,' Furnas,% nd Hougen and Marshall." where G = mass velocity of the inert constituents (assumed to be methane), lb/hr-sq ft, y = weight of an adsorbing component in the gas per unit weight of inert, lb of a given constituent per lb of methane, x = bed length, ft, p, = packed bed density, lb/cu ft, P, = gas density, Ib/cu ft, f = void fraction in the bed, t = time, hours, and w = weight of a given component adsorbed per unit weight of adsorbate free solid, Ib/lb pure adsorbent. The term on the left side of Eq. 1 represents the flow rate per unit bed volume of a component entering less the flow rate per unit bed volume of that component leaving the differential bed length. The terms on the right side represent, respectively, the accumulation rates per unit bed volume on the solid and in the gas phase within the differential bed section. The last term is negligible for this application since pgfv is quite small in comparison with p, and G. The partial differential is determined by the mass-transfer rate between gas and solid in the differential section.

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By Walter Gaby

L. C. GRATON, Cambridge, Mass.-May I ask, in connection with one point in the summary, to what extent the author regards actinolite equivalent to tourmaline as an index of high-temperature and presumably magmatic conditions of deposition of the accompanying sulphides? W. E. GARY.-I merely advanced the idea that the mineral actinolite might have some such significance. In the copper deposit at Braden in South America, the ore occurs in an andesite breccia which is cemented by a matrix of sulphides, quartz, and tourmaline. Tourmaline is a high-temperature mineral, and when we find it associated with ores, these are regarded as having come from a volcanic or deep-seated source, hence a primary hypogenetic deposit. Thus we can count on greater continuation of the ore with depth than in some other kinds of deposit, and I thought that the actinolite, being also a high-temperature mineral, might have some such bearing in the case of Mount Morgan. I did not advance this idea as a final conclusion from a study of such phenomena, but thought that it might bear some discussion in view of the fact of the peculiar occurrence of this mineral in a notable orebody. It also occurs with the copper ores at Ducktown, Tenn., and in both cases may only be due to general regional metamorphism.

Jan 12, 1916

By Bjorn Bolviken

Bjorn Bolviken (Geochemist, Geological Survey of Norway, Trondheim, Norway)-Under the heading "Recognition of Anomalies," the author states, "If the frequency distribution is actually log-normal, the probability of these high values being part of the background population is small (less than 0.023 and 0.0013 for 2 and 3 standard deviation, respectively)." The figures quoted seem to be the probabilities of these high values being the mean rather than part of the background population unless "background" is defined as one single concentration. If the background is considered to be a statistical distribution of concentrations,50 (which is probably the case here since the author uses the term "background population"), the probability of any observed value being part of the background may be estimated through a calculation of the number of observed values that are in excess of (or below) the number expected to belong to the background. Apparently, some confusion exists in the literature regarding this point. Many authors accept the concept of background as being a statistical distribution, but do not seem to recognize the consequences of this concept. One of these consequences would be that the background of a chemical element should comprise any concentration between zero and a theoretical maximum, which is governed by the chemistry and mineralogy of the material

Jan 1, 1974

By John Tyssowski

IN 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temper-atures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several parti-cles had become one unit. From this dis-covery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the appli-cation of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper pro-duced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable

Jan 1, 1940

Following the declaration of a national emergency by the President on Dec. 16, 1950 the Office of Defense Mobilization was established with Charles Wilson as director. It has been obvious since the entry of Red China into the Korean War that the previous defense setup was not adequate for accelerated mobilization.

Jan 2, 1951

By Lewis V. Wade

U.S. Bureau of Mines efforts under longwall research programs to develop the capability to predict support requirements for longwall/ shortwall support systems are discussed. Ground control studies are being conducted in conjunction with several longwall/shortwall demonstration projects. Geologic, support performance, and strata behavior are being documented on these projects. A hypothesis is presented for the prediction of support requirements.

Jan 1, 1978

By Walter Weeks

THE process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. CASE I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the Joule-Thompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected.

Jan 1, 1937

CALAMINE is one of the semiminerals that have great similarity to the metals. It is a very heavy mineral earth of a yellowish color. It is found in Germany near the lead mines and in Italy in a mountain between Milan and Como. It is also found, as I have heard, in other places, as at Fosini in the territory of Siena. I believe that it is almost certain that some exists there because there are many other kinds of minerals there- about, although none is mined there in these times. But this does not mean that it could not be mined or that there is not some there that is real. Someone says that he med to melt what he could find with copper [36v]

Jan 1, 1942

By Thomas N. Walthier

If current trends continue, the shrunken world of exploration will keep on shrinking and the number of new mines will be insufficient to meet production requirements. Mineral shortages-not natural, but government induced-will then occur.

Jan 5, 1976

By G. Cartaud, F. Osmond

WE have already devoted two previous memoirs to this question. In the first we collated and discussed the existing literature on the subject; in the second, we described the crystalline forms obtained by the reduction, at different temperatures, of ferrous chloride by hydrogen or by zinc-vapor. The conclusion from these researches was that the three allotropic states of iron-a, stable below A2; 19, stable between A2 and A3; and 7, stable above A3-all crystallize in the cubic system. The differences observed were such as are customarily encountered in the crystallographic records of many minerals of which allotropic varieties or isomerides are not known, but did not conform to the ordinary definition of polymorphism. It is, however, improbable that allotropic transformations, which are placed beyond doubt by a series of positive facts, do not involve some changes in the intimate structure. As a matter of fact, the crystals we did obtain were too small to allow of a precise examination, and this might introduce an element of uncertainty in the firm establishment of our conclusions. Professor H. Le Chatelier was even led to think from some of our results that iron could very well be a rhombohedron simulating a cube, and not a true cube, and it will be remembered that the crystalline form of bismuth was for a long time incorrectly regarded as cubic. Allotropy does not, however, necessarily involve such a deduction. Without departing from the cubic system at all, a whole

Nov 1, 1906

By P. Ramakrishnan, Ramjilal

Fine powders of lead zirconate titanate have been prepared by three different methods such as ball milling, conventional coprecipitation and spray drying. Different powders have also been prepared by changing the process variables in each method. These powders were analysed for particle size chemical composition and reactivity. DTA, TGA and x-ray analysis have been carried out to study the lead zirconate titanate formation with reference to calcination temperatures. The calcined powders were then consolidated by compaction and sintering. An attempt has bean made to explain the consolidation behaviour of these powders on the basis of powder characteristics.

Jan 1, 1980

Jan 1, 1944

By G. M. Schwartz, J. N. Gundersen

John W. Gruner (Professor Emeritus, College of Science, Literature, and the Arts, Dept. of Geology, University of Minnesota, Minneapolis) — It is surprising that two men as well acquainted with the taconite rocks of the Mesabi District as Drs. J. N. Gundersen and G. M. Schwartz should have concluded that the taconite of the Eastern Mesabi before the intrusion of the Duluth gabbro consisted largely of quartz and magnetite. These minerals were "locally reconstituted" into "a wide variety of silicate mineral assemblages" by the gabbro. It is well known, of course, that the silicate mineralogy of the Eastern Mesabi ('about 14 miles in length) is quite different from that of the Main Mesabi which is over 60 miles long. The change from one to the other is abrupt and cannot be attributed to any other cause than the thermal effects of the gabbro. Are we to assume or believe that the taconite of the Eastern Mesabi was radically different from that of the Main range before the gabbro metamorphosed it?

Jan 1, 1962

By Barry S. Epstein

Financing the acquisition of a going coal mine operation has not had the exposure other finance-oriented projects have had. Therefore, C.I.T. feels that coal mining people and financial people should improve their understanding of the factors involved in this important type of acquisition. The discussion consists of two major subjects: analysis of the acquisition of the property, and sources and terms of funding the acquisition. Source and Terms of Funding There is a need to keep the competent medium-sized independent operator in the coal business, especially in these times of energy shortage. The creation of a resale market for coal mines encourages new investment in the coal mining business by medium-sized operators and their financial backers. Who provides debt and equity financing to acquire going coal mine operations and on what terms?

Jan 9, 1975

By John R. Wynnyckyj

Results of correlations between strength-development and sintering shrinkage occurring during induration are presented. A mathematical treatment of the shrinkage kinetics is, next, given and is based on the use of semi-empirical equations. The discussion stresses the significance of kinetic constants and activation energies in the assessment of iron ore concentrates for pelletizing and induration. Next, starting with the assumption that there is a need for parameters to characterize the iron-ore concentrates and relate these parameters to shrinkage-kinetic constants and balling behaviour, results of compaction measurements and pore structure characterization (mercury porosimetry) are presented and discussed.

Jan 1, 1977

By AIME AIME

HE State of Utah has an area of 84,990 sq. mi., and like other inland states in the West its population, although steadily increasing, is relatively small. The fact that it is a state possessing vast mineral resources is attested by a careful study of statistics which have been compiled by Federal and State investigators. Some idea of the extent of these resources and the degree of development of a particular state or region may be gained by such a study, but in the case of Utah statistics and other available information fail to portray completely the true extent and value of its existing metallic and non-metallic resources. The State is probably more widely known for its production of metallic ores which has placed it in an eminent position among the metal mining states of the Nation.

Jan 1, 1925

Jan 1, 1890

Jan 1, 1902

By Richard W. Brummett, Robert L. Dubms

Located some 180 miles east of Los Angeles in Riverside County, California, the Eagle Mountain mine supplies iron ore concentrates for the Kaiser Steel Corporation steel plant in Fontana, California, and for export to Japan. Although the deposits were first discovered in the early 1890's, no production was realized from the area until 1948 when Kaiser Steel Corporation commenced operations. A part of the large Basin and Range province, the Eagle Mountain area's geologic column comprises a thick series of metasediments resting on Precambrian gneisses and schists that have been intruded by sill-like masses of porphyritic quartz monzonite. The metasediments are composed of three quartzite units that are separated by a schistose meta-arkose and by two ore zones. They have been folded into a large east-west trending anticlinal structure that extends completely across the Eagle Mountains. The iron ore deposits occur in two well-defined horizons in the metasedimentary series, and they are found only along the north limb of the major anticline. Host rocks for the ore zones were a series of limestones and dolomites with associated quartzites. Magnetite plus pyrite comprised the primary mineralization that formed many replacement lenses and stringers of ore within the ore zones. The primary ore has been oxidized to hematite and goethite in a broad zone at higher elevations in the deposits. Hydrothermal alteration formed actinolite- tremolite granofels, local phlogopite, and minor tourmaline in the ore zones. This alteration and the ore deposition seem related to the same magmatic event that formed the porphyritic quartz monzonite intrusion

Jan 1, 1968