Search Documents

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury's3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell's rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800' and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,',' in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

Alexander N. Winchell, Butte, Mont. (communication to the Secretary): Mr. Spurr calls attention to the fact that an ore-deposit may be due to a succession of concentrations at different geological epochs. He cites an example of such a condition on Napoleon creek, a branch of Forty-Mile creek, Alaska. It will perhaps be of interest to call attention to another example of the same general character, not so remotely situated. The example referred to is located on Pole creek, a tributary of Cherry creek, in the extreme northeastern part of Madison county, Montana. An excellent geological map of this region is to be found in the Three Forks folio (No. 24) of the United States Geological Survey. According to this map, Pole creek, in its upper course, occupies the contact between the " Flathead " formation, which Peale correlates with the Middle and Lower Cambrian, and an area of gneisses and schists supposed

Jan 1, 1903

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

Jan 1, 1893

Jan 1, 1947

William Metcalf, Pittsburg, Pa. (communication to the Secretary*): I am greatly pleased that some one has at last reached what I have long regarded as the only rational explanation yet given of the reasons why steel hardens. Mr. Field claims originality; and doubtless he is entitled to it, but not to priority, mhich must be granted to Prof. John W. Langley.' The difference between them is that Langley says " Tension, probably molecular," and Field says " Tension, probably atomic "; in either case the vital thing after solution is tension. Mr. Field's argument carries with it the idea of increase of density with hardness; if he mill study the facts farther he will observe that the case is just the reverse; that is, the greater the hardness the less the specific gravity; it was just this fact that led Langley to his conclusion, in mhich I have always concurred. Field agrees with Langley that the first requisite for perfect hardening is complete solution of the carbon, not combination; and all of the facts agree with this conclusion. The fact that increase of hardness causes reduction of density was first brought to my notice some 40 years ago, when Major William Wade was testing Jones & Laughlin's cold-rolled iron, and I mas his assistant. We found the well-known increase of tenacity, compressive strength, torsional resistance, and hardness. Specific-gravity tests showed that the cold-rolled iron was less dense than the hot-rolled bars. Major Wade was so surprised at this result that he gave me a lot of samples to weigh, saying that he was not satisfied with

Jan 1, 1904

Jan 1, 1927

Jan 1, 1940

Jan 1, 1922

Jan 1, 1946

Jan 1, 1895

Jan 1, 1943

Jan 1, 1891

Jan 1, 1945

Jan 1, 1932