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By George J. Bancroft

AT the New York meeting of the Institute, April, 1907, I presented a paper entitled, The Formation and Enrichment of Ore-Bearing Veins,1 in which paper I advanced the following propositions (1) That the majority of mineralized veins are the product of expiring vulcanism ; (2) that most of these veins were primarily mineralized by comparatively rich solutions in comparatively short periods of time; (3) that the solutions gained their metal-values from a comparatively rich source; (4) that there is a barysphere containing large amounts of the useful metals; (5) that eruptions spring from various depths and bring various kinds of magmas towards the surface; and (6) that only those eruptions which disturb the barysphere and bring a magma rich in metals sufficiently near the surface to be leached by vein-making solutions are productive of valuable ore-deposits, other eruptions producing barren veins. Ore-deposits due to magmatic segregation were not included in this general survey. As a result of considerable further study I have modified my views in some respects, while in others I feel more sure than ever of the ground taken at that time. That ore-bodies are infrequent occurrences and born of extraordinary conditions I think is now generally accepted. The theory that persisted for a time-namely, that ore-bodies were formed by the ordinary ground-water, which consists of extremely dilute solutions, derived from leaching extremely lean surface-rocks, and which must occupy enormously long periods of time in concentrating the values so leached, is, I think, now pretty generally regarded as not applicable to the great majority

Jan 1, 1913

JOHN.B. HASTINGS, Los Angeles, Cal. (written discussion).-This paper reminds me that when I had an option on a Nevada mine, where the only orebodies assayed $4 gold, I went to San Francisco to learn the cost of putting broken ore in a 25-ft, vein on the mine cars, and sought Mr. Alfred Wartenweiler, who said "There is not a mine in California that can tell what it costs to move ore in the stopes." When building small mills in the mountains, and with only 30 or 40 employees, by entering in a log at night the work performed by each man, I have been able to plot the costs with the accuracy shown in this paper, and very good discipline it is. Cost of new construction and repairs is carefully kept by most companies, and is compiled after completion; probably the outlay of labor and material in pieces of work sufficiently important to call for blueprints is estimated beforehand, but numberless odd jobs of construction and repairs are so itemized. . Might it not be worth while, at a large plant, to have these smaller daily tasks described in advance in a central repair office, and then let inspectors look over the job, report time and material needed, and enter it in sufficient detail in proper ledgers, the men then being sent to accomplish it, and reporting when finished? The forecasts would soon be made quickly and correctly and would give the head mechanic, carpenter, and electrician easy supervision of their men, and the results could be seen at a glance by the managers.

Jan 4, 1918

By Eben E. Olcott

The Mine.-For some years attention has been drawn to the copper deposits of the Appalachian range of mountains, and especially to those in that portion crossing the corners of Virginia, North Carolina, and Tennessee. Certain it is that in many places in this locality available deposits of copper await the miner, and one after another are being opened and worked. The parts of these three States alluded to are but sparsely settled, and communications are insufficient to meet the demand for transportation. Railroads are wanted, as the existing wagon roads are unfitted for heavy hauling; these circumstances increase very much the difficulties in the way of mining enterprises. Notwithstanding this, the success of some of the mines of this section is an established fact, and Ducktown has for some years held a high rank among the copper-producing localities of the United States. Of all these deposits, however, none is more interesting or more deserving of attention than the one now under consideration. The works of the Ore Knob Copper Company have been energetically pushed forward, since the reopening of the mine, in the spring of 1873, by Mr. J. E. Clayton, the superintendent and one of the chief owners of the property, and if one thing more than another can insure success it is the combination in this gentleman of rare business capabilities with the deepest personal interest in the pros¬perity of the undertaking. The copper vein -at Ore Knob* is a clearly defined fissure traversing the gneissic rocks of Pre-silurian age in a direction 61° east of north. * The reader is referred to a paper by Dr. T. Sterry Hunt, in the second volume of the Transactions of the Institute, on the "Ore Knob Mine, and some related Deposits," pages 123 to 129.

Jan 1, 1875

By B. J. Dotson, P. N. McCreery, R. L. Slobod, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By P. N. McCreery, R. L. Slobod, B. J. Dotson, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

Clarence M. Haight, Franklin Furnace, N. J. (communication to the Secretary*).—In that part of Mr. Wilson's paper describing the Gilman cut-and-fill system, a few features do not appear to be fully explained. In what way is the waste used for filling obtained? The text mentions that if waste is encountered when driving the filling raises, these raises are stopped until the fill is needed; that seems to suggest mining the capping for fill, which might make the backs of the stopes bad as the stopes approach the top of the ore. If, on the other hand, the fill is brought to the raises in cars, are the crosscuts that are necessary in ore or waste? Is the cost of this fill included in the stoping costs given? The second, or lower, series of stopes will present a different problem to that which the first series (under the capping) gave. Although no mention is made in the text, it would seem that the second series of stopes will have to be worked on center lines which are offset half the stope width, 20 ft., from the centers of the stopes above, in order to take advantage of the "rafter" effect of the stringers so named. How is the fill to be introduced into the lower stopes? There are no crosscuts mentioned to provide for this; or is it intended to tap the filled stopes above for the fill? In the latter case the method of control of this fill will be of interest. Ore that will admit of a stoping width of 40 ft. with the lengths mentioned in the description is stronger than any with which many mining men are familiar. Has the practice of starting to mine a second stope before the preceding one is filly completed been tried to any extent? If

Jan 1, 1917

By W. S. Ayres

I AM well aware that this subject is not strictly in the line of mining engineering, yet as it is a subject with which mining engineers at times have something to do, I have thought, perhaps, it might not be wholly out of place to communicate to the Institute something of the method used in determining deflection, and of its final issue. Having felt a need of some simple formula for determining the deflection of girders of uniform cross-section under any load, I have been led through the counsel of Mr. Frederick J. Slade, to whom I am indebted for many suggestions, to undertake a labor of which I shall in this paper give only some of the most important features. The results arrived at agree with those obtainable from the received formula; of Weisbach, Rankine, and others, but the expressions given by these authors, and by all others that I have at hand, are of such a form that they are not easily applied by those whose higher mathematics have become rusty from disuse, and they require, moreover, too much labor in their application to be of practical value. The general formula that I have adopted is similar to that given by Rankine, and is deflection = [mWl3 -El], in which l is the span, W the total load, E the modulus of elasticity, I the moment of inertia of the uniform cross-section of the girder, and m a factor depending for its value on the mode of distribution of the load. The problem then is to find the value of this factor m in the formula, and for some distributions of the load it leads to a number of mathematical difficulties. In this place I shall consider first the girder to be loaded symmet-

Jan 1, 1877

By W. F. Rogers, J. A. Stewart, P. J. Kalish, E. O. Bennett

Detailed descriptions are given of materials, apparatus and the experimental procedure used to study the effect of bacteria on sandstone permeability. The factors affecting permeability during injection of bacterial suspensions which have been investigated are: (I) concentration of bacteria; (2) core permeability and median pore size; (3) species of bacteria, mode of aggregation and relative size; (4) injection rate or pressure differential; (5) mean pressure; and (6) depth of penetration of bacteria. The investigation demonstrated that bacteria cannot reduce core pertneability to zero and that their effect on permeability is subject to definite limitations. Remedial or permeability restoration studies also were made. Acidization in combination with reverse flow war found to be an effective method for restoring permeability In cores partially plugged with bacteria. The relationship between the bacterial quantities in the laboratory tests and those found in field operations is discussed. The linear laboratory flow data have been translated into terms of field radial systems; these data indicate the most practical methods of maintaining injection rates in the presence of bacteria are to increase injection pressures or hydraulically fracture the formation. INTRODUCTION It has long been known that various bacteria flourish in the above-ground components of oil field water-injection systems. The presence of these bacteria has led to the suspicion that they might enter into the causes for reduction of injection well permeability, but only recently has an attempt been made to describe the effects quantitatively.1 Biocides are used in many cases without a firm knowledge as to whether the bacteria are killed, or if they are, whether the dead cells affect formation permeability. This project was undertaken as part of a study to determine the effect of bacteria, residual oil and precipitated solids such as iron sulfide or calcium carbonate on the permeability of sandstones and to learn whether any of these materials adversely affect brine injectivity in secondary recovery or disposal operations. This report deals with that portion relating to the effect of bacteria. MATERIALS CORES Three different permeability ranges of Berea sandstone cores were used in the study. The range of initial, absolute brine permeabilities kj were: high — 278 to 400 md: medium—130 to 162 md; and low—17.7 to 48.3 md. The permeability data for the cores used in the tests are included in Table 1. All cores were cut to a nominal 1 in. diameter. Following air permeability determinations, they were molded with an epoxy resin in 1.5 in. ID aluminum sleeves. The sleeves had drilled and tapped holes for intermediate pressure connections along the length of the cores. After molding, the high- and medium-permeability cores were trimmed to 4 in. in length and the low-permeability cores to 2 in. These lengths resulted in pore volumes of approximately 10.9, 10.4 and 4.4 ml, respectively, for the high-, medium- and low-permeability cores. Pressure-transmitting channels were drilled through the plastic into the core proper, using the sleeve holes as drill guides. Width and depth of channel penetration into the core proper were approximately 0.03 in. and 0.05 in., respectively. Three pressure taps were used with all cores; for the high- and medium-permeability cores the taps were spaced 1 in. apart; for the low-permeability cores the taps were spaced 0.4, 0.8 and 1.2 in. from the inlet end. Pore size distributions were calculated from restored-state capillary pressure curves for representative cores in each of the three permeability ranges. In each case the pore size range with the greatest percentage of the pore space included the very small pores up to 0.5 micron in radius. The median pore radii were in the 5.5 to 6 micron range for the high-permeability cores; in the 4.5 to 5 micron range for the medium-permeability cores; and in the 3.5 to 4 micron range for the low-permeability cores.

Jan 1, 1965

"The Southern Cross mining district was discovered during the early rush of gold seekers over Montana following the discovery of gold in 1861. Placers were worked near the Atlantic Cable mine in 1866, and soon attention was turned to quartz lode mining. High grade ores were discovered in the North Atlantic claim, adjoining the present Southern Cross group. The early metallurgical treat¬ment of these ores was by means of arrastres, a crude form of amalgamating mill, illustrated on the page opposite. This old arrastre located by the roadside on Warm Springs creek, was built by Barker Bros. in 1879. Further discoveries overtaxed the capacity of this plant, and in 1875 Thomas' Stuart employed a contractor named Jeptha J. Corner to convert the old Wilson & Fifer sawmill located at the Big Spring into an up-to-date gold quartz mill. 'For this trans¬formation Corner received the sum of $1,400.00. The illustrations give a good idea of the nature of its construction. Practically no iron was used in the mill, excepting for the stamps, dies and cams and cam shafts. Whether or not the saving attained reached the limits of present day perfection is not known. There being no steam boilers available, the early prospectors believed in the principle of conservation of fire wood, water power was therefore used, generated by a ""direct-connected"" over-shot wheel. Water for power purposes was supplied by the nearby spring. History fails to record the tonnage treated in this relic of early Montana milling practice.The ores of the Southern Cross district have not proved readily amenable to mill treatment, but being largely composed of iron oxides, they are most desirable fluxing ores for smelter operations. The B. A. & P. Ry. extends into the district. Electric power is furnished by the Flint Creek 'station, three miles distant."

Jan 1, 1913

By M. O. Holowaty, C. M. Squarcy

Blast furnaces are the tools of men, and it is men who have made them great. Here is presented the story of the Ironmakers-the men who first poured hot metal into what would someday be the sinews of a nation. W HEN the Jacobean merchant adventurers bade farewell to the first ship of colonists sailing for the new land, they instructed them to direct all their skill and energy to grow silk worms in Virginia. The adventurers felt sure that they could flood the market with highly priced and much desired goods like silk, sugar, tea, and indigo. They were also convinced that they would fill the needs of the mother country for iron. Early iron production in the colonies The merchants certainly had a wonderful imagination, for silk and indigo were just as exotic in Virginia as they were in England. The settlers found it more profitable to raise tobacco on the vast stretches of the free, fertile land. Thus the plans of settlers clashed with those of The Virginia Co.; and only point of agreement was the desire to produce iron. But, even there the motives of the settlers and those of The Virginia Co. of London were worlds apart. The settlers wanted to produce the tools badly needed in the colony, while the Company desired to cash in on the rising demand for iron which the home industry could not satisfy. Both the settlers and the Company lost no time trying to find iron ore. Locations of the early mines are not known. If, however, the reports of the Irishman, Francis Maguel, can be trusted, as early as 1609 a ship sailed for England with a load of 17 tons of crude iron which the East India Co. purchased at £ 4 per ton. The iron was of excellent quality and considered the best iron made of non-English ore that was ever purchased.

Jan 1, 1961

By George J. Bancroft

At the New York meeting of the Institute, April, 1907, I presented a paper entitled, The Formation and Enrichment of Ore-Bearing Veins,' in which paper I advanced the following propositions: (1) That the majority of mineralized veins are the product of expiring vulcanism; (2) that most of these veins were primarily mineralized by comparatively rich solutions in comparatively short periods of time; (3) that the solutions gained their metal-values from a comparatively rich source; (4) that there is a bary-sphere containing large amounts of the useful metals; (5) that eruptions spring from various depths and bring various kinds of magmas towards the surface; and (6) that only those eruptions which disturb the barysphere and bring a magma rich in metals sufficiently near the surface to be leached by vein-making solutions are productive of valuable ore-deposits, other eruptions producing barren veins. Ore-deposits due to magmatic segregation were not included in this general survey. As a result of considerable further study I have modified my views in some respects, while in others I feel more sure than ever of the ground taken at that time. That ore-bodies are infrequent occurrences and born of extraordinary conditions I think is now generally accepted. The theory that persisted for a time—namely, that ore-bodies were formed by the ordinary ground-water, which consists of extremely dilute solutions, derived from leaching extremely lean surface-rocks, and which must occupy enormously long periods of time in concentrating the values so leached, is, I think, now pretty generally regarded as not applicable to the great majority

Jan 1, 1910

By A. Perry Thompson

Discussion of the paper of A. PERRY THOMPSON, presented at the San Francisco meeting, September, 1915, and printed 'in Bulletin No. 100, April, 1915, pp. 645 to 677. ARTHUR S. EAKLE, Berkeley, Cal.-At the old Morning Star mine in Alpine County, where large masses of enargite were found some years ago, I looked particularly for evidences of replacement of pyrite by the enargite. While I have not made a particular study of any of the specimens, I judge that the pyrite and enargite were precipitated together. They were both primarily in those rocks. Of course, by using Mr. Graton's method of determination we might possibly find a situation somewhat different, but I should say that the enargite is not replacing the pyrite, but was simply precipitated at the same time. The bodies occurred there within 50 ft. of the surface, so it is probably not a case of secondary enrichment. H. W. TURNER, San Francisco, Cal.-In the case where secondary chalcocite shows a crystalline structure and cleavage lines, what is the evidence of the secondary nature of it? C. F. TOLMAN, Stanford University, Cal.-You can find practically all the evidences we have discovered in the microscopic study of ores. You can find all stages in the process of replacement of earlier minerals, especially bornite, by chalcocite, from a stage, in which the process has but just started with only occasional fragments of chalcocite set in bornite, to a stage where remnants of bornite are set in chalcocite. The replacement may take place along the cleavage lines or along the crystallographic directions of the earlier mineral, or it may take place irregularly. In one type of replacement you may find in one spot a few cross-cutting veins, and in another spot the latter may be so enlarged that there remain only a few individual specks of the replaced mineral.

Jan 12, 1915

By Stanley M. Jarrett

Operating one of the world's largest underground copper mines, Braden Copper Co. has been able to reduce its total accident frequency rate per million manhours by 84 pct, from 27.4 pct in 1945 to 4.45 pct for the first ten months of 1958. It has also won the Inter-American Safety Trophy for 12 consecutive years. The record may seem to indicate a secret formula, but there is none. The results stem only from hard work, and more and more of it.

Jan 11, 1959

In many lines of engineering, much excellent standardization work had been done before the war but the war emphasized its importance and showed most clearly the need of cooperation to prevent the confusion caused by the promulgation of overlapping standards by independent bodies. The American Institute of Mining and Metallurgical Engineers, American Institute of Electrical Engineers, American Society of Civil Engineers, American Society of Mechanical Engineers, and American Society for Testing Materials, recognizing the value of what had been done, invited the Government Departments of War, Navy and Commerce to appoint representatives to act with them to continue this work; the body so formed is the American Engineering Standards Committee. It has required time to definitely formulate its objects and to arrange methods for accomplishing them that would be effective without interfering with the many organizations that have been doing such excellent work in this line. The American Engineering Standards Committee has just completed and adopted a revision of its Constitution, which has been sent to the Governing Boards of all the Departments and Societies represented on the Committee with a request for its ratification. The new Constitution changes the name to American Engineering Standards Association as more fittingly indicating the wide scope of the interests involved. The objects of the association are stated as follows: 1. To unify and simplify the methods. of arriving at engineering standards, to secure cooperation between various organizations and to prevent duplication of standardization work. 2. To promulgate rules for the development and adoption of standards, 3. To receive and pass upon recommendations for standards submitted as provided in the Rules of Procedure, but not to initiate, define, or develop the details of any particular standard. 4. To act as a means of intercommunication between organizations and individuals interested in the problems of standardization. 5. To give an international status to approved American engineering standards. 6. To cooperate with similar organizations in other countries and to promote international standardization.

Jan 7, 1919

By V. R. Garfias

Although the work on which this paper is based was carried on by the writer as Special Commissioner of the Petroleum Department of the Mexican Government, the opinions expressed are only his personal views for which the Mexican Government can in no way be held responsible. Notwithstanding that the appointment covers all phases of the so-called petroleum question, as the one question of immediate importance was that relating to taxation, it was decided to devote all the time to this phase of the work. The present report has been divided into two closely related parts, the first dealing with the production and marine transportation of Mcxican petroleum, and the second, with the Mexican taxation on petroleum and its products. The writer wishes to acknowledge the loyal cooperation rendered by Mr. M. C. Ehlen, who had charge of the statistical work, and by Miss S. Stern and Messrs. E. P. Heiles and J. E. Morrissey. The aim throughout the work has been to pave the way for a thorough understanding between the Mexican Government and the oil operators and to present a true and clear statement of facts relating to the questions at issue. Mexican Oil Fields Development The salient features in the development of the Mexican oil fields may be summarized as follows: 1901. First commercially productive well in Ebano field. 1902. Tehuantepee field came in; Diaz Government granted concession to Pearson & Son on practically all Federal lands along the Gulf of Mexico. 1907. First producing well in the Furbero field. 1908. Dos Bocas well caught fire, advertising tremendous productivity of Southern oil fields of Mexico.

Jan 1, 1921

By W. K. Lewis, Lombard Squires, W. I. Thompson

The authors presented an article2† last year on colloidal properties of clay suspensions in which they attempted to sustain the position that the behavior of clay suspensions is due primarily to the mechanical interference of the platy particles, the nature and extent of the interference being profoundly influenced by the character of the surfaces of the particles, which in turn is determined primarily by the nature and amount of adsorbed foreign materials held on the surface of the particles by forces which are predominantly chemical in type. The following discussion is a continuation of that article to extend these same interpretative points of view to the behavior of clay gels. Insight into the mechanism of gelation is certainly of outstanding importance in the handling of drilling muds. In the former article it was suggested that the thin, flat plates that constitute the ultimate clay particles may build up aggregates by the overlapping of the ultimate plates face to face much longer and perhaps also much wider than the ultimate plates themselves, but not appreciably thicker. Exhaustive microscopic examinations of characteristic clays show no tendency for the larger particles, clearly visible under the microscope, to orient themselves in this way. It is true that the gelation of the clays is due primarily to the smallest particles, unresolvable other than by the ultramicroscope, so that the possibility of the deve1opment by them of an overlapping structure is not excluded. Furthermore, as one approaches the limit of resolving power of the microscope, the difficulty of observing accurately the shapes and relative positions of particles incresses excessively. However, in the absence of any observable tendency toward overlapping orientation of the large, visible particles, one hesitates to ascribe such a tendency to the smaller particles beyond the range of visibility. Should it develop that one must exclude the assumption of overlapping orientation, the explanations offered in the previous article are changed in only one respect; namely, one would now have to assume that the ultimate particles themselves have length, and probably also width, very large in comparison with their thickness.

Jan 1, 1936

By Lombard Squires, W. K. Lewis, W. I. Thompson

The authors presented an article2† last year on colloidal properties of clay suspensions in which they attempted to sustain the position that the behavior of clay suspensions is due primarily to the mechanical interference of the platy particles, the nature and extent of the interference being profoundly influenced by the character of the surfaces of the particles, which in turn is determined primarily by the nature and amount of adsorbed foreign materials held on the surface of the particles by forces which are predominantly chemical in type. The following discussion is a continuation of that article to extend these same interpretative points of view to the behavior of clay gels. Insight into the mechanism of gelation is certainly of outstanding importance in the handling of drilling muds. In the former article it was suggested that the thin, flat plates that constitute the ultimate clay particles may build up aggregates by the overlapping of the ultimate plates face to face much longer and perhaps also much wider than the ultimate plates themselves, but not appreciably thicker. Exhaustive microscopic examinations of characteristic clays show no tendency for the larger particles, clearly visible under the microscope, to orient themselves in this way. It is true that the gelation of the clays is due primarily to the smallest particles, unresolvable other than by the ultramicroscope, so that the possibility of the deve1opment by them of an overlapping structure is not excluded. Furthermore, as one approaches the limit of resolving power of the microscope, the difficulty of observing accurately the shapes and relative positions of particles incresses excessively. However, in the absence of any observable tendency toward overlapping orientation of the large, visible particles, one hesitates to ascribe such a tendency to the smaller particles beyond the range of visibility. Should it develop that one must exclude the assumption of overlapping orientation, the explanations offered in the previous article are changed in only one respect; namely, one would now have to assume that the ultimate particles themselves have length, and probably also width, very large in comparison with their thickness.

Jan 1, 1936

By C. D. Hunter, J. B. Browning

During the year 1934, Kentucky oil and gas operators have partly overcome their past depression fears and in the oil industry, with possibly more abandonments of old oil producers than the completion of new oil wells, produced 4,814,904 bbl. of oil in 1934 against 4,501,511 bbl. in 1933. In the gas industry of eastern Kentucky, 115 gas wells were completed during 1934. This production is delivered through two 20-in., one 16-in., one 12-in., one 10-in., and two 8-in. pipe lines to supply both domestic and industrial markets in Cincinnati, Ohio; Louisville, Lexington, Frankfort, Winchester, Ashland, Covington and other Kentucky towns; Washington, D.C., and other eastern cities. The largest percentage of these gas wells and production are from the Devonian black shale area of Floyd, Pike, Knott, Martin and Magoffin counties, Kentucky. In this area the largest percentage of 1889 wells, developing 421,-215 acres, has been completed in the past 10 years, of which 55.3 per cent produce from the 400 to 550 ft. of Carbonaceous Devonian black shales. The successful results obtained from these Devonian shales are due to the physical effects of the 5000 to 6000 lb. of gelatinated nitroglycerin with which the entire 400 to 550 ft. of shale is shot. A very small number of the shale wells are natural producers and do not require shooting. Other than the Devonian shale gas production, the remaining 44.5 per cent of the gas in this field is encountered throughout the entire strati-graphic section above this horizon; namely, salt sands of Pennsylvanian age and Maxon, Big Lime and Weir of Mississippian Age. A very small percentage is encountered in the Corniferous Devonian lime and the Silurian Big 6 below the black shales. In western Kentucky, in the counties of Henderson, Webster, Hopkins, McLean, Christian, Muhlenburg, Ohio, Daviess, Hancock, Brecken-ridge, Hart, Barren and Warren, many gas wells have been completed, but, because of insufficient market, activity has been somewhat desultory. The area is served by the pipe lilies of the Kentucky Natural Gas Corporation, with headquarters at Owensboro. Their market is increasing and the gas is delivered to Owensboro, Henderson, Madisonville, and many

Jan 1, 1935

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By Jose A. Ruiz

INTRODUCTION For heterogeneous non-catalytic solid-gas reactions carried out in fluidized bed reactors, nominal bed temperature is an average value between gas and solid. For highly exothermic reactions, actual particle temperature can be up to hundred degrees above termocouple temperature, since heat dissipate at slower rate than heat generation during some steps of transformation. These micro instabilities at particle level can displace thermodynamic equilibrium from the desired phase to others. This effect is important when relatively narrow range of phase stability exists, like in sulphation roasting of sulphides, where bed discharge contains, in addition to the desired sulphate others metastable phases such as basic sulphate and ferrite. For example, for copper-iron sulphide concentration roasted below 680°C, no cupric ferrite is formed, as shown by Jakob et al., therefore the separate Kellogg's stability phase diagrams Cu-S-O represent the roasting (Fig.l). At temperature above this one, like 760°C for example, phase stability changes from CuSO4 to the basic sulphate Cu0•CuSO4. Solid state reaction between Cu0•CuSO4 and Fe203 also occurs to form cupric ferrite, Cu0•Fe2O3, therefore the Cu-Fe-S-O Kellogg's phase diagram of Fig. 1 (continuous line) represents this condition of roasting. Although both Cu0•CuSO4 and Cu0•Fe2O3 are metastable phases under normal operating conditions of sulphation roasting(1-10% SO2, 1-10% 02 and 680°C, points A and B,Fig. 1) sulphation of these species and particularly ferrite are slow and limited due to diffusional control. This explain why reactors discharge contains several phases: CuSO4, Cu0•CuSO4, CuO•Fe203 plus small amounts of CuS and FeS due to the baclonixed conditions of fluidized bed reactors. The presence of cuprous ferrite due to reducing conditions inside individual particles also occurs, but in very limited extent at the reaction interface, as it is demonstrated by the low soluble iron levels of calcines. On the other hand, the presence of cupric ferrites can be explained only due to the higher temperature achieved by particles, since below 680°C cupric ferrite formation does not take place. [ ] This phenomena also occurs for others non-ferrous metal sulphides concentrates roasted under sulphation conditions, such as 7n, Co and Ni. Therefore the prediction of discharge composition of fluidized beds is not possible based only on kinetics and mechanistics models alone or purely thermodynamical considerations, since all factors should be integrated to describe the overall phenomena. SINGLE PARTICLE TRANSFORMATION Assuming a first order reaction with respect to the gas and zero for solid, such as

Jan 1, 1984