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By W. E. Stiles

A method is presented for predicting the performance of water flooding operations in depleted, or nearly depleted, petroleum reservoirs. The method makes use of permeability variations and the vertical distribution of productive capacity. From these two parameters can be calculated the produced water cut versus the oil recovery. Derivations of the mathematical analogy is shown and sample calculations and curves of prediction are presented. Comparison is made of the predicted and actual performance of a typical 5-spot in an Illinois water flood. INTRODUCTION The use of water as a flooding medium in both depleted and "flush" oil reservoirs is gaining greater recognition and acceptance. Many of the shallower fields, depleted by primary production, have been and are being subjected to water injection in order to obtain some part of the large volume of oil remaining after primary production. Some of the earlier water flood installation proved highly discouraging and the value of water flooding was often questioned. Many of these earlier floods were haphazardly selected and developed as little was known of the physical characteristics and contents of the producing formations. The prior evaluation of the flood performance was impossible. During the past decade the development of the required reservoir engineering tools-—core analysis, reservoir fluid analysis, electric logs, fluid flow formulae, etc.—has allowed the engineer to construct and apply the methods which are presently being used to evaluate the economic and mechanical susceptibility of a reservoir to flooding. This discussion will present a method for taking into account the effect of permeability variations in predicting the performance of water floods in depleted reservoirs. PERMEABILITY AND CAPACITY DISTRIBUTION It is generally agreed by most investigators that in a single phase system fluid will flow in a porous and permeable medium in proportion to the permeability of the medium. Producing formations are usually highly irregular in permeability, both vertically and horizontally. However, zones of higher or lower permeability are often found to exhibit lateral continuity. Thus, while structurally comparable stringers in adjacent wells may differ several fold in permeability values, they usually bear resemblance as being part of a general continuous higher or lower permeability section. It is generally agreed that where such stratification of permeability exists, injected water sweeps first the zones of higher permeability, and it is in these zones that "break-through" first occurs in the producing well. It is a basic assurnption of the presently described method that penetration of a water front follows the individual permeability variations as if such variations were continuous from input to producing well. This is admittedly not rigorously true, but can be justified as making possible a simplifying mathematical approach to an otherwise extremely complicated three dimensional flow problem. As a basis for study of the lateral flow of fluids in formations of irregular permeability, the irregularities may be conveniently represented by a permeability distribution curve and a capacity distribution curve. In obtaining these curves, the permeability values, regardless of their structural position in the formation, are rearranged in order of decreasing permeability. If these permeability values so arranged are plotted against the cumulative thickness, a permeability distribu- tion curve is obtained. This curve may then be likened to a "smoothed" permeability profile of the formation. In making comparison between different distribution curves it is convenient to state the permeabilities in terms of the ratio of the actual permeability values to the average permeability of the formation. These ratios termed "dimensionless permeabilities", are used in this paper rather than the permeabilities in terms of millidarcys. The capacity distribution curve is a lot of the cumulative capacity (starting with the highest permeabilities) versus the cumulative thickness. The capacity and thickness are given as fractions of the total capacity and thickness. Mathematically, the capacity distribution is the intergration of the permeability distribution curve. In practice it is convenient to first obtain the capacity distribution curve and derive from it a smoothed dimen-sionaless permeability curve. The method of obtaining the capacity distribution curve is illustrated in the successive column of Table 1, in which capacity and thickness are derived as fractions of their respective totals. If only a small number of permeability values are available, it is generally desirable to smooth the resultant curve. This has been done to give the capacity distribution curve shown in Figure 1. The differentiation of the capacity distribution curve to obtain the permeability distribution curve is shown in Table 2. Here, the capacity values are read from the smoothed curve at intervals of cumulative thickness, and the increments of capacity are divided by the increments of thickness to obtain the dimensionless permeability, K. Due to this stepwise procedure of calculation these premeability values must be plotted at the midpoints of the successive increments of thickness. The curve so obtained from these data is shown in Figure 1. The total area under the K' curve is equal to unity.

Jan 1, 1949

By W. E. Stiles

A method is presented for predicting the performance of water flooding operations in depleted, or nearly depleted, petroleum reservoirs. The method makes use of permeability variations and the vertical distribution of productive capacity. From these two parameters can be calculated the produced water cut versus the oil recovery. Derivations of the mathematical analogy is shown and sample calculations and curves of prediction are presented. Comparison is made of the predicted and actual performance of a typical 5-spot in an Illinois water flood. INTRODUCTION The use of water as a flooding medium in both depleted and "flush" oil reservoirs is gaining greater recognition and acceptance. Many of the shallower fields, depleted by primary production, have been and are being subjected to water injection in order to obtain some part of the large volume of oil remaining after primary production. Some of the earlier water flood installation proved highly discouraging and the value of water flooding was often questioned. Many of these earlier floods were haphazardly selected and developed as little was known of the physical characteristics and contents of the producing formations. The prior evaluation of the flood performance was impossible. During the past decade the development of the required reservoir engineering tools-—core analysis, reservoir fluid analysis, electric logs, fluid flow formulae, etc.—has allowed the engineer to construct and apply the methods which are presently being used to evaluate the economic and mechanical susceptibility of a reservoir to flooding. This discussion will present a method for taking into account the effect of permeability variations in predicting the performance of water floods in depleted reservoirs. PERMEABILITY AND CAPACITY DISTRIBUTION It is generally agreed by most investigators that in a single phase system fluid will flow in a porous and permeable medium in proportion to the permeability of the medium. Producing formations are usually highly irregular in permeability, both vertically and horizontally. However, zones of higher or lower permeability are often found to exhibit lateral continuity. Thus, while structurally comparable stringers in adjacent wells may differ several fold in permeability values, they usually bear resemblance as being part of a general continuous higher or lower permeability section. It is generally agreed that where such stratification of permeability exists, injected water sweeps first the zones of higher permeability, and it is in these zones that "break-through" first occurs in the producing well. It is a basic assurnption of the presently described method that penetration of a water front follows the individual permeability variations as if such variations were continuous from input to producing well. This is admittedly not rigorously true, but can be justified as making possible a simplifying mathematical approach to an otherwise extremely complicated three dimensional flow problem. As a basis for study of the lateral flow of fluids in formations of irregular permeability, the irregularities may be conveniently represented by a permeability distribution curve and a capacity distribution curve. In obtaining these curves, the permeability values, regardless of their structural position in the formation, are rearranged in order of decreasing permeability. If these permeability values so arranged are plotted against the cumulative thickness, a permeability distribu- tion curve is obtained. This curve may then be likened to a "smoothed" permeability profile of the formation. In making comparison between different distribution curves it is convenient to state the permeabilities in terms of the ratio of the actual permeability values to the average permeability of the formation. These ratios termed "dimensionless permeabilities", are used in this paper rather than the permeabilities in terms of millidarcys. The capacity distribution curve is a lot of the cumulative capacity (starting with the highest permeabilities) versus the cumulative thickness. The capacity and thickness are given as fractions of the total capacity and thickness. Mathematically, the capacity distribution is the intergration of the permeability distribution curve. In practice it is convenient to first obtain the capacity distribution curve and derive from it a smoothed dimen-sionaless permeability curve. The method of obtaining the capacity distribution curve is illustrated in the successive column of Table 1, in which capacity and thickness are derived as fractions of their respective totals. If only a small number of permeability values are available, it is generally desirable to smooth the resultant curve. This has been done to give the capacity distribution curve shown in Figure 1. The differentiation of the capacity distribution curve to obtain the permeability distribution curve is shown in Table 2. Here, the capacity values are read from the smoothed curve at intervals of cumulative thickness, and the increments of capacity are divided by the increments of thickness to obtain the dimensionless permeability, K. Due to this stepwise procedure of calculation these premeability values must be plotted at the midpoints of the successive increments of thickness. The curve so obtained from these data is shown in Figure 1. The total area under the K' curve is equal to unity.

Jan 1, 1949

Jan 1, 1966

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By David B. Burrows, Francis R. Conley

INTRODUCTION A prerequisite to the evaluation and management of oil properties is accurate information derived from the analysis of core samples; but reliable data, such as porosity and permeability, can result only if all oil and water have been removed from the core samples analyzed. The most common method of core cleaning used to date has been Soxhlet extraction—a somewhat static technique, which depends upon the slow diffusion of hot solvent through the core sample. Soxhlet extraction performs satisfactorily only with highly permeable samples and at best requires long cleaning periods. The centrifuge method was developed in 1951 by Continental Oil Co. to overcome the inefficiencies inherent in the Soxhlet method. The new method is basically an operation in which hot solvents are caused to flow through the samples under the influence of centrifugal force. The centrifuge unit has proved so successful that samples which formerly required days for partial extraction can now be completely cleaned in approximately one hour. The original idea was conceived in 1950 by Elmer S. Messer, whose early experiments consisted of flowing solvent over sandstone samples suspended in a revolving basket and driven by a vertically mounted vacuum cleaner motor. Results were so outstanding that more permanent units were constructed. A modified model using this basic design was recently built by Core Laboratories, Inc., and is now used regularly in their operations. DESIGN Fig. 1 shows a photograph of the two extractors routinely used to clean small core plugs in the Production Research Div. of Continental Oil Co.'s Ponca City laboratories. For illustrative purposes, the basket from one of the units has been removed, and because both extrac- tors are of identical design only one is described in the following discussion. Each extractor unit consists of a centrifuge and a solvent still. The core basket of the centrifuge is made of mild cold rolled steel 7 1/2 in. in diameter and 1 1/8 in. deep. The basket holds 18 1-in. samples (cubical or cylindrical) and is attached directly to a cone fitted to the shaft of the motor. Both the outer rim and the hollow hub of the basket contain perforations for the passage of solvent and extract. The solvent is delivered to the perforations by means of a copper tube inserted into the hollow hub. The motor is a vertical tool post grinder motor; (115 v, 5.6 amp, 0-60 cycles, AC-DC, rated at 1/3 hp). It has a rated speed of 10,000 rpm under full load and 15,000 rpm with no load. Variation of speed is obtained by the use of a variable transformer. The solvent still was constructed from one end of a stainless steel oxygen bottle by inserting a heating element, sight glass, and piping as shown on the schematic diagram, Fig. 2. The heater used was a three-position, 1,000 w, 115-v, immersion type. Intermittent flow of solvent to the centrifuge is obtained by means of a siphon bottle inserted between the condenser and the centrifuge.

Jan 1, 1957

By Frank C. Smith

THE following article covers the history of a metallurgical campaign, commenced in March, 1905, at the mines of the Socorro Gold Co., in the so-called desert region of Yuma county, Arizona. The results obtained were simply a function of necessity, as will be seen from the description of the local economic conditions and the character of the ores treated. The mines and mill of the Socorro Gold Co. are located near the small village of Harrisburg, about 60 miles from Congress Junction, Arizona, which, at the time this work was undertaken, was the nearest railroad station, and from which all supplies were brought by wagon through the desert, at a cost varying from $10 to $15 per ton in addition to the railroad freights. Wood, the only available fuel, cost $7 per cord. Water for all purposes was pumped to the plant from a well in the valley about 4 miles away. Under the Arizona law, a working-shift is 8 hr. Wages were $6 per day for foremen and mill-men, $4 per day for blacksmiths and engineers, $3.50 per day for miners, and $3 per day for shovelers and trammers. The ore consisted of quartz, in which, above the 250-ft. level, the iron-minerals were largely oxidized and some free gold was visible; below that level few traces of oxidation occurred, and pyrite constituted the principal mineralizer in the quartz, together with occasional pockets of galena and a few eccentric specks of covellite. The 20-stamp mill was equipped with plates for amalgamation, and three Standard tables for concentration. The tails from the tables were elevated by a centrifugal pump to a launder, by which they were conveyed to a 60-ton cyanide-mill for further treatment. The cyanide-mill was erected at so great a distance from the stamp-mill that a separate crew of workers and a separate power-plant were necessary. No arrangement had been made for the treatment of the concen-

Jan 1, 1907

By C. E. Siebenthal

produce attractive and consequently more salable products. It would seem, however, that if solder and babbitt were cast in closed molds, just as good practical results would be obtained by the user, without his being able to give preference to solders of unnecessarily higher grade on account of their appearance. It would be hopeless for any one. manufacturer of solder to undertake a change of this kind, but if all manufacturers of solder agreed upon it, they would be able, in my opinion, to get the users of solder to take, and to approve by their practical tests, metals containing less tin than they have been accustomed to. The same is true with regard to babbitt metals. An illustration of how, in the use of an alloy, appearance sometimes is deceptive, is to be found in the case of what may be called intermediate grades of babbitt. I am thoroughly convinced that high-tin or high-lead babbitts are better than those containing both lead and tin with relatively high percentages of each. A high-tin babbitt should not contain more than about 10 per cent. of lead, and a high-lead babbitt should not contain more than 10 per cent. of tin, unless the percentage of antimony can be correspondingly increased. The intermediate babbitts, such as those that contain from 30 to 70 per cent. of lead or tin, may give nice appearing castings that flow easily, but they have not the serviceability of the high-lead or high-tin babbitts. Their hardness diminishes very rapidly as the temperature rises, and they have a relatively low softening point due to the eutectic components present. The Cadmium Supply of the united States* C. E. Siebenthal, † Washington., D. C.—From being one of the most maligned of metals—a veritable bugaboo—cadmium has almost overnight become respectable, though its slender claim to respectability rests almost wholly on the possibility of its substitution for tin. Preliminary to any campaign for such substitution, particularly for enforced substitution, the possible supply of cadmium should be determined as closely as possible; for that reason the statistical inquiry of which this paper embodies the results was undertaken. Production Cadmium is marketed in two forms, as metallic cadmium, in sticks or bars, and as cadmium sulfide, the pigment. The metal has found its greatest field of use in this country as a component of an easily fusible alloy that is used in automatic fire extinguishers. The sulfide is used to some extent in paints but chiefly to give color and luster to glass and porcelain. The metal was first made in this country by the Grasselli Chemical

Jan 1, 1919

By G. S. Hume

Production of petroleum and natural .gas increased in Canada in 1940 over the previous year. Alberta produced more than 97 per cent of the total Canadian production of 8,718,053 bbl. of oil, an increase for this province of nearly 12 per cent, whereas in Ontario and New Brunswick, where the production is relatively small, there was a slight decline. In Alberta the main producing field is Turner Valley, on the eastern edge of the foothills southwest of Calgary, and development continued in this field in 1940 with the completion of 36 wells, all of which obtained production. In the Red Coulce field, close to the International Boundary, near Coutts, no new wells were drilled and the seven producing wells showed a decline of 900 bbl. below the previous year. Also, in the Wainwright field of east central Alberta, four wells, yielding heavy crude oil, produced 4000 bbl. less oil than in 1939, owing possibly rather to discontinuous operation than to actual decline in potential yield. This decline was more than offset by production from a new field 40 miles northeast of Wainwright, at Borradaile, producing oil of 14" to I 5° A.P.1. There was a small increase in production during 1940 from the Del Bonita field, in southern Alberta, where the production is from two wells. The outstanding development of the year was the completion of Standard Oil Princess No. 2 well in the Steveville area, on the Plains 100 miles east of Calgary. This well was completed late in December with an initial flow1 of 520 bbl. of 26.3" A.P,I. oil, and 12,750 M cu. ft. of gas from the upper part of the Mississippian limestone. It has opened up a new field and given a further proof of the potentialities of the Southern Plains. The production of petroleum in Canada is shown in Table I. Since most of the yield comes from Alberta, the production is shown from the various fields in Table 2. The sale value of the petroleum produced in Canada in 1940 exceeded 11.1 million dollars, which is still somewhat less than the value of the natural gas production, shown in Table 3. Table i.—Production of Petroleum in Canada" Barrels Province 1939 1940 New Brunswick........ 20,101 21,161 Ontario............... 206,196 186,471 Alberta............... 7,595,000 8,493,237 Northwest Territories. . 17,013 8,493,23717.184 Total............... 7,838,310 8,718,053 Value............... $10,353,351 $11.113,000 0 Bureau of Statistics, Ottawa. Turner Valley, Alberta Turner Valley continues to be by far the largest producing field in Canada (details are given in Table 4), The limits of the Pr in- field are now Known. On the east the oil area is bounded by the gas cap, which in turn is cut off on its east side by a major overthrust fault; on the west, ii is defined by edge water at a level of 4roc

Jan 1, 1941

By G. S. Hume

Production of petroleum and natural .gas increased in Canada in 1940 over the previous year. Alberta produced more than 97 per cent of the total Canadian production of 8,718,053 bbl. of oil, an increase for this province of nearly 12 per cent, whereas in Ontario and New Brunswick, where the production is relatively small, there was a slight decline. In Alberta the main producing field is Turner Valley, on the eastern edge of the foothills southwest of Calgary, and development continued in this field in 1940 with the completion of 36 wells, all of which obtained production. In the Red Coulce field, close to the International Boundary, near Coutts, no new wells were drilled and the seven producing wells showed a decline of 900 bbl. below the previous year. Also, in the Wainwright field of east central Alberta, four wells, yielding heavy crude oil, produced 4000 bbl. less oil than in 1939, owing possibly rather to discontinuous operation than to actual decline in potential yield. This decline was more than offset by production from a new field 40 miles northeast of Wainwright, at Borradaile, producing oil of 14" to I 5° A.P.1. There was a small increase in production during 1940 from the Del Bonita field, in southern Alberta, where the production is from two wells. The outstanding development of the year was the completion of Standard Oil Princess No. 2 well in the Steveville area, on the Plains 100 miles east of Calgary. This well was completed late in December with an initial flow1 of 520 bbl. of 26.3" A.P,I. oil, and 12,750 M cu. ft. of gas from the upper part of the Mississippian limestone. It has opened up a new field and given a further proof of the potentialities of the Southern Plains. The production of petroleum in Canada is shown in Table I. Since most of the yield comes from Alberta, the production is shown from the various fields in Table 2. The sale value of the petroleum produced in Canada in 1940 exceeded 11.1 million dollars, which is still somewhat less than the value of the natural gas production, shown in Table 3. Table i.—Production of Petroleum in Canada" Barrels Province 1939 1940 New Brunswick........ 20,101 21,161 Ontario............... 206,196 186,471 Alberta............... 7,595,000 8,493,237 Northwest Territories. . 17,013 8,493,23717.184 Total............... 7,838,310 8,718,053 Value............... $10,353,351 $11.113,000 0 Bureau of Statistics, Ottawa. Turner Valley, Alberta Turner Valley continues to be by far the largest producing field in Canada (details are given in Table 4), The limits of the Pr in- field are now Known. On the east the oil area is bounded by the gas cap, which in turn is cut off on its east side by a major overthrust fault; on the west, ii is defined by edge water at a level of 4roc

Jan 1, 1941

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By B. F. Zwick

The entire production of oil in Ecuador so far has come from the Santa Elens Peninsula, Province of Guayas. Both the shallow fields of the northern and the deeper fields of the southern part of the peninsula have been in constant exploitation, though the former are of doubtful economic value. In Table I herewith, which commences with the total amounts produced by the various companies up to 1940, annual company totals are given for the succeeding years. The figures for 1944 have been partly estimated. Table 2 gives figures on casinghead gasoline. Shell Company of Ecuador (formerly known as Anglo-Saxon) has continued active exploration in the Oriente region east of the Andes, and during 1944 the Company's first wildcat well was spudded in. International Ecuadorean Petroleum Co. (formerly International Petroleum Co., Limited) has pursued an active exploration campaign since the latter part of 1939, and a drilling string was placed in operation about a year later. A second string of tools was added during 1943 and a third a few months ago. Ten wildcats, all dry, have been completed in this period, two wells are drilling at the present time and other locations are on the program. Seven of the wells thus far drilled are in the area between Guayaquil and the Santa Elena Peninsula, one up the Daule River beyond Balzar, one on Puna Island in the Guayas Estuary and one in the northern province of Esmeraldas. Both the present drilling wells are in the Guayaquil-Santa Elena zone. The situation in regard to concessions has changed during the past four years because I.E.P.C. has made its selections from the extensive Daule-Guayas Study Concession, as a result of which large tracts were returned to the Government; because of the expropriation of the holdings of the "Ecuapetrol," a German concern whose acreage has passed into other hands; the Peruvian-Ecuadorean boundary settlement, which has reduced Shell's holdings somewhat; and the transfer of most of the holdings of the Cia. Minero-Petrolera del Pacifico to I.E.P,C. The greater part

Jan 1, 1945

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

Jan 1, 1943

Jan 1, 1943

By Henry Schwellenbach

LABOR shortages, rising wages, and changes in moisture and fines content of the ore necessitated a review of the flowsheet at Warren Foundry & Pipe Co's. Mt. Hope, N. J. Mines Div. This plant had been designed prior to World War II, and started operations in January 1945. When this operation was designed there was an oversupply of labor in the area, wages were at a reasonable level, the run-of-mine ore was low in moisture, and there was a limited amount of fines. These factors all favored use of hand picking for cleaning rougher lump concentrate. Since that time, many changes have occurred. The proximity of defense industries and large military installations, has created one of the most acute labor shortages in the country. This labor shortage together with present wage levels, and the increase in moisture and fines in the ore created several problems. The increase in moisture and fines may be attributed to changed mining methods, the extensive use of sprays, and the opening of new mining areas bringing an increase in ground water. [ ] Two problems were presented by the increase in moisture and fines. The first was that lump ore arrived at the open hearth in an unacceptable condition, due to the segregation enroute of the large amount of fines that had adhered to the lumps. The second problem was that high magnetite content fines coated the large lumps, making it difficult for pickers to distinguish middling by other than the relative weight. [ ]

Jan 1, 1952

The income of the Institute is derived from dues, subscriptions to MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization and at a minimum of expense. J. V. W. Reynders is chairman of the Endowment Committee.

Jan 1, 1923

By C. D. Thurmond

Jan 1, 1968